A kinetic and thermochemical database for organic sulfur
and oxygen compounds
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Citation
Class, Caleb A., Jorge Aguilera-Iparraguirre, and William H.
Green. “A Kinetic and Thermochemical Database for Organic
Sulfur and Oxygen Compounds.” Phys. Chem. Chem. Phys. 17,
no. 20 (2015): 13625–13639.
As Published
http://dx.doi.org/10.1039/c4cp05631k
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Royal Society of Chemistry
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Author's final manuscript
Accessed
Thu May 26 19:34:48 EDT 2016
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http://hdl.handle.net/1721.1/102378
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Cite this: DOI: 10.1039/x0xx00000x
A kinetic and thermochemical database for organic
sulfur and oxygen compounds
Caleb A. Classa, Jorge Aguilera-Iparraguirrea,b and William H. Greena, *
Received 00th January 2012,
Accepted 00th January 2012
Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and
DOI: 10.1039/x0xx00000x
elementary tautomerization reactions, which are potentially relevant in the combustion and
www.rsc.org/
oxygen. This includes 11 H2O addition, 8 H2S addition, 11 hydrogen abstraction, 7 beta scission, and 3
desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and
frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential
energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated
using conventional transition state theory, with corrections for internal rotations and tunneling.
Additionally, thermochemical parameters were calculated for each of the compounds involved in these
reactions. With few exceptions, rate parameters calculated using the two potential energy methods
agreed reasonably, with calculated activation energies differing by less than 5 kJ/mol. The computed
rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling.
Introduction
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Sulfur compounds can be found in almost every aspect of life,
and their interactions with oxygenated species play an
important role in fuels, geochemistry, and environmental
chemistry.1, 2 The formation of petroleum in geochemical
reservoirs may be accelerated by the presence of weak carbonsulfur bonds, and the reaction mechanisms of these species can
be affected by the presence of water.3-5
One of the most important sources of sulfur compounds is crude
oil, and these compounds will react to form toxic sulfur dioxide
if not removed prior to combustion. The desulfurization of
crude oil has become a very important topic of study, as sulfur
emission standards have tightened and the availability of sulfurlean feedstock has lessened.6 The current industry standard,
hydrodesulfurization, requires the use of hydrogen and
expensive catalyst to achieve the proper sulfur level, so multiple
alternatives are being studied to potentially achieve similar
results at a lower cost. Oxidative desulfurization converts
thiophenic compounds into more easily removable polar
compounds using hydrogen peroxide and a catalyst.7 Microbial
desulfurization removes sulfur from organic compounds at
ambient temperature and pressure.8 Treating oil with super-
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a)
25
Dept. of Chemical Engineering, Massachusetts
Institute of Technology, Cambridge, MA 02139
b) Present address: Dept. of Chemistry and Chemical
Biology, Harvard University, Cambridge, MA 02138
†Electronic supplementary information (ESI) available. See
DOI:
-critical water
This journal is © The Royal Society of Chemistry 2013
accomplishes
desulfurization without the
30 requirement of any catalyst.9 Work in supercritical water
55
upgrading has demonstrated that water generates products with
reduced sulfur content and molecular weight.10, 11 Water’s
involvement in this process has been explored via model
compound experiments, and investigators have proposed
pathways to explain the reactivity of various sulfur compounds
in aqueous and supercritical systems.12 Additional experiments
and the advancement of computational chemistry techniques
have assisted in the elucidation of this mechanism, showing
water to be both a reactant and a hydrogen-transfer catalyst in
the mechanism of alkyl sulfide desulfurization.9 Based on
intermediate studies and quantum chemistry calculations, a
plausible pathway for water-aided desulfurization was
proposed,9 and this is shown schematically in Figure 1. In the
proposed mechanism, the water prevents the conversion of the
reactive thioaldehyde (reactant 3) to an oligomer, which is
known to occur in the absence of water.13 Water participates by
adding to the carbon-sulfur double-bond in reaction c to form
reactant 4, which readily reacts at high temperature to form
hydrogen sulfide, carbon monoxide, and a smaller alkane.
Many other pathways are possible, and a full kinetic mechanism
of the system based on accurate thermochemical and kinetic
data is necessary to evaluate and validate them. Extensive
libraries of thermochemical data and reaction rate parameters
for hydrogen abstraction, beta scission, and substitution
reactions involving organosulfur compounds have been
generated by Vandeputte et al.14-16 Rate constants have also
been calculated for small-molecule reactions involved in
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combustion to form SOx compounds.17, 18 However, these data
are not sufficient for accurately modeling the reactions of thiols,
sulfides, and thiophenes with oxygenated species. This work
focuses on the reactions of sulfur compounds and other species
that are likely to be produced in the presence of water at high
temperatures. Many of the reactions considered here could also
be relevant to organosulfur combustion systems.
Rate parameters in modified Arrhenius form were calculated for
40 reactions that involve organic sulfur and oxygen. These
provide rate constants for use in simulations of hydrocarbon
mixtures including both sulfur and oxygen, as well as in
training sets to develop more general rate estimation rules.
Thermochemical parameters, which are required for the
calculation of equilibrium constants and temperature changes in
reacting systems, have also been computed for each of the
species involved in the reactions and compared to the limited
data available.
Methods
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Thermochemical data were computed using the Gaussian 03
and Molpro quantum chemistry packages.19, 20 All species with
an even number of electrons were calculated in their singlet
state, and radical compounds were calculated in their doublet
states. Geometry optimizations and frequency calculations were
conducted using B3LYP/CBSB7 in Gaussian 03,19, 21, 22 and it
was tested that all the reactants and products were indeed
minima on the potential energy surface and that all the
transition states showed one and only one imaginary frequency
that corresponded to the expected reaction coordinate.
Multidimensional scans, and additional optimizations when
applicable, were also conducted to ensure that the lowestenergy transition state was found for each reaction. These
geometries were then used for single point energy calculations
at higher levels of theory. Electronic energies were calculated
using both the composite CBS-QB3 method20, 22, 23 in Gaussian
03 and the explicitly-correlated CCSD(T)-F12a/VTZ-F12
method in Molpro (this will be referred from now on as
CCSD(T)-F12).20, 24-27
The slow convergence of CCSD(T) with the basis set size has
been known for a long time.28, 29 That restricted its application
to very small systems.30, 31 In the last few years explicitlycorrelated methodologies have been introduced to circumvent
this problem.32, 33 They directly address the fact that
conventional
coupled-cluster
methods
approximate
wavefunctions based on one-electron basis functions and can
hardly describe the electron-electron correlation. This drawback
was overcome with the introduction of functions depending
explicitly on the inter-electronic distance, as used in the
CCSD(T)-F12 family. That makes the basis set convergence
much faster and allows us to describe medium-sized systems
with basis-set error of less than 1 kcal/mol. These properties
have allowed it to be successfully applied in all sorts of fields,
including thermochemistry and kinetics.32-36
CBS-QB3 has previously been used in a variety of kinetic
studies, including some relevant to sulfur chemistry, and the
reaction barriers calculated have been shown to have an
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uncertainty of a few kcal/mol.22, 23, 37, 38 CBS-QB3
thermochemistry is usually more accurate due to the availability
of empirical Bond Additivity Corrections (BAC).39 It appears
that CBS-QB3 is becoming obsolete, as new density functionals
like M06 and BMK provide comparable accuracy at a much
lower cost, and CCSD(T)-F12 methods provide improved
accuracy at a still-reasonable cost.40, 41 We include CBS-QB3
calculations here nevertheless since a big part of the data
available in the literature from the last two decades has been
calculated in this way, so a good assessment of its accuracy is
still useful.
Partition functions were calculated using the CanTherm
software package,42 using a scaling factor of 0.99 for the
frequency analysis. Enthalpies, entropies, and heat capacities
were calculated using CBS-QB3 energies in CanTherm,
including the BAC’s that are available in literature.39
Preliminary studies on No correction was available for the C=S
bond due to the scarcity of experimental data for thiocarbonyl
compounds. Calculated parameters were used to generate
NASA polynomials for each of the reactants and products.
These calculations were used to extend the group additivity
scheme for thermochemical properties, which was originally
proposed by Benson and Buss, and extended by Vandeputte et
al. using CBS-QB3 for compounds containing sulfur.16, 41, 42
Using the thermochemical parameters calculated in this work,
group additivity values (GAV’s) of enthalpy and entropy of
formation, and heat capacities between 300 and 1500 K for 15
groups containing both sulfur and oxygen were derived using
the regression method discussed by Vandeputte et al.16
Hydrogen Bond Increments (HBI’s), as defined by Lay et al.,43
were derived for two radical groups including sulfur and
oxygen. The values for groups with previously calculated
GAV’s (i.e. those that do not contain all of sulfur, carbon, and
oxygen) were held constant at the literature values.
Transition states were optimized for each elementary reaction,
and transition state theory in CanTherm was used to calculate
rate coefficients under the ideal gas assumption, correcting for
the internal rotations of each single bond within the reactants,
products, and transition states. One-dimensional hindered
rotations were used in the analysis, optimizing the geometries at
the B3LYP/6-311G(2d,p) level at 10-degree increments for
each rotatable bond. Asymmetric Eckart tunneling corrections
were also calculated, and these corrections were applied to
generate the reaction rate constants between 300 and 2000 K. 44,
45
Rate constants were fitted to the modified Arrhenius form,
−𝐸𝑎
𝑘 (𝑇) = 𝐴 ∗ 𝑇 𝑛 ∗ 𝑒 𝑅∗𝑇 ,
105
where T is the temperature in Kelvin, R is the gas constant, A
and n are fitted constants, and Ea is the fitted activation energy.
It is important to note that the fitted Ea is not the same as the
reaction energy barrier ΔEo , the calculated energy difference
between the reactants and transition state including zero-point
energies (ZPE’s). Ea and ΔEo can differ by multiple kJ/mol. The
modified Arrhenius form has been demonstrated to fit rate
constants for a variety of organic systems better than the
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standard Arrhenius form without the Tn term.44, 45 However, due
to greater tunnelling effects at lower temperatures, the fitting
uncertainty of this form at this limit can exceed a factor of two.
Thus, some rate constants were calculated for smaller
temperature ranges, and these are noted in the data tables. Care
should be taken when extrapolating outside these ranges.
These rate parameters were calculated assuming reactant
activity coefficients αi=1. The activity for water can vary
significantly at supercritical conditions: for example, in the 400
°C and 275 bar experiments of Kida et al.,9 the activity
coefficient of water is calculated to be approximately 0.5[H 2O],
reducing the rates by this factor when water is a reactant or
collision partner. Thus, the rate parameters in this work should
be adjusted to account for the conditions being modeled to
avoid introducing additional errors.
Calculation of Rate Constants for Reactions with Submerged
Transition States
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The reaction barrier was calculated to be significantly negative
(i.e. greater than the uncertainty of the calculations) for two of
the reactions studied in this work, implying the existence of
reactive complexes at lower energy levels than the reactants of
the respective reactions. Examples of these reactions are
presented in Figure 11 and Figure 14. The same methods as
discussed previously for reactants and products were used to
calculate energies and frequencies for the reactive complex of
each reaction.
The parameters for each submerged reaction were calculated for
the high-pressure limit using CanTherm. The rate k1 for the
formation of complex was assumed to be the collision rate, 10 13
cm3/(mol*s), and k-1 was calculated using thermochemical
consistency. The rate of formation of products from the prereactive complex, k2, was calculated using transition-state
theory. The complex is short-lived, so it can be modeled using
the quasi-steady-state approximation. The overall rate of
product formation for a reaction with two reactants is therefore
𝑘1 𝑘2
𝑑𝐶𝑃
=
𝐶 𝐶
𝑑𝑑
𝑘−1 + 𝑘2 𝑅1 𝑅2
and the effective rate constant is
𝑘𝑒𝑒𝑒 (𝑇) =
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𝑘1 𝑘2
𝑘−1 + 𝑘2
The effective rate constant keff(T) was calculated at temperatures
between 300 and 2000 K, and modified Arrhenius parameters
were fit to these calculations to obtain the values reported in the
Tables for Reactions 21 and 37. As our primary interest is in
supercritical water reactions (with pressures greater than 200
bar), rate constants are reported in the high pressure limit. In
some gas-phase situations, the low-pressure limit might be
more appropriate than the high-pressure limit values reported
here. Even at higher pressures, the collision rate used is a
relatively rough estimate, so further refinement of the rate
parameters for these two reactions will be necessary if
mechanistic model predictions are particularly sensitive to
them.
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50 Basis Set benchmarking for CCSD(T)-F12 Calculations
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Experimental data for the elementary reactions of sulfur
compounds is scarce, but a test set of four reactions similar to
the types being considered for this work was selected to test the
accuracy of CBS-QB3 against CCSD(T)-F12. This includes two
hydrogen abstraction reactions,46, 47 one radical addition,48 and
one H2O elimination reaction.49 The first three reactions in this
set were previously used to benchmark CBS-QB3 for sulfur
chemistry.38 Rate constants were calculated with the previously
described methods, and the results are presented in Table 1.
Overall, CCSD(T)-F12 calculations outperform those of CBSQB3. All three basis sets (even double zeta) match the
published data within roughly a factor of 2. This suggests that
our methods are reasonable for these reaction types, although
additional experimental data would be very useful for more
substantial benchmarking.
An additional procedure to establish the accuracy of the basis
set in the Coupled-Cluster calculations for our particular set of
reactions, including both oxygen and sulfur, was defined as
follows: in each of the different classes of reactions, the one
with the smallest number of electrons was used. These are
reactions 1 for the molecular additions of water, 12 for the
molecular additions of hydrogen sulfide, 20 for the hydrogen
abstractions and 31 for the beta-scissions. The restriction on the
size of the reactions allows us to perform calculations on a
bigger basis that would it be practical otherwise, and use its
results as a benchmark.
We obtained both reactants and transitions states for our set of
reactions and performed a consistent set of CCSD(T)-F12a
calculations with the basis set series VDZ-F12, VTZ-F12, and
VQZ-F12.50 CCSD(T)-F12b energies were also calculated with
the VQZ-F12 basis set, and these agreed with the F12a energies
for the same basis set with an average error of 0.17 kJ/mol.
The convergence with respect to basis set is shown on Table 1.
Triple-zeta F12 barrier heights are converged to better than 1
kJ/mol. Double-zeta basis set on the other hand lead to errors
above 1 kJ/mol. This is in good agreement with previous
studies.51 In a compromise between accuracy and computational
cost, we chose VTZ-F12 basis set as the standard for this study.
It is important nevertheless to be aware of the error introduced
by such a choice.
While the calculations reported here are converged with respect
to basis set, this does not mean they are exact. CCSD(T) is not
full-CI, and there are several small neglected terms (BornOppenheimer breakdown, relativistic, anharmonicity) which
can contribute errors on the order of kJ/mol. Still, we expect
that the numbers computed here are rather close to the true
energies.
Results and Discussion
Molecular Addition of Water (Hydration of Double Bonds)
100 Reaction coefficients calculated for the ten reactions involving
the molecular addition of water to double bonds, the reverse of
which is the elimination of water from an alcohol, are presented
in Table 3. These reactions progress via a four-membered ring
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transition state. Transition states for reactions 3, 8 and 9 were
previously calculated.9, 52 All the other geometries were
determined in this work and are reported in the Supporting
Information. Those geometries were used in this study.
Reaction 8 corresponds to the addition of water to the
thiocarbonyl group of carbonyl sulfide, while reaction 9 is
addition to the carbonyl group. Reactions 10 and 11 are for the
addition of water to the carbon-carbon double-bond of
thiophene, which also occurs through a four-membered ring
transition state. All of these reaction coefficients were
calculated using CCSD(T)-F12a//VTZ-F12 energies, with the
exception of reaction 6, for which the CBS-QB3 energies were
used. A full set of rate parameters calculated for each reaction
using CBS-QB3 has also been included in the Supplementary
Materials.
The transition state of reaction 1, addition of water to
thioformaldehyde, is presented in Figure 2. Calculated reaction
parameters for the molecular elimination of water from
methanediol and ethanol are available in literature, and using
available thermochemistry data we can estimate the activation
energy of these reactions in the addition direction. 53, 54 These
are compared with the activation energies of reaction 1 in Table
4. The instability of thiocarbonyl compounds, which are known
to polymerize at room temperature, provides for a low-energy
pathway for the conversion of this type of compound. 13 Table 4
shows that the activation energy in both directions is lowest for
the thiocarbonyl case, as the 4-center reaction is much more
facile for sulfur-containing systems than for C/H/O systems.
Lower A-factors and higher n-factors are calculated with the
substitution of a methyl or ethyl group on the thioaldehyde, as
in reactions 2 and 3. These reactions have very similar
Arrhenius constants, n-factors, and activation energies, and they
are predicted to agree within 50% for all temperatures between
300 and 2000 K. This suggests that increasing the length of the
thiocarbonyl compound has a minor effect, and will likely have
a lesser effect as this chain length increases. Reaction 4 has
similar activation energies but a lower A-factor than reactions
1-3 due to the presence of a methyl group on both sides of the
thiocarbonyl group, providing a small steric hindrance. The
steric effect will increase for addition to branched
thioaldehydes, and especially branched thioketones, so these
should be explored further when these reactions are of interest.
We compute a barrier height of 144 kcal mol for the addition of
water to benzenethial using CBS-QB3, which is significantly
greater than that calculated for addition to an alkyl
thioaldehyde, which ranges between 122 and 124 kcal/mol
(using CCSD(T)-F12a//VTZ-F12 energies). The transition state
geometries for reactions 5 and 6, the addition of water to 2propenethial and benzenethial, are presented in Figure 3. The
lengths of the C-S bonds in the two transition states differ by
less than 0.01 Å, and this similarity is reflected in the rate
constant calculations. CBS-QB3 calculations on reaction 5
resulted in a reaction barrier of 145 kJ/mol, which is within 1
kJ/mol of the calculated barrier for hydration of benzenethial.
As expected, very similar Arrhenius parameters are calculated
for the addition of water to a thioaldehyde bonded to an sp 2
carbon.
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Reactions 8 and 9 correspond to the addition of water to
carbonyl sulfide, as investigated by Deng et al.,52 and transition
state geometries for these reactions (as calculated in literature)
are presented in Figure 4. Energies were recalculated in this
study using CCSD(T)-F12a//VTZ-F12, and the barrier height is
calculated to be 42 kJ/mol greater for the addition to the C=O
bond than when water attacks the C=S bond. Comparing
reaction 8 with the other hydration reactions with thiocarbonyl
groups, we see that addition to carbonyl sulfide requires an
activation energy more than 70 kJ/mol greater than reactions 1
through 4.
Because of the aromaticity of thiophene, addition reactions 10
and 11 are endothermic, in contrast to the exothermic addition
of water to C-C double-bonds in alkenes. As such, these
reactions proceed via much higher-energy pathways, and the
parameters calculated in this study show that water will not
appreciably react directly with thiophene at temperatures below
1500 K.
In each of the reactions where both single-point energy
calculation methods were used, the addition reaction barrier
height is calculated to be less using CCSD(T)-F12 than CBSQB3, by an average of 4.5 kJ/mol. This is within the combined
uncertainty of the two methods, but it suggests a systematic
difference. Experimental data for this type of reactions will be
quite useful for more substantial validation, but based on what
we have seen so far in this and other works, we prefer the
CCSD(T)-F12 calculations.
85 Molecular Addition of Hydrogen Sulfide
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Reaction coefficients for eight reactions involving the addition
of H2S to a carbonyl bond, the reverse of which is the
elimination of H2S from a thiol, are presented in Table 5. The
optimized transition states for reactions 14 and 19, addition of
H2S to propanal and carbon dioxide, respectively, were
available in literature 9, 52. The other geometries were
determined in this work and are reported in the Supporting
Information. This type of reaction progresses in a similar
fashion as the molecular addition of water to a thiocarbonyl
compound. For this initial database, the bimolecular reaction
was considered without an additional catalyst like water. As
previous calculations have shown that water may catalyse this
reaction in supercritical conditions,9 additional work in this area
will be important to fully understanding this chemistry, and
these calculations are currently being conducted. All of these
reaction coefficients were calculated using CCSD(T)F12a//VTZ-F12 energies, with the exception of reaction 17, for
which the CBS-QB3 energies were used. CCSD(T)-F12 again
predicts smaller barrier heights for each of these reactions, but
by only an average of 2.2 kJ/mol for this reaction type.
This reaction occurs via a four-membered transition state, as in
the addition of water to a double-bond, but the bond lengths and
angles are greatly different. This is shown in Figure 5, which
shows the optimized transition state for reaction 12, the addition
of H2S to formaldehyde. An IRC scan confirmed that this
transition state corresponded to the expected reaction, and the
potential energy surface was scanned using b3lyp/6311G(2d,p), stepping the C—S and O—H bond distances while
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optimizing the remaining variables. This is presented in Figure
6, and it shows that the reaction happens in a somewhat
sequential fashion, with the translation of the hydrogen atom to
form an OH group largely complete while the carbon and sulfur
atoms are still separated by a distance of 2.7 Å (in comparison
with the final C—S bond length of 1.8 Å). Thus, we expect that
a separate disproportionation pathway exists with a similar
transition state, although the addition reaction’s transition state
is over 100 kJ/mol more stable than the sum of the CH2OH and
SH radicals that would be the intermediates of a disproportionrecombination pathway. This reaction type is also a likely
candidate for a roaming radical pathway, which has previously
been investigated for the decomposition of formaldehyde.55, 56
In addition, investigating the possibility of reaction pathway
bifurcation57 may be an area of future research for this type of
reaction system.
The carbon-sulfur distance in Figure 5 is calculated to be 46%
greater in the transition state than the bond length in the product
compound (compared to only a 12% difference for the carbonoxygen distance in reaction 1). This is reflected in the general
trend of activation energies, where the addition of water to a
thioaldehyde is calculated to be a significantly more favorable
reaction than the addition of H2S to an aldehyde.
Similarly to the case with the addition of water to a
thiocarbonyl compound, the reaction barrier in both directions
is slightly lower when an alkyl group is substituted on the
carbonyl compound, as shown by reactions 13 and 14 for
addition to acetaldehyde and propanal, respectively. The
transition states for these two reactions are presented in Figure
7. Again, this effect decreases as the chain length increases, so
the calculated rate parameters for reaction 14 should be
acceptable approximations for the addition of H2S to a longer
aldehyde. Substituting an alkyl group on both sides of the
carbonyl group leads to slight steric hindrances, and a lower
Arrhenius constant and greater n-factor is predicted for addition
reaction 15.
Substitution of a phenyl group stabilizes the transition state of
this reaction. In contrast to hydration reactions 5 and 6 which
had very similar Arrhenius parameters, the energy barrier for
the addition of H2S to 2-propenal is calculated to be 6 kJ/mol
lower than that calculated using CBS-QB3 for addition to
benzaldehyde. However, the rate constants estimated using
these parameters agree within a factor of two at temperatures
above 600 K, and the disagreement will decrease at higher
temperatures.
The optimized transition states of the addition of H2S to acetic
acid and carbon dioxide are presented in Figure 8. These are the
only ones in Table 5 calculated to be endothermic in the
addition direction, as these require addition to a stable
carboxylic acid or carbon dioxide. The activation energies of
these reactions are calculated to be the greatest of the reactions
calculated in the addition direction, but the lowest in the H2S
elimination direction. These transition states have the shortest
carbon-sulfur distance of any calculated for this type of
reaction, and this length is 14% less for the addition of H2S to
CO2 than for the addition to acetic acid.
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Hydrogen Abstraction Reactions
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Modified Arrhenius parameters for the 10 hydrogen abstraction
reactions calculated in this work using CCSD(T)-F12a//VTZF12 energies are presented in Table 6.
Reactions 20-25 show the abstraction of hydrogen from a sulfur
compound by an oxygen radical center. The first four reactions
correspond to hydrogen transfer between hydrogen sulphide or
methanethiol and hydroxyl or methoxy radical. These are
favored in the forward direction, due to the much greater
hydrogen-affinity of an oxygen atom relative to the sulfur atom.
Linear transition states were found for most of these reactions,
which is typical for hydrogen abstractions. However, linear and
nonlinear transition states were found for hydrogen abstraction
from H2S by hydroxyl radical, and these are presented in Figure
9. IRC scans were conducted for the converged geometries, and
they showed that both versions of each transition state
corresponded to the correct reaction. Lower potential energies
were calculated using the bent transition state, so this geometry
was used to calculate rate parameters for this reaction.
The reaction between hydrogen sulphide and hydroxyl radical
has previously been studied in experimental58-62 and
theoretical63 investigations. The rate constants estimated in this
work are compared with experimental data in Figure 10. Only
the M06-X calculation approximated the experimentally
observed temperature dependence (although with quite a bit of
scatter, and hence uncertainty is observed in the experimental
data) due to an addition complex below the reactants’ total
energy. Using our methods, the optimized prereactive complex
had an energy approximately equal to the reactants, so our TST
calculations do not capture the negative temperature
dependence at very low temperatures (below 300 K, where rate
parameters were not directly calculated for this study).
However, all of the methods employed in this work come
within about 20% of the experimental data at the temperatures
relevant to combustion and pyrolysis, and slightly better
agreement was obtained using the quadruple-zeta than the
triple-zeta basis set.
For hydrogen abstraction from methanethiol by hydroxyl
radical, a valid transition state was only found for the angled
geometry. The energy of the transition state for this reaction
was calculated to be 12.3 kJ/mol lower than the initial reactants,
and a prereactive complex was optimized at an energy 19.4
kJ/mol lower than that of the reactants, which is illustrated in
Figure 11. The estimated rate of this reaction approximately
equals the collision rate at temperatures above 400 K, and this
is reflected in the optimized effective rate parameters (the actual
keff’s calculated are provided in the Supplementary
Information).
Nearly linear transition state geometries were found for
hydrogen abstraction from H2S and methanethiol by vinyloxy
radical (reactions 24 and 25, respectively), as both saddle point
geometries had an O-H-S angle greater than 170°. Reaction 24
was the only one found to be exothermic in the direction of
hydrogen abstraction from the hydroxyl group, while reaction
25 is isothermal (within the margin of error for the
calculations). This is in agreement with published
PCCP, 2012, 00, 1-3 | 5
ARTICLE
5
10
15
20
25
30
thermochemistry data, from which standard enthalpies of
reaction are estimated to be -18.2 and -4.3 kJ/mol for reactions
24 and 25, respectively.16, 64-67
Reactions 26 and 27 represent the abstraction of an aldehydic
hydrogen by a sulfur-containing radical (mercapto radical and
1-thioethyl radical, respectively). Low activation energies are
calculated for reaction 26 in both directions, while abstraction
of the hydrogen of the carbon adjacent to a thiol group is found
to be significantly less favorable. However, this activation
energy is 27 kJ/mol lower than that calculated for the
abstraction of hydrogen from propane by acetyl radical to form
isopropyl radical and acetaldehyde,68 as the alpha radical in a
thiol or sulfide is stabilized by the presence of sulfur. These two
values are compared in Table 7.
Reactions 28-30 were calculated as possible intermediate steps
in the desulfurization of alkyl sulfides and thiols in supercritical
water. Reactions 28 and 29, hydrogen abstraction from a
germinal mercaptoalcohol by a methyl or thiyl radical, show
significantly lower activation energies than generally observed
for the abstraction of a hydrogen from tetravalent carbon, as the
resulting radical is stabilized by the neighboring sulfur and
oxygen atoms. These reactions will be slightly sterically
hindered by the neighboring groups, and this effect will
increase in similar reactions with larger attacking species.
Treatment of the coupling of hindered rotors will likely lead to
more accurate rate predictions, so this should be considered
when kinetic model predictions are particularly sensitive to this
type of reaction.
Reaction 30, the abstraction of hydrogen from thioformic acid
by a methyl radical, is highly exothermic, and the radical
formed in this reaction is stabilized by the carbonyl group. A
negative activation energy was fit to this reaction, but the ΔEo is
positive and the positive relationship between temperature and
rate constant is expressed by the n-factor of 3.5.
35 Radical Addition to Double Bonds (Reverse Beta-Scission)
40
45
50
55
Modified Arrhenius parameters for the seven radical addition
reactions calculated in this work using CCSD(T)-F12a//VTZF12 energies are presented in Table 8. A mean absolute
deviation of only 2.5 kJ/mol is calculated for the barrier height
calculated using CCSD(T)-F12a versus CBS-QB3.
Optimized transition states for the addition reactions of radicals
on thioformic acid are presented in Figure 12. The reverse of
reaction 31, which forms thioformic acid and a hydrogen atom,
is calculated to be significantly less favorable than the beta
scission reactions (reverse of 32 and 33) that form the same
thioformic acid and alkyl radicals. The transition state of
reaction 34, addition of hydrogen to the sulfur atom of the C—S
double-bond, is calculated to have a slightly negative activation
energy and barrier height. The transition state for this reaction
is presented in Figure 13, showing that the lowest energy
conformer for this transition state corresponds to attack of
hydrogen from the alcohol side of the other reactant. Interaction
between the two hydrogen atoms leads to a slight decrease in
the barrier height, and suggested that this was actually an H2
insertion reaction. Additional scans were conducted to confirm
that this was indeed a radical addition/beta-scission reaction.
6 | J. Name., 2012, 00, 1-3
Journal Name
60
65
70
Reverse reactions 35 and 36 form the stable carbonyl sulfide
and either the hydrogen or methyl radical. These are calculated
to be significantly less endothermic than reverse reactions 3134; so as expected, much lower activation energies are
calculated in the beta scission direction, while greater activation
energies are predicted in the addition direction.
A significantly submerged reaction barrier was calculated for
the addition of thiyl radical to 1-propenol, and a pre-reactive
complex was optimized near the transition state geometry. The
potential energy surface of this reaction is presented in Figure
14. The conversion of the pre-reactive complex to form the
product is calculated to occur significantly faster than the
reverse reaction to reform the reactants at temperatures greater
than 400 K: thus, the overall k eff is calculated to exhibit very
little temperature dependence and remain approximately equal
to the collision rate (additional details available in the
Supplementary Information).
Tautomerization of Thiocarboxylic Acids
75 Three elementary tautomerization reactions were calculated in
80
85
90
95
100
this work using CCSD(T)-F12a//VTZ-F12 energies, and they
are shown in Table 9. These occur via the translation of a
hydrogen atom from an alcohol group of a thiocarboxylic acid
to the sulfur atom.
The three reactions calculated in Table 9 proceed via very
similar transition states, as shown in Figure 15. Interatomic
distances vary by less than 0.03 Å between the saddle point
geometries for reactions 38 and 39 (tautomerization of
thioformic and thioacetic acid, respectively), and the rate
parameters calculated vary only slightly. The transition state is
stabilized to some extent by the substitution of an alkyl group,
but this only leads to a difference of 6 kJ/mol in the forward
barrier height of reactions 39 and 40 in comparison with
reaction 38. Reactions 39 and 40 are calculated to have nearly
identical Arrhenius parameters, and Figure 15 shows that the
relevant interatomic distances for these two reactions are nearly
identical. We expect that further increasing of the alkyl chain
length should have a negligible effect. Thus, the coefficients
calculated for reaction 40, the tautomerization of thiopropionic
acid, should be acceptable for elementary tautomerization
reactions of thiocarboxylic acids containing alkyl chains.
Based on the rate coefficients calculated for the tautomerization
of thiopropionic acid, a thiocarboxylic acid with a C=S bond
would have a half-life of less than 0.1 s at temperatures above
500 K. It is recommended to include this pathway in any model
where this type of compound is likely to be produced.
Thermochemical Library
105
110
Thermochemistry Group Additivity Values (GAV)69 for the 15
groups calculated in this work using CBS-QB3 are presented in
Table 10, and Hydrogen Bond Increments (HBI)43 for the two
radical groups are presented in Table 11. Previous comparisons
with a small set of sulfur compounds with experimental
thermochemistry showed that these calculations are generally
accurate within 4 kJ/mol.16, 38 These groups are primarily
relevant to the SCW pyrolysis of sulfides and thiols; they
represent a small subset of all possible groups containing
This journal is © The Royal Society of Chemistry 2012
Journal Name
5
10
ARTICLE
carbon, sulfur, and oxygen. Future expansion of this group
library will be necessary for modeling more oxidized systems,
for which more extensive experimental data are available for
benchmarking.70-74 In addition, regression of BAC and GAV
using CCSD(T)-F12 for organic compounds should provide
more accurate estimates for thermochemical parameters, and
these calculations are currently being conducted.
Standard heats of formation, entropies, and heat capacities
between 300 and 2400 K were calculated using CBS-QB3 for
each of the molecules involved in the reactions investigated in
this work, as well as for some additional molecules for use as a
training set in GAV regression. These are included in the
supporting information as both a data table and a file of NASA
polynomials.
11. L.-Q. Zhao, Z.-M. Cheng, Y. Ding, P.-Q. Yuan, S.-X. Lu and W.-K.
55 12.
Yuan, Energy & Fuels, 2006, 20, 2067.
A. R. Katritzky, R. A. Barcock, M. Balasubramanian and J. V.
Greenhill, Energy & Fuels, 1993, 8, 498-506.
13. N. J. Cooper, Compr. Org. Funct. Group Transform. II, 2005, 3, 355396.
60
14. A. G. Vandeputte, M. K. Sabbe, M.-F. Reyniers and G. B. Marin,
Phys Chem Chem Phys, 2012, 14, 12773-12793.
15. A. G. Vandeputte, University of Ghent, 2012.
16. A. G. Vandeputte, M. K. Sabbe, M.-F. Reyniers and G. B. Marin,
Chemistry-A European Journal, 2011, 17, 7656-7673.
65
17. K. J. Hughes, A. S. Tomlin, V. A. Dupont and M. Pourkashanian,
Faraday Discuss., 2001, 2001, 337-352.
18. P. Glarborg, D. Kubel, K. DamJohansen, H. M. Chiang and J. W.
Bozzelli, International Journal of Chemical Kinetics, 1996, 28,
15 Conclusions
20
25
30
773-790.
Rate coefficients and thermochemical parameters were
calculated for 40 reactions involving sulfur and oxygen
compounds. These have applicability in studies of sulfur
chemistry in an environment rich in water or other oxygenated
species, such as the reactions of organosulfur compounds in
supercritical water reactors or in geological formations where
water is present.
Although the calculation methods employed in this work are
among the most accurate available, rate coefficients calculated
using these methods can still have greater than factor-of-2
uncertainty. In situations where more accurate rate parameters
are required, experiments (if possible) or calculations using
higher-level quantum chemistry methods and improved
treatments of anharmonicity should be conducted. 75, 76 The
parameters calculated in this work provide a good starting point
for the kinetic modeling of organosulfur chemistry in
supercritical water.
70
Robb, J. R. Cheeseman, J. Montgomery, J. A., T. Vreven, K.
N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi,
V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.
A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R.
75
Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O.
Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts,
R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C.
Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A.
80
Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S.
Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K.
Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V.
Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B.
Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L.
85
Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A.
Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez and J. A. Pople, Gaussian 03,
(2004) Gaussian, Inc., Wallingford CT.
Acknowledgements
35
19. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
20. H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby and M. Schütz,
Saudi Aramco is gratefully acknowledged for financial support
(contract number 6600023444).
90
Molpro: a general-purpose quantum chemistry program
package. In Wiley Interdisciplinary Reviews: Computational
Molecular Science, 2011, 2, 242-253.
References
40
21. A. D. Becke, Journal of Chemical Physics, 1992, 98, 5648-5652.
22. J. A. Montgomery Jr., M. J. Frisch, J. W. Ochterski and G. A.
1.
C. Song, Catalysis Today, 2003, 86, 211-263.
2.
D. T. Johnston, Earth-Science Reviews, 2011, 106, 161-183.
3.
M. D. Lewan, Geochimica et Cosmochimica Acta, 1997, 61, 3691-
95
Petersson, Journal of Chemical Physics, 2000, 112, 6532-6542.
3723.
24. T. B. Adler, G. Knizia and H.-J. Werner, Journal of Chemical
4.
M. D. Lewan, Nature, 1998, 391, 164-166.
5.
M. D. Lewan and S. Roy, Organic Geochemistry, 2011, 42, 31-41.
6.
EIA.
45 7.
Retrieved
03/19/2014
Physics, 2007, 127, 221106.
from
100
http://www.eia.gov/dnav/pet/pet_pnp_crq_dcu_nus_m.htm.
50
9.
Y. Kida, C. A. Class, A. J. Concepcion, M. T. Timko and W. H.
Green, Phys Chem Chem Phys, 2014, 16, 9220-9228.
10. M. Morimoto, Y. Sugimoto, Y. Saotome, S. Sato and T. Takanohashi,
Physics, 2009, 130, 054106.
Physics, 2009, 130, 054104.
27. K. A. Peterson, T. B. Adler and H.-J. Werner, Journal of Chemical
J. D. V. Hamme, A. Singh and O. P. Ward, Microbiology and
Molecular Biology Reviews, 2003, 67.
25. T. B. Adler, H.-J. Werner and F. R. Manby, Journal of Chemical
26. G. Knizia, T. B. Adler and H.-J. Werner, Journal of Chemical
L. A. Gonzalez, P. Kracke, W. H. Green, J. W. Tester, L. M. Shafer
and M. T. Timko, Energy & Fuels, 2012, 26, 5164-5176.
8.
Petersson, Journal of Chemical Physics, 1998, 110, 2822-2827.
23. J. A. Montgomery Jr., M. J. Frisch, J. W. Ochterski and G. A.
105
Physics, 2008, 128, 084102.
28. R. J. Bartlett and M. Musial, Reviews of Modern Physics, 2007, 79,
291-352.
29. K. Raghavachari, G. W. Trucks, J. A. Pople and M. Head-Gordon,
Chemical Physics Letters, 1989, 157, 479-483.
The Journal of Supercritical Fluids, 2010, 55, 223.
This journal is © The Royal Society of Chemistry 2012
PCCP, 2012, 00, 1-3 | 7
ARTICLE
Journal Name
30. J. D. Watts, J. Gauss and R. J. Bartlett, Journal of Chemical Physics,
1993, 98, 8718-8733.
50
A, 2010, 114, 765-777.
32. J. Aguilera-Iparraguirre, A. D. Boese, W. Klopper and B. Ruscic,
56. L. B. Harding and S. J. Klippenstein, J. Phys. Chem. Lett., 2010, 1,
Chemical Physics, 2008, 346, 56-68.
33. J. Aguilera-Iparraguirre, H. J. Curran, W. Klopper and J. M. Simmie,
Journal of Physical Chemistry A, 2008, 112, 7047-7054.
55 57.
34. W. Klopper, R. A. Bachorz, D. P. Tew, J. Aguilera-Iparraguirre, Y.
Rychlewski, Dordrecht, 2003.
Faraday Trans. 2, 1987, 83, 731-739.
60
36. J. Noga and W. Kutzelnigg, Journal of Chemical Physics, 1994, 101,
61. G. S. Tyndall and A. R. Ravishankara, International Journal of
65
Account, 2009, 123, 391-412.
20
63. B. A. Ellingson and D. G. Truhlar, J. Am. Chem. Soc., 2007, 129,
Montgomery and M. J. Frisch, Journal of Chemical Physics,
1998, 109, 10570-10579.
12765-12771.
70
41, 157-167.
25
66. D. P. Tabor, M. E. Harding, T. Ichino and J. F. Stanton, J. Phys.
75
Cambridge, MA, 2010.
30
68. W. Tsang, Journal of Physical and Chemical Reference Data, 1988,
Chem., 1995, 99, 14514-14527.
66, 532-533.
17, 887-952.
80
45. C. Eckart, Physical Review, 1930, 35, 1303-1309.
35
71. W. K. Busfield, H. Mackle and P. A. G. O'Hare, Trans. Faraday Soc.,
85
761.
73. H. Mackle and P. A. G. O'Hare, Trans. Faraday Soc., 1961, 57, 1070-
F. A. Bischoff, S. Wolfsegger and D. P. Tew, Molecular Physics,
2009, 107, 963-975.
51. A. Jalan, I. M. Alecu, R. Meana-Pañeda, J. Aguilera-Iparraguirre, K.
1074.
90
R. Yang, S. S. Merchant, D. G. Truhlar and W. H. Green, J.
45
2059.
83, 1915-1924.
52. C. Deng, Q.-G. Li, Y. Ren, N.-B. Wong, S.-Y. Chu and H.-J. Zhu,
Journal of Computational Chemistry, 2007, 29, 466-480.
74. H. Mackle and W. V. Steele, Trans. Faraday Soc., 1969, 65, 205375. B. C. Garrett and D. G. Truhlar, Journal of Physical Chemistry, 1979,
Am. Chem. Soc., 2013, 135, 11100-11114.
53. J. Li, A. Kazakov and F. L. Dryer, J. Phys. Chem. A, 2004, 108,
1961, 57, 1054-1057.
72. H. Mackle and D. V. McNally, Trans. Faraday Soc., 1969, 65, 17381741.
49. N. M. Marinov, Int. J. Chem. Kinet., 1999, 31, 1999.
40 50.
546-572.
Havlas, Collect. Czech. Chem. Commun., 1988, 53, 2140-2158.
5311.
48. L. G. S. Shum and S. W. Benson, Int. J. Chem. Kinet., 1985, 17, 749-
69. S. W. Benson and J. H. Buss, Journal of Chemical Physics, 1958, 29,
70. F. Turecek, L. Brabec, T. Vondrak, V. Hanus, J. Hajicek and Z.
46. J. Pen, X. Hu and P. Marshall, J. Phys. Chem. A, 1999, 103, 530747. H. Arican and N. L. Arthur, Aust. J. Chem., 1983, 36, 2195-2202.
Chem. A, 2012, 116, 7668-7676.
67. W. D. Good, J. L. Lacina and J. P. McCullough, J. Phys. Chem.,
1961, 65, 2229-2231.
43. T. H. Lay, J. W. Bozzelli, A. M. Dean and E. R. Ritter, J. Phys.
44. H. S. Johnston and J. Heicklen, Journal of Physical Chemistry, 1962,
1951.
110, 7925-7934.
121, 3405-3416.
software package, Massachusetts Institute of Technology,
64. M. W. Chase, Jr., J. Phys. Chem. Ref. Data, 1998, Monograph 9, 165. G. da Silva, C.-H. Kim and J. W. Bozzelli, J. Phys. Chem. A, 2006,
41. A. D. Boese and J. M. L. Martin, Journal of Chemical Physics, 2004,
42. S. Sharma, M. R. Harper and W. H. Green, CanTherm open-source
Chemical Kinetics, 1991, 23, 483-527.
62. A. A. Westenberg and N. deHaas, J. Chem. Phys., 1973, 59, 66856686.
39. G. A. Petersson, D. K. Malick, W. G. Wilson, J. W. Ochterski, J. A.
40. Y. Zhao and D. G. Truhlar, Accounts of Chemical Research, 2008,
Stlef, J. Phys. Chem., 1982, 86, 81-84.
3237-3239.
37. J. Zheng, Y. Zhao and D. G. Truhlar, J. Chem. Theory Comput.,
2009, 5, 808-821.
59. J. V. Michael, D. F. Nava, W. D. Brobst, R. P. Borkowski and L. J.
60. R. A. Perry, R. Atkinson and J. N. Pitts Jr., J. Chem. Phys., 1976, 64,
7738-7762.
38. A. G. Vandeputte, M.-F. Reyniers and G. B. Marin, Theor Chem
D. H. Ess, S. E. Wheeler, R. G. Iafe, L. Xu, N. Çelebi-Ölçüm and K.
58. C. Lafage, J.-F. Pauwels, M. Carlier and P. Devolder, J. Chem. Soc.
113, 11679-11684.
35. W. Klopper and J. Noga, in Chemistry and Physics, ed. J.
3016-3020.
N. Houk, Angew. Chem. Int. Ed., 2008, 47, 7592-7601.
Carissan and C. Hättig, Journal of Physical Chemistry A, 2009,
10
15
of Chemical Physics, 2003, 119, 5117-5120.
55. L. B. Harding, Y. Georgievskii and S. J. Klippenstein, J. Phys. Chem.
31. J. M. L. Martin, Chemical Physics Letters, 1996, 259, 669-678.
5
54. D. R. Kent, S. L. Widicus, G. A. Blake and W. A. Goddard, Journal
76. J. Zheng, T. Yu, E. Papajak, I. M. Alecu, S. L. Mielke and D. G.
95
Truhlar, Phys Chem Chem Phys, 2011, 13, 10885-10907.
7671-7680.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012
Journal Name
ARTICLE
9
Figure 1. Proposed mechanism for conversion of hexyl sulfide to pentane and CO2
Table 1. Comparison of CBS-QB3 and CCSD(T)-F12 calculations with published data. Published value for reaction c was theoretically
estimated. T (K), kf [cm3/(mol*s) for bimolecular reactions, s-1 for unimolecular reaction]
Reaction
a. H2S + H
b. H2S + CH3
Reference
Published
CBS-QB3
k f (T)
VDZ-F12
VTZ-F12
VQZ-F12
400
1.4 × 106
2.0 × 106
2.2 × 106
2.5 × 106
2.3 × 106
CH4 + SH Arican [47]
400
8.8 × 10
3
1.6 × 104
9.3 × 103
9.4 × 103
8.1 × 10
Shum [48]
700
9.4 × 104
9.3 × 105
4.3 × 105
4.7 × 105
4.6 × 105
Marinov [49]
500
700
c. H2C=S + CH3
d.
OH
Pen [46]
H2 + SH
S
C2H4 + H2O
T
3
5.8 × 10−16 9.8 × 10−17 7.3 × 10−16 5.6 × 10−16 4.2 × 10−16
1.1 × 10−7 1.4 × 10−8 6.0 × 10−8 5.0 × 10−8 4.1 × 10−8
Table 2. Mean absolute difference in barrier height (kJ/mol) calculated using double-, triple-, and quadruple-zeta basis sets with CCSD(T)-F12a.
|DZ-QZ|
|TZ-QZ|
1
1.21
0.01
This journal is © The Royal Society of Chemistry 2012
Reaction #
12
20
0.31
1.57
0.57
0.34
31
1.67
0.16
Average
1.19
0.27
PCCP, 2012, 00, 1-3 | 9
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Journal Name
Table 3. Modified Arrhenius coefficients for the molecular addition of water to sulfur-containing compounds. A [cm3/(mol*s) forward, s-1
reverse], n (unitless), Ea, ΔEo, and ΔH°rxn (kJ/mol). Parameters for reaction 6 computed using CCSD(T)//B3LYP, the rest computed using
CCSD(T)-F12a//VTZ-F12// B3LYP/CBSB7. ΔEo,F12 calculated using CCSD(T)-F12a//VTZ-F12, ΔEo,CBS calculated using CBS-QB3.
Reaction
S
1.
HO
H2O
SH
Forward Rate Parameters
ΔE o,CBS
ΔE o,F12
Ea
122.7
127.6
101.8
ΔH° rxn
-54.1
123.5
127.2
-48.1
8.57
1.12
157.9
101.3
121.6
125.3
-46.7
8.94
1.03
154.6
4.54
101.7
125.0
125.9
-46.9
8.32
1.19
154.6
-1.22
3.75
122.8
140.9
145.6
-28.4
8.01
1.32
157.0
300-2000
-1.78
3.90
123.1
n.c.
144.3
-29.6
7.75
1.44
158.5
400-2000
-2.32
3.87
141.3
160.2
163.7
-8.3
4.92
1.98
150.4
500-2000
0.20
3.50
172.9
187.8
193.9
13.8
11.87
0.33
171.2
500-2000
-0.66
3.70
209.9
230.4
235.4
35.6
11.91
0.38
182.9
600-2000
-2.8
4.32
244.7
313.8
269.3
274.7
33.9
7.59
1.79
215.2
500-2000
-1.6
4.13
244.0
264.4
271.2
37.0
8.60
1.63
210.4
T
log 10 A
300-2000 -0.62
n
3.55
300-2000
-2.42
3.96
102.7
300-2000
-2.58
3.95
300-2000
-4.30
300-2000
Reverse Rate Parameters
n
Ea
log 10 A
163.9
8.74
1.07
SH
S
2.
H2O
OH
SH
S
3.
H2O
OH
S
SH
4.
H2O
OH
SH
S
5.
H2O
OH
Ph
6.
S
Ph
SH
H2O
OH
S
7.
SH
H2O
OH
OH
OH
O
O
8.
H2O
C
HS
S
S
O
9.
C
H2O
HO
S
S
10.
OH
S
H2O
S
11.
OH
OH
S
H2O
OH
S
H2O
HO
SH
Figure 2. Optimized transition state for the hydration of thioformaldehyde. Distances (Ångstroms).
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012
Journal Name
ARTICLE
Table 4. Reaction barriers (kJ/mol) for hydration of thioformaldehyde, formaledehyde, and ethene. Data for the first reaction calculated using
CCSD(T)-F12.
ΔE o,f
ΔE o,r
Ref.
H2O
HO
SH
123
173
this work
H2O
HO
OH
166
189
Kent [54]
H2O
HO
209
254
Li [53]
Reaction
S
H2C
O
H2C
CH2
H2C
Ph
SH
S
S
Ph
H 2O
SH
H2O
OH
OH
Figure 3. Transition states for the hydration of 2-propenethial (left) and benzenethial (right). Distances (Ångstroms).
S
O
C
S
Figure 4. Transition states
52
C
HO
O
O
H2O
OH
S
H 2O
HS
OH
for the hydration of carbonyl (left) and thiocarbonyl (right) group of carbonyl sulfide. Distances (Ångstroms).
This journal is © The Royal Society of Chemistry 2012
PCCP, 2012, 00, 1-3 | 11
ARTICLE
Journal Name
Table 5. Modified Arrhenius coefficients for the molecular addition of hydrogen sulfide to carbonyl compounds. A [cm3/(mol*s) forward, s-1
reverse], n (unitless), Ea, ΔEo, and ΔH°rxn (kJ/mol). Parameters for reaction 17 computed using CCSD(T)//B3LYP, the rest computed using
CCSD(T)-F12a//VTZ-F12 energies. ΔEo,F12 calculated using CCSD(T)-F12a//VTZ-F12, ΔEo,CBS calculated using CBS-QB3.
Reaction
12.
O
HO
H2S
SH
Forward Rate Parameters
Ea
ΔE o,F12
ΔE o,CBS
156.7
170.0
172.7
ΔH° rxn
-50.1
Reverse Rate Parameters
log 10 A
n
Ea
10.5
0.82
209.9
T
300-2000
log 10 A
1.09
n
3.27
300-2000
1.78
2.93
153.5
161.8
164.4
-34.1
12.9
0.13
189.5
300-2000
1.49
2.96
152.0
159.9
162.8
-32.9
13.4
0.01
187.3
300-2000
0.22
3.45
158.0
168.7
169.1
-26.1
13.0
0.16
184.0
300-2000
2.58
2.72
151.8
159.1
159.2
-22.0
12.5
0.20
177.3
300-2000
2.09
2.83
145.1
n.c.
153.0
-20.5
11.6
0.45
169.9
300-2000
-0.68
3.60
159.7
170.4
171.8
31.9
7.04
1.65
120.6
500-2000
0.71
3.52
190.2
204.0
209.4
40.7
11.44
0.59
154.8
SH
13.
O
H2S
OH
SH
O
14.
H2S
OH
O
SH
H2S
15.
OH
SH
O
16.
H2S
OH
Ph
17.
O
Ph
SH
H2S
OH
O
18.
SH
H2S
OH
OH
OH
O
O
19.
C
O
H2S
HS
OH
O
H2S
HO
SH
Figure 5. Transition state for the molecular addition of H2 S to formaldehyde. Distances (Ångstroms).
12 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012
Journal Name
ARTICLE
Figure 6. Potential energy surface for H2S addition reaction 12. Energies (kJ/mol) relative to the mercaptoalcohol.
SH
O
SH
O
H2S
H2S
OH
OH
Figure 7. Transition states for the molecular addition of H2S to acetaldehyde (left) and propanal (right). Distances (Ångstroms).
O
SH
H 2S
OH
C
OH
OH
O
O
O
H2S
HS
OH
Figure 8. Transition states for the endothermic addition of H2S to acetic acid (left) and carbon dioxide (right). Distances (Ångstroms).
This journal is © The Royal Society of Chemistry 2012
PCCP, 2012, 00, 1-3 | 13
ARTICLE
Journal Name
Table 6. Modified Arrhenius coefficients for hydrogen abstraction reactions. Reaction 21 estimated for overall pathway including pre-reactive
complex at high-pressure limit. A [cm3/(mol*s)], n (unitless), Ea, ΔEo, and ΔH°rxn (kJ/mol). Parameters computed using CCSD(T)-F12a//VTZF12//B3LYP/CBSB7. ΔEo,F12 calculated using CCSD(T)-F12a//VTZ-F12// B3LYP/CBSB7, ΔEo,CBS calculated using CBS-QB3.
Reaction
20.
H2S + OH
21.
SH
SH + H2O
Forward Rate Parameters
Ea
ΔE o,F12
ΔE o,CBS
-2.8
4.4
3.1
ΔH° rxn
-114.1
Reverse Rate Parameters
log 10 A
n
Ea
7.08
2.00
109.60
T
log 10 A
300-2000
7.80
n
1.71
300-2000
13.0
0.03
1.9
-12.3
-3.2
-136.7
2.22
3.56
114.86
300-2000
4.32
2.44
5.0
14.9
20.7
-56.3
2.99
2.92
59.78
300-2000
6.12
2.09
-2.0
-1.0
13.6
-78.9
2.41
3.43
72.47
•
22.
S
OH
O
H 2S
H 2O
OH
SH
•
23.
24.
H 2S
25.
26.
27.
S
O
SH
O
OH
SH
•
1.71
3.34
63.6
77.0
81.1
22.5
2.53
3.21
37.54
1.65
3.28
68.4
79.4
78.9
-0.10
-0.06
4.06
61.62
300-2000
4.08
2.90
0.74
6.8
2.2
-9.8
2.63
3.07
10.07
500-2000
0.26
3.63
35.2
44.9
39.4
-19.4
0.11
3.78
53.90
CH4
400-2000
1.03
3.44
17.9
35.2
31.3
-55.2
0.29
3.81
74.34
H 2S
300-2000
5.04
2.47
3.1
18.1
4.6
-0.17
3.91
2.60
3.64
300-2000
0.13
3.51
-3.6
4.9
5.2
-59.3
-2.34
4.58
54.41
OH
O
SH
O
O
O
H 2S
SH
SH
O
OH
OH
28.
CH3
SH
SH
OH
OH
29.
SH
SH
SH
30. O
500-2000
500-2000
OH
S
SH
SH
CH3
•
O
S
CH4
H2S + OH
SH + H2O
Figure 9. Linear (left) and angled (right) transition states optimized for hydrogen abstraction from hydrogen sulfide by the hydroxyl radical. Distances
(Ångstroms) and angle (degrees).
14 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012
Journal Name
ARTICLE
Figure 10. Comparison of rate coefficient calculations (cm3/molecules/s) with experimental data for H2S + OH = SH + H2 O. Lafage (o), Michael (x), Perry
( ), Westenberg (+), Ellingson (hashed): M06-2X (black), MPWB1K (blue), MPW1K (green), BB1K (red), This Work (solid): CBS-QB3 (red), CCSD(T)F12a/VTZ-F12 (black), CCSD(T)-F12a/VQZ-F12 (blue)
SH
OH
S
H2O
Figure 11. Potential energy surface for hydrogen abstraction from methanethiol by hydroxyl radical. Energies (kJ/mol), distances (Ångstroms), angles
(degrees). Note the submerged TS (saddle point energy less than energy of reactants).
This journal is © The Royal Society of Chemistry 2012
PCCP, 2012, 00, 1-3 | 15
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Journal Name
Table 7. Forward reaction barriers (kJ/mol) for hydrogen abstraction reactions by the acetyl radical.
Reaction
SH
O
O
SH
O
O
ΔEo
Ref.
44.9
this work
67.9
Tsang [68]
Table 8. Modified Arrhenius coefficients for radical addition to double bonds. Reaction 37 estimated for overall pathway including pre-reactive
complex at high-pressure limit. A [cm3/(mol*s) forward, s-1 reverse], n (unitless), Ea, ΔEo, and ΔH°rxn (kJ/mol). Parameters computed using
CCSD(T)-F12a//VTZ-F12 energies. ΔEo,F12 calculated using CCSD(T)-F12a//VTZ-F12, ΔEo,CBS calculated using CBS-QB3.
Reaction
31.
HO
S
32.
HO
S
H
HO
S
Forward Rate Parameters
Ea
ΔE o,F12
ΔE o,CBS
ΔH° rxn
Reverse Rate Parameters
log 10 A
n
Ea
T
log 10 A
n
300-2000
8.45
1.63
11.4
16.0
15.9
-132.1
7.83
1.83
143.4
300-2000
4.36
2.35
23.0
28.5
29.4
-99.3
10.98
0.99
123.3
300-2000
3.22
2.54
16.3
20.7
19.0
-96.0
12.35
0.55
112.8
300-2000
9.30
1.21
-5.3
-0.41
3.3
-101.2
10.86
0.46
98.6
300-2000
9.92
1.23
32.2
38.4
39.7
-38.8
9.03
1.33
73.7
300-2000
6.91
1.68
54.2
59.1
56.3
-28.3
11.86
0.59
84.6
300-2000
13.08
0.00
1.7
-9.3
-16.2
-41.6
12.61
0.14
24.6
OH
CH3
S
OH
33.
HO
C2H5
S
S
OH
OH
34.
H
S
SH
S
35.
H
C
S
O
O
S
36.
CH3
C
O
O
S
SH
37.
OH
SH
OH
R
HO
S
R
HO
S
R = H, CH3, C2H5
Figure 12. Transition states for radical additions to C=S bonds: reactions 31 (left), 32 (middle), and 33 (right). Distances (Ångstroms).
16 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012
Journal Name
ARTICLE
OH
OH
H
SH
S
Figure 13. Transition state for radical addition to the S atom in thioacetic acid (reaction 34). Distances (Ångstroms).
SH
OH
SH
OH
Figure 14. Potential energy surface for addition of thiol radical to carbon-1 in 1-propen-1-ol. Energies (kJ/mol), distances (Ångstroms). Note this reaction
has a submerged TS, i.e. saddle point energy is lower than energy of reactants.
This journal is © The Royal Society of Chemistry 2012
PCCP, 2012, 00, 1-3 | 17
ARTICLE
Journal Name
Table 9. Modified Arrhenius coefficients for elementary tautomerization reactions that include sulfur and oxygen. A (s-1), n (unitless), Ea, ΔEo,
and ΔH°rxn (kJ/mol). Parameters computed using CCSD(T)-F12a/VTZ-F12 energies. ΔEo,F12 calculated using CCSD(T)-F12a//VTZ-F12, ΔEo,CBS
calculated using CBS-QB3.
Reaction
SH
S
38.
H
H
OH
S
Reverse Rate Parameters
log 10 A
n
Ea
n
300-2000
1.50
3.33
86.6
112.2
121.0
-8.6
1.12
3.25
96.8
300-2000
1.79
3.26
81.7
106.2
115.7
-9.9
1.64
3.09
95.5
300-2000
1.77
3.27
82.0
107.1
115.6
-8.6
1.85
3.05
94.4
SH
OH
CH3
S
O
SH
40.
C2H5
ΔH° rxn
log 10 A
O
39.
CH3
Forward Rate Parameters
Ea
ΔE o,F12
ΔE o,CBS
T
OH
C2H5
O
SH
S
R
OH
R
O
R = H, CH3, C2H5
Figure 15. Transition states for tautomerization reactions 38 (left), 39 (middle), and 40 (right). Distances (Ångstroms).
18 | J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
Table 10. GAV for groups containing carbon, sulfur, and oxygen, based on CBS-QB3 calculations available in the Supplementary Material.
Groups presented in Benson notation 69. ΔfH° (kJ/mol), S°int (J/mol/K) C p° (J/mol/K)
Group
Benson Group Additivity Values
C °p
400 K
500 K
600 K
39.92
46.03
49.85
43.19
46.44
47.28
42.46
44.72
44.02
1.
2.
3.
C-(O)(S)(H) 2
C-(C)(O)(S)(H)
C-(C) 2(O)(S)
∆fH°
298 K
-48.47
-46.45
-47.10
4.
C-(O) 2(S)(H)
-82.52
-55.49
26.61
36.47
42.37
45.52
48.36
49.85
52.41
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15
C-(C)(O) 2(S)
CO-(S)(H)
CO-(C)(S)
CO-(O)(S)
CS-(O)(H)
CS-(C)(O)
CS-(O) 2
O-(CS)(H)
O-(CS)(C)
S-(CO)(H)
S-(CO)(C)
-89.59
-41.18
-58.64
-48.22
11.93
-5.54
-95.08
-131.29
-60.84
-88.10
-64.13
-153.57
122.84
35.77
40.19
126.10
36.08
11.15
134.20
41.92
148.14
46.48
27.84
23.04
18.29
20.68
18.76
16.31
12.89
29.22
23.26
33.66
24.17
35.28
25.77
21.09
23.57
22.17
17.46
15.03
34.92
26.40
38.09
28.16
38.63
28.04
23.04
26.55
25.50
19.24
16.30
39.68
29.30
41.65
31.80
39.64
30.01
24.38
29.24
28.55
21.35
16.88
43.43
31.86
44.55
34.89
39.44
33.71
26.32
31.74
33.70
25.44
16.68
48.47
35.66
48.63
38.96
38.48
36.79
27.10
32.47
37.63
28.27
15.69
51.30
37.63
51.30
40.88
37.17
41.14
26.70
34.23
43.40
31.14
13.53
54.35
38.87
55.46
42.44
S°int
298 K
19.17
-67.54
-166.24
300 K
31.30
35.04
34.12
800 K
53.77
47.28
40.76
1000 K
56.65
46.90
37.69
1500 K
62.45
48.55
34.90
Table 11. HBI for radical groups containing carbon, sulfur, and oxygen, based on CBS-QB3 calculations available in the Supplementary
Material. ΔfH° (kJ/mol), S°int (J/mol/K) Cp° (J/mol/K)
Group
16. C•−(C)(O)(S)
17. S•−(CO)
ΔfH°
298 K
385.35
375.97
S°int
298 K
34.14
-5.27
300 K
-24.14
-40.79
This journal is © The Royal Society of Chemistry 2012
Hydrogen atom bond increment
C°p
400 K
500 K
600 K
-23.10
-20.84
-19.96
-49.37
-56.02
-62.13
800 K
-24.35
-72.84
1000 K
-33.97
-80.71
1500 K
-59.54
-89.62
PCCP, 2012, 00, 1-3 | 19
Supplementary Material for:
A kinetic and thermochemical database for organic sulfur and oxygen
compounds
Calculation of rate parameters for Reactions 21 and 37
Rate parameters were calculated for the two reactions with submerged transition states using the
method described in the main article, and the component rate coefficients are presented in the
following tables. k1 is estimated for the high-pressure limit, k2 is calculated using transition state theory
(with the CCSD(T)-F12 energies), K1 is calculated using thermochemical parameters calculated using CBSQB3, and k-1 is calculated using thermodynamic consistency. keff provides the effective rate constant
calculated at each temperature, while kfit shows the rate constant obtained using the best-fit modified
Arrhenius parameters. The ratio of the fitted rate constants to the rate constants calculated at each
temperature show that low fitting error was obtained for temperatures between 400 and 2000 K, but
significantly greater error was obtained at 300 K. Thus, the specific keff(300 K) should be used at this
temperature.
Rate parameters for Reaction 21 (Hydrogen Abstraction)
T
300
400
500
600
800
1000
1500
2000
k1
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
k-1
1.27E+11
1.69E+10
5.36E+09
2.58E+09
1.11E+09
7.12E+08
4.41E+08
3.80E+08
K1
1.27E-02
1.69E-03
5.36E-04
2.58E-04
1.11E-04
7.12E-05
4.41E-05
3.80E-05
k2
1.89E+10
9.28E+10
2.42E+11
4.62E+11
1.05E+12
1.76E+12
3.60E+12
5.26E+12
keff
1.30E+12
8.46E+12
9.78E+12
9.94E+12
9.99E+12
1.00E+13
1.00E+13
1.00E+13
kfit
5.58E+12
6.81E+12
7.68E+12
8.34E+12
9.25E+12
9.86E+12
1.08E+13
1.13E+13
kfit/keff
4.30
0.81
0.79
0.84
0.93
0.99
1.08
1.13
Rate parameters for Reaction 37 (Radical Addition to Double Bond)
T
300
400
500
600
800
1000
1500
2000
k1
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
1.00E+13
k-1
5.10E+11
7.20E+10
2.33E+10
1.14E+10
4.91E+09
3.14E+09
1.96E+09
1.71E+09
K1
5.10E-02
7.20E-03
2.33E-03
1.14E-03
4.91E-04
3.14E-04
1.96E-04
1.71E-04
k2
2.82E+11
3.96E+11
4.93E+11
5.77E+11
7.19E+11
8.34E+11
1.04E+12
1.18E+12
keff
3.56E+12
8.46E+12
9.55E+12
9.81E+12
9.93E+12
9.96E+12
9.98E+12
9.99E+12
kfit
6.23E+12
7.36E+12
8.13E+12
8.69E+12
9.44E+12
9.93E+12
1.06E+13
1.10E+13
kfit/keff
1.75
0.87
0.85
0.89
0.95
1.00
1.06
1.10
Rate parameters calculated using CBS-QB3
All rate parameters in the Supplementary Materials were calculated using CBS-QB3.
Units: A [cm3/(mol*s) for bimolecular reactions, s-1 for unimolecular reactions], n (unitless), Ea (kJ/mol).
H2O Addition
Reaction
1.
Forward Rate Parameters
T
log 10 A
n
Ea
300-2000 -0.63
3.56
106.8
Reverse Rate Parameters
log 10 A
n
Ea
8.72
1.07
167.4
2.
300-2000
-2.44
3.96
106.3
8.56
1.12
161.3
3.
300-2000
-2.59
3.95
104.3
8.93
1.03
158.0
4.
300-2000
-4.31
4.55
103.9
8.31
1.20
158.5
5.
300-2000
-1.24
3.75
126.7
0.99
1.33
160.4
6.
300-2000
-1.78
3.90
123.1
7.75
1.44
158.5
7.
400-2000
-2.53
3.93
143.5
4.79
2.02
151.9
8.
500-2000
0.20
3.50
172.9
11.87
0.33
171.2
9.
500-2000
-0.66
3.70
209.9
11.91
0.38
182.9
10.
600-2000
-2.8
4.32
250.1
313.8
7.58
1.79
220.4
11.
500-2000
-1.6
4.14
250.8
8.60
1.63
216.5
H2S Addition
Reaction
Forward Rate Parameters
log 10 A
n
Ea
1.09
3.27
159.6
Reverse Rate Parameters
log 10 A
n
Ea
10.5
0.82
210.4
12.
T
300-2000
13.
300-2000
1.78
2.93
155.3
12.9
0.13
191.4
14.
300-2000
1.49
2.96
153.6
13.4
0.01
189.5
15.
300-2000
0.22
3.45
159.0
13.0
0.16
187.7
16.
300-2000
2.58
2.72
151.9
12.5
0.20
177.7
17.
300-2000
2.09
2.83
145.1
11.6
0.45
169.9
18.
300-2000
-0.69
3.60
161.3
7.04
1.65
124.7
19.
500-2000
0.71
3.52
190.2
11.44
0.59
154.8
Hydrogen Abstraction
Reaction
20.
Forward Rate Parameters
T
log 10 A
n
Ea
300-2000
7.76
1.72
-1.4
Reverse Rate Parameters
log 10 A
n
Ea
7.04
2.02
112.01
21.
300-2000
5.3
2.40
-7.6
2.22
3.56
126.20
22.
300-2000
4.15
2.49
10.6
2.82
2.97
65.62
23.
300-2000
6.12
2.09
11.7
2.41
3.43
87.10
24.
500-2000
1.70
3.34
67.2
2.52
3.21
37.62
25.
500-2000
1.69
3.27
66.2
-0.03
4.05
56.67
26.
300-2000
4.44
2.80
-2.41
3.00
2.97
5.63
27.
500-2000
0.34
3.60
29.9
0.19
3.76
47.89
28.
400-2000
1.14
3.41
13.7
0.40
3.78
72.53
29.
300-2000
5.79
2.35
-3.0
4.35
2.48
-2.17
30.
300-2000
0.13
3.51
-5.0
-2.33
4.58
56.23
Radical Addition to Double Bonds
Reaction
Forward Rate Parameters
log 10 A
n
Ea
T
Reverse Rate Parameters
log 10 A
n
Ea
31.
300-2000
8.45
1.63
10.8
7.84
1.83
141.0
32.
300-2000
4.36
2.35
22.9
10.98
0.99
124.1
33.
300-2000
3.08
2.58
14.3
12.35
0.55
113.7
34.
300-2000
9.30
1.21
-0.6
10.86
0.46
100.8
35.
300-2000
9.92
1.23
33.5
9.02
1.33
71.9
36.
300-2000
6.91
1.68
51.2
11.86
0.59
80.1
37.
300-2000
13.08
0.00
1.7
12.61
0.14
23.7
Tautomerization
Reaction
T
Forward Rate Parameters
log 10 A
n
Ea
Reverse Rate Parameters
log 10 A
n
Ea
38.
300-2000
1.18
3.42
91.0
0.81
3.34
99.8
39.
300-2000
1.49
3.35
85.9
1.34
3.17
97.9
40.
300-2000
1.49
3.35
86.1
1.57
3.13
96.6
Thermochemical Properties Tables
Thermochemical parameters were calculated using CBS-QB3. Enthalpies are presented in units of
kJ*mol-1, while the remaining parameters are presented in units of J*mol-1*K-1.
(298 K)
-26.31
(298 K)
205.59
Cp
300 K
34.19
400 K
35.45
500 K
37.03
600 K
38.76
800 K
42.22
1000 K
45.30
1500 K
50.63
2000 K
53.44
2400 K
54.72
-26.82
255.54
50.43
58.06
65.60
72.59
84.40
93.46
107.74
115.37
119.08
-52.91
302.57
73.81
87.41
100.10
111.56
130.53
144.87
167.19
178.92
184.56
-74.88
340.89
97.48
116.26
134.07
150.19
176.69
196.47
226.81
242.58
250.12
44.25
325.41
87.04
102.61
116.87
129.62
150.54
166.20
190.28
202.76
208.69
111.00
230.69
38.45
43.20
47.86
52.07
58.95
64.02
71.73
75.80
77.80
64.83
273.70
58.88
69.48
79.40
88.31
102.86
113.70
130.26
138.84
142.93
41.84
317.85
81.00
97.23
112.57
126.30
148.53
164.86
189.50
202.13
208.14
19.74
305.35
79.64
95.27
110.34
124.01
146.47
163.15
188.54
201.63
207.86
157.40
287.09
72.11
88.08
102.09
113.85
131.31
142.74
157.97
165.85
169.76
185.42
343.03
114.98
147.35
175.41
198.84
233.70
256.85
288.35
303.91
311.15
111.89
278.57
73.41
95.08
112.97
127.26
147.75
161.27
180.41
190.28
195.18
-185.89
292.73
77.15
88.08
96.00
101.93
110.54
117.05
129.16
136.75
140.22
-226.10
322.99
102.87
120.04
132.78
142.58
144.72
168.50
188.49
200.30
205.66
-247.67
360.90
129.63
150.72
167.18
180.79
202.74
219.85
248.31
263.80
271.01
-269.89
350.78
129.73
152.91
170.33
184.01
204.94
220.95
248.49
264.14
271.28
-113.75
345.00
118.96
139.20
153.86
164.90
180.91
192.70
213.02
224.86
230.30
-86.99
398.69
159.40
196.79
226.36
249.81
284.13
307.88
343.75
362.61
371.37
-378.54
328.69
88.41
100.15
109.48
117.11
128.78
137.17
150.03
156.88
160.26
(298 K)
-26.31
(298 K)
205.59
Cp
300 K
34.19
400 K
35.45
500 K
37.03
600 K
38.76
800 K
42.22
1000 K
45.30
1500 K
50.63
2000 K
53.44
2400 K
54.72
-26.82
255.54
50.43
58.06
65.60
72.59
84.40
93.46
107.74
115.37
119.08
-86.99
-52.91
398.69
302.57
159.40
73.81
196.79
87.41
226.36
100.10
249.81
111.56
284.13
130.53
307.88
144.87
343.75
167.19
362.61
178.92
371.37
184.56
-74.88
340.89
97.48
116.26
134.07
150.19
176.69
196.47
226.81
242.58
250.12
-378.54
44.25
328.69
325.41
88.41
87.04
100.15
102.61
109.48
116.87
117.11
129.62
128.78
150.54
137.17
166.20
150.03
190.28
156.88
202.76
160.26
208.69
111.00
230.69
38.45
43.20
47.86
52.07
58.95
64.02
71.73
75.80
77.80
-426.47
64.83
361.32
273.70
116.25
58.88
132.31
69.48
145.43
79.40
156.49
88.31
174.09
102.86
187.23
113.70
208.03
130.26
219.38
138.84
225.00
142.93
41.84
317.85
81.00
97.23
112.57
126.30
148.53
164.86
189.50
202.13
208.14
-450.73
19.74
393.78
305.35
137.83
79.64
160.28
95.27
179.23
110.34
195.38
124.01
220.90
146.47
239.60
163.15
268.28
188.54
283.39
201.63
290.73
207.86
157.40
287.09
72.11
88.08
102.09
113.85
131.31
142.74
157.97
165.85
169.76
-96.92
326.83
105.02
130.86
152.51
185.42
343.03
114.98
147.35
175.41
-93.86
325.22
106.93
133.52
155.54
111.89
278.57
73.41
95.08
112.97
127.26
147.75
161.27
180.41
190.28
195.18
-132.92
-185.89
269.68
292.73
56.32
77.15
63.77
88.08
70.05
96.00
75.32
101.93
83.46
110.54
89.20
117.05
97.25
129.16
100.62
136.75
101.79
140.22
170.23
198.84
173.28
196.44
233.70
198.79
214.27
256.85
215.61
240.44
288.35
240.42
254.37
303.91
254.62
311.15
261.47
-124.29
260.64
49.01
58.00
66.13
73.07
83.52
90.44
99.17
-226.10
322.99
102.87
120.04
132.78
142.58
144.72
168.50
188.49
-185.29
312.44
78.23
92.09
103.65
-247.67
360.90
129.63
150.72
167.18
-175.45
296.90
70.07
84.29
97.43
-269.89
350.78
129.73
152.91
170.33
-207.91
346.14
105.14
122.52
137.92
-113.75
345.00
118.96
139.20
153.86
-199.29
338.89
92.67
112.71
131.12
147.26
172.70
190.72
216.47
228.68
234.13
-86.99
-379.42
398.69
290.84
159.40
70.25
196.79
82.58
226.36
92.47
249.81
100.15
284.13
110.49
307.88
116.41
343.75
122.33
362.61
123.80
371.37
124.15
-378.54
-357.65
328.69
279.56
88.41
71.32
100.15
84.88
109.48
95.65
117.11
103.74
128.78
113.62
137.17
118.29
150.03
122.22
156.88
124.48
160.26
125.56
-426.47
-150.44
361.32
231.53
116.25
41.04
132.31
45.19
145.43
48.51
156.49
51.08
174.09
54.51
187.23
56.52
208.03
59.09
219.38
60.50
225.00
61.13
-199.83
-450.73
323.88
393.78
100.56
137.83
119.48
160.28
133.64
179.23
144.26
195.38
159.03
220.90
169.37
239.60
187.63
268.28
199.46
283.39
205.17
290.73
113.31
180.79
109.02
184.01
151.48
164.90
128.30
202.74
127.34
204.94
173.46
180.91
139.08
219.85
140.25
220.95
189.67
192.70
155.07
248.31
158.05
248.49
213.85
213.02
102.45
261.00
200.30
162.77
263.80
165.83
264.14
225.74
224.86
103.57
205.66
166.10
271.01
169.01
271.28
231.14
230.30
(298 K)
-26.31
(298 K)
205.59
Cp
300 K
34.19
400 K
35.45
500 K
37.03
600 K
38.76
800 K
42.22
1000 K
45.30
1500 K
50.63
2000 K
53.44
2400 K
54.72
-379.42
-26.82
290.84
255.54
70.25
50.43
82.58
58.06
92.47
65.60
100.15
72.59
110.49
84.40
116.41
93.46
122.33
107.74
123.80
115.37
124.15
119.08
-52.91
302.57
73.81
87.41
100.10
111.56
130.53
144.87
167.19
178.92
184.56
-357.65
-74.88
279.56
340.89
71.32
97.48
84.88
116.26
95.65
134.07
103.74
150.19
113.62
176.69
118.29
196.47
122.22
226.81
124.48
242.58
125.56
250.12
44.25
325.41
87.04
102.61
116.87
129.62
150.54
166.20
190.28
202.76
208.69
111.00
-150.44
230.69
231.53
38.45
41.04
43.20
45.19
47.86
48.51
52.07
51.08
58.95
54.51
64.02
56.52
71.73
59.09
75.80
60.50
77.80
61.13
64.83
-199.83
41.84
-166.71
273.70
323.88
69.48
119.48
97.23
113.83
79.40
133.64
88.31
144.26
102.86
159.03
113.70
169.37
130.26
187.63
138.84
199.46
142.93
205.17
317.85
327.62
58.88
100.56
81.00
98.54
112.57
126.26
126.30
136.81
148.53
154.00
164.86
167.33
189.50
189.01
202.13
200.54
208.14
205.87
19.74
-185.28
305.35
353.85
79.64
115.21
95.27
136.37
110.34
155.22
124.01
171.78
146.47
198.62
163.15
218.61
188.54
249.58
201.63
265.94
207.86
273.86
-144.57
157.40
297.81
287.09
72.53
72.11
85.83
88.08
97.67
102.09
108.04
113.85
124.76
131.31
137.06
142.74
155.23
157.97
163.84
165.85
167.52
169.76
-86.24
294.92
66.89
80.46
93.17
104.46
122.53
135.54
154.40
163.43
167.46
185.42
-211.47
343.03
335.39
114.98
92.91
147.35
113.76
175.41
132.75
198.84
149.06
233.70
174.10
256.85
191.39
288.35
215.64
303.91
227.14
311.15
232.35
111.89
-156.45
278.57
332.77
73.41
91.43
95.08
109.38
112.97
127.03
127.26
143.33
147.75
170.18
161.27
189.71
180.41
217.30
190.28
229.56
195.18
234.62
-185.89
292.73
77.15
88.08
96.00
101.93
110.54
117.05
129.16
136.75
140.22
-236.37
-226.10
382.97
322.99
117.06
102.87
142.80
120.04
166.80
132.78
187.85
142.58
220.80
144.72
243.93
168.50
276.70
188.49
292.26
200.30
299.28
205.66
-247.67
360.90
129.63
150.72
167.18
180.79
202.74
219.85
248.31
263.80
271.01
-269.89
350.78
129.73
152.91
170.33
184.01
204.94
220.95
248.49
264.14
271.28
-113.75
345.00
118.96
139.20
153.86
164.90
180.91
192.70
213.02
224.86
230.30
-86.99
398.69
159.40
196.79
226.36
249.81
284.13
307.88
343.75
362.61
371.37
-378.54
328.69
88.41
100.15
109.48
117.11
128.78
137.17
150.03
156.88
160.26
-426.47
361.32
116.25
132.31
145.43
156.49
174.09
187.23
208.03
219.38
225.00
-450.73
393.78
137.83
160.28
179.23
195.38
220.90
239.60
268.28
283.39
290.73
(298 K) (298 K)
139.62
192.04
Cp
300 K
29.03
400 K
29.10
500 K
29.35
600 K
29.75
800 K
30.80
1000 K
31.90
1500 K
34.08
2000 K
35.34
2400 K
35.90
115.62
238.93
40.17
45.80
51.44
56.69
65.61
72.48
83.40
89.28
92.14
122.58
305.71
71.22
82.63
93.42
103.13
119.00
130.78
148.78
158.11
162.57
153.80
306.64
77.50
92.35
105.99
118.07
137.54
151.83
173.38
184.42
189.66
208.47
324.42
77.01
90.00
103.03
114.98
134.49
148.75
169.94
180.59
185.59
-38.40
283.93
58.01
67.81
76.28
83.35
93.88
101.01
111.57
117.75
120.89
-76.45
314.30
83.71
99.46
112.64
123.65
140.65
152.87
171.47
181.32
186.14
-58.61
333.89
95.52
109.32
120.73
130.31
145.29
156.10
172.29
180.52
184.41
-99.21
356.87
107.82
128.96
147.34
163.05
187.63
205.29
231.67
245.19
251.67
-81.89
368.63
118.50
139.98
156.92
170.58
191.23
206.06
229.20
241.99
248.45
-52.02
369.04
123.28
142.78
158.28
171.07
191.08
205.93
229.48
242.38
248.76
28.76
268.52
47.04
52.03
56.42
60.16
65.96
70.02
75.83
78.60
79.86
-31.64
304.74
66.73
77.97
88.00
96.65
110.20
119.90
134.21
141.42
144.82
-51.99
345.39
92.09
106.93
121.06
133.81
154.59
169.88
192.80
204.41
209.88
Z-Matrices for Reaction Transition States
D6
D7
-62.73455333
59.62031099
Reaction 1 (H2O Addition)
Reaction 3 (H2O Addition)
01
C
H
S
H
O
H
H
01
C
H
S
H
O
H
C
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
D2
D3
D4
1
1
1
1
5
1
B1
B2
B3
B4
B5
B6
2
3
3
1
5
A1
A2
A3
A4
A5
2
2
3
3
D1
D2
D3
D4
1.09017221
1.78421227
2.10766562
1.57202431
1.15450839
1.08707034
117.41379967
103.92142842
97.84146984
82.86264147
103.58888573
87.65439124
113.14359777
1.69897839
-120.24280193
Reaction 2 (H2O Addition)
01
C
H
S
H
O
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
A1
A2
A3
A4
A5
A6
A7
A8
D1
D2
D3
D4
D5
1
1
1
1
5
1
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
1.09134866
1.79542051
2.12670833
1.59983409
1.15706391
1.50622240
1.09267319
1.09403545
1.09066297
114.67815208
102.02343744
96.48856122
82.05750160
106.38409353
108.34478150
111.63792524
110.34986003
83.74759670
109.03443995
2.27957436
-122.92886315
177.66230166
2
3
3
1
5
1
1
1
A1
A2
A3
A4
A5
A6
A7
A8
2
2
3
3
5
5
5
D1
D2
D3
D4
D5
D6
D7
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
1
1
1
1
5
1
7
7
7
10
10
10
B1
B2 2
B3 3
B4 3
B5 1
B6 5
B7 1
B8 1
B9 1
B10 7
B11 7
B12 7
A1
A2 2
A3 2
A4 3
A5 3
A6 5
A7 5
A8 5
A9 1
A10 1
A11 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1.09241006
1.79658311
2.12327006
1.59671168
1.15532024
1.51209272
1.09654537
1.09297196
1.53242997
1.09220528
1.09168655
1.09424066
114.59448553
102.07345850
96.55246307
82.19312673
106.23520644
108.90981510
108.35071455
111.33938850
110.26078754
110.54686150
111.54751453
84.00842439
109.35927488
2.33201560
-123.24658056
-59.01941864
58.01521388
179.26799570
179.45862584
-60.67338652
59.72805879
Reaction 4 (H2O Addition)
01
C
C
H
H
H
C
H
H
H
1
2
2
2
1
6
6
6
B1
B2
B3
B4
B5
B6
B7
B8
1
1
1
2
1
1
1
3
4
3
2
2
2
H
O
H
S
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
1
1
11
1
B9
B10
B11
B12
6
6
1
6
A8 2
A9 2
A10 6
A11 11
D7
D8
D9
D10
1.51645709
1.09174552
1.09202585
1.09556253
1.51344540
1.09436117
1.09250161
1.08917737
1.84815030
1.62342398
0.97085608
1.81232413
111.06292678
108.27815756
111.89594122
114.24038294
111.55925655
108.40918331
110.47764536
117.19857465
104.01180661
108.53901415
116.24452023
117.32750898
118.97844448
174.71921852
-50.29977559
69.46649687
-172.47257991
155.08030502
116.40836204
-138.18293074
103.23612351
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
1
1
1
1
5
1
7
7
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
1.09078142
1.79865269
2.14194386
1.60547164
1.16487525
1.48036433
1.08530346
1.33120582
1.08565011
1.08342230
115.05186072
104.16716637
2
3
3
1
5
1
1
7
7
95.68790466
82.26163300
107.28147536
115.52921217
122.83447466
121.73926623
121.47530880
85.21272811
109.37004587
-1.29309548
-122.13382908
61.48411045
-122.48015823
2.54182009
-175.88078465
Reaction 6 (H2O Addition)
01
C
C
C
C
C
C
H
H
H
H
H
C
H
S
O
H
H
Reaction 5 (H2O Addition)
01
C
H
S
H
O
H
C
H
C
H
H
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
A1
A2
A3
A4
A5
A6
A7
A8
A9
2
2
3
3
5
5
1
1
D1
D2
D3
D4
D5
D6
D7
D8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
A12
A13
1
2
3
4
5
1
2
3
5
6
4
12
12
12
15
15
B1
B2 1
B3 2
B4 3
B5 4
B6 2
B7 1
B8 2
B9 4
B10 5
B11 3
B12 4
B13 4
B14 4
B15 12
B16 12
1.39242070
1.39249311
1.39873197
1.39860331
1.38965698
1.08424430
1.08403460
1.08573194
1.08313936
1.08411689
1.49423944
1.09028348
1.79828556
1.61739360
1.17561394
0.97153264
119.80845608
120.59719482
119.22890460
120.17006798
120.04263380
120.23539897
119.75446152
118.88745778
119.74215418
119.12504538
111.26037646
121.68130130
107.96795048
A1
A2 1
A3 2
A4 3
A5 3
A6 6
A7 1
A8 3
A9 4
A10 2
A11 3
A12 3
A13 3
A14 4
A15 4
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
D13
D14
A14
A15
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
D13
D14
81.58289588
109.91378487
-0.43102031
-0.13282595
0.71510654
179.97480680
-179.43051088
-179.92397736
-178.24335556
179.93056774
179.83085613
10.79661499
149.65212200
-102.11373971
-127.68003888
122.66994456
H
O
H
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
3
2
5
B3 2
B4 1
B5 2
A2 1
A3 3
A4 1
D1
D2
D3
2
1
3
1
A1
A2 2
A3 2
A4 3
D1
D2
D3
1
2
1
2
A1
A2 1
A3 3
A4 1
D1
D2
D3
1.17191997
1.71475143
1.64450012
1.61682062
0.97144213
143.87237283
66.15992574
119.33921613
111.50060975
174.59101077
179.17272137
-54.37793466
Reaction 7 (H2O Addition)
Reaction 8 (H2O Addition)
01
C
C
H
H
H
O
H
S
H
O
H
01
C
S
O
H
O
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
1
2
2
2
1
6
1
1
1
10
B1
B2 1
B3 1
B4 1
B5 2
B6 1
B7 6
B8 6
B9 6
B10 1
A1
A2 3
A3 3
A4 5
A5 2
A6 2
A7 2
A8 2
A9 6
1.51060678
1.09208388
1.09623366
1.08756516
1.36698555
0.96713169
1.79537711
2.12601341
1.66613069
1.19989784
108.30095172
111.20327611
110.54145008
114.37433702
109.20373029
114.85054214
81.29559583
106.65854425
78.86291215
120.14102435
-118.75861990
169.93614413
-23.23994867
-142.40633694
121.22054211
114.31226953
119.23164284
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
B1
B2
B3
B4
B5
1.60125438
1.25451279
1.25617409
1.64141675
0.96844971
143.91265748
81.08325874
93.42604067
112.09596803
-176.27146736
-179.77554394
-119.72158327
Reaction 9 (H2O Addition)
01
O
C
S
H
O
H
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
Reaction 8 (H2O Addition)
01
O
C
S
D1
D2
D3
D4
D5
D6
D7
D8
1
1
3
1
5
1
2
3
2
5
B1
B2
B3
B4
B5
1.16161333
2.31115069
1.34598659
1.24876178
1.21730164
122.77946511
92.32819014
147.41493079
91.42671239
85.96673118
-179.64576783
-179.66288293
Reaction 10 (H2O Addition)
1
2
B1
B2 1
A1
01
C
C
C
C
S
H
H
H
H
O
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
1
2
3
1
1
2
3
4
1
10
10
B1
B2 1
B3 2
B4 2
B5 2
B6 1
B7 2
B8 3
B9 2
B10 1
B11 1
A1
A2 1
A3 3
A4 3
A5 5
A6 1
A7 2
A8 3
A9 2
A10 2
D1
D2
D3
D4
D5
D6
D7
D8
D9
1.46181898
1.46015815
1.34477022
1.73790453
1.07906490
1.08604021
1.08314159
1.07908017
1.91246862
0.96938809
1.32286184
109.69957096
114.93080097
111.27816270
125.29914585
119.13761225
122.27509585
129.08823966
89.52387383
111.48081220
63.93677881
1.31313110
2.03997675
154.45150183
-143.37425032
177.79403673
174.36570624
-111.58751100
109.64385961
3.01309568
B1
B2
B3
B4
B5
B6
1
2
3
1
1
2
3
4
3
10
4
B1
B2 1
B3 2
B4 2
B5 2
B6 1
B7 2
B8 3
B9 2
B10 3
B11 3
1.36679654
1.41961460
1.45795706
1.71835951
1.08180541
1.08129894
1.07883597
1.08526562
2.06569549
0.96844066
1.26194395
112.74425826
113.03444774
114.62748153
126.21124849
123.52628789
123.43613671
120.39574359
111.58056836
124.36752276
85.88905227
0.68624824
1.69774083
-176.93490576
-179.56023536
-164.89762285
-136.76051575
93.51777423
4.14413208
107.89007128
Reaction 12 (H2S Addition)
01
C
H
H
S
H
O
H
Reaction 11 (H2O Addition)
01
C
C
C
C
S
H
H
H
H
O
H
H
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
A1
A2 1
A3 3
A4 3
A5 5
A6 1
A7 2
A8 1
A9 2
A10 2
D1
D2
D3
D4
D5
D6
D7
D8
D9
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
D2
D3
D4
1
1
1
1
1
4
B1
B2
B3
B4
B5
B6
2
3
4
4
1
A1
A2
A3
A4
A5
2
3
5
6
D1
D2
D3
D4
A1
A2
A3
A4
A5
A6
A7
A8
2
2
1
3
5
5
5
D1
D2
D3
D4
D5
D6
D7
1.08969160
1.08158277
2.72782771
1.81723435
1.27225209
1.34534178
119.59886546
71.44720185
44.27884888
77.79311639
89.28049073
129.44192593
-115.20049569
-15.17264646
72.87591482
Reaction 13 (H2S Addition)
01
C
H
S
H
O
H
C
H
H
H
1
2
1
1
3
1
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
1
3
3
2
5
1
1
1
B1
B2
B3
B4
B5
B6
B7
B8
B9
A1
A2
A3
A4
A5
A6
A7
A8
D1
D2
D3
D4
D5
D6
D7
1.08207438
2.57783332
1.81778015
1.28222502
1.34561337
1.47745109
1.09277643
1.08893567
1.09839600
88.10031074
46.11917006
78.22584260
112.04740588
119.60992962
109.72974081
111.40474012
108.86128785
-113.72635989
-128.53515484
22.12735050
134.38770233
-140.86809741
-18.12246775
102.76938697
D2
D3
D4
D5
D6
D7
D8
D9
D10
Reaction 15 (H2S Addition)
01
C
H
H
H
C
C
H
H
H
O
H
S
H
Reaction 14 (H2S Addition)
01
C
H
S
H
O
H
C
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
1
2
1
1
3
1
7
7
7
10
10
10
B1
B2 1
B3 3
B4 3
B5 2
B6 5
B7 1
B8 1
B9 1
B10 7
B11 7
B12 7
1.08263566
2.58419939
1.81750188
1.28309019
1.34560587
1.48152946
1.10267814
1.09595158
1.52767534
1.09072160
1.09136697
1.09172499
87.63527427
46.23955852
78.32047736
112.93879552
120.16257597
105.86882580
106.87857733
115.68609744
111.25641026
110.11418597
110.80784736
-113.31573096
-128.09409136
21.36069627
134.07509410
104.74702722
-144.37231026
-18.84596679
58.83587233
179.08327593
-61.16090483
A1
A2 2
A3 2
A4 1
A5 3
A6 5
A7 5
A8 5
A9 1
A10 1
A11 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
1
1
1
1
5
6
6
6
5
10
10
12
B1
B2 2
B3 2
B4 4
B5 1
B6 5
B7 5
B8 5
B9 1
B10 5
B11 5
B12 10
1.08871620
1.10282556
1.08650026
1.49386005
1.48943356
1.08862981
1.08999815
1.09920820
1.28993680
1.06142789
2.73250815
1.34604967
107.78989122
110.33004286
111.79951531
119.31437751
110.39692426
111.39720920
108.27586628
121.27146952
102.99695157
78.40316862
121.50766783
118.44193043
116.95719952
174.35609944
-165.02339533
-41.56012878
76.66707489
160.49693221
60.80414988
83.87754436
-78.11837068
Reaction 16 (H2S Addition)
01
C
S
1
B1
A1
A2 3
A3 3
A4 4
A5 1
A6 1
A7 1
A8 6
A9 1
A10 1
A11 5
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
H
H
H
O
C
H
C
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
2
1
1
1
1
7
7
9
9
B2
B3
B4
B5
B6
B7
B8
B9
B10
1
2
2
2
6
1
1
7
7
A1
A2
A3
A4
A5
A6
A7
A8
A9
3
3
3
2
6
6
1
1
D1
D2
D3
D4
D5
D6
D7
D8
2.80957852
1.34557404
1.08168206
1.82662576
1.29462894
1.43370938
1.08483581
1.34318959
1.08491292
1.08290748
89.02384163
68.64251991
47.01191812
78.04367645
119.18841243
116.80966450
121.41733935
121.40438694
121.54869228
157.19643507
-87.86782341
-73.72861180
-133.62919208
7.90681073
-171.92589798
-1.24184038
179.67861776
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
1
2
1
1
1
1
7
7
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
2.80957852
1.34557404
1.08168206
1.82662576
1.29462894
1.43370938
1.08483581
1.34318959
1.08491292
1.08290748
89.02384163
68.64251991
47.01191812
78.04367645
119.18841243
116.80966450
121.41733935
121.40438694
121.54869228
157.19643507
-87.86782341
-73.72861180
-133.62919208
7.90681073
-171.92589798
-1.24184038
179.67861776
Reaction 18 (H2S Addition)
01
C
O
H
O
H
C
H
H
H
S
H
Reaction 17 (H2S Addition)
01
C
S
H
H
H
O
C
H
C
H
H
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
1
2
2
2
6
1
1
7
7
A1
A2
A3
A4
A5
A6
A7
A8
A9
3
3
3
2
6
6
1
1
D1
D2
D3
D4
D5
D6
D7
D8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
1
2
1
4
1
6
6
6
1
10
B1
B2 1
B3 2
B4 1
B5 4
B6 1
B7 1
B8 1
B9 4
B10 1
A1
A2 3
A3 2
A4 2
A5 4
A6 4
A7 4
A8 2
A9 4
D1
D2
D3
D4
D5
D6
D7
D8
A1
A2 1
A3 3
D1
D2
1.31297615
0.97080269
1.29997291
1.06808038
1.48990568
1.08592019
1.08752840
1.09920339
2.69771811
1.34548660
108.01892395
116.86327814
100.00928937
124.14841169
110.55562826
110.86126191
106.82092126
79.38950509
93.92842804
-14.74954915
128.02081375
155.72504653
35.50310735
158.44994891
-83.04422441
-116.26648536
79.79975255
Reaction 19 (H2S Addition)
01
O
C
S
H
O
1
2
3
2
B1
B2 1
B3 2
B4 1
H
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
5
B5 2
A4 1
D3
02
S
H
H
O
C
H
H
H
1.16161333
2.31115069
1.34598659
1.24876178
1.21730164
122.77946511
92.32819014
147.41493079
91.42671239
85.96673118
-179.64576783
-179.66288293
Reaction 20 (H Abstraction)
02
S
H
O
H
H
B1
B2
B3
B4
A1
A2
A3
D1
D2
1
2
3
1
B1
B2 1
B3 2
B4 3
A1
A2 1
A3 2
D1
D2
1.38468523
1.62057545
0.97256743
1.34351886
127.02134243
105.26482070
83.80557650
62.34538442
-106.99012005
B1
B2
B3
B4
B5
B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
1
2
3
1
5
5
5
B1
B2
B3
B4
B5
B6
B7
B1
B2
B3
B4
B5
B6
B7
2
2
1
4
4
4
A1
A2
A3
A4
A5
A6
3
2
1
1
1
D1
D2
D3
D4
D5
A1
A2
A3
A4
A5
A6
A7
A8
A9
2
3
3
3
1
2
2
2
D1
D2
D3
D4
D5
D6
D7
D8
1.34419961
1.45479920
2.74742624
1.39117885
1.09724632
1.09689110
1.10257753
92.49590712
87.84686134
109.15799405
112.28549688
113.55498664
105.12913349
13.01778789
136.12626705
-71.23263401
55.16747303
173.09417135
Reaction 23 (H Abstraction)
Reaction 21 (H Abstraction)
02
S
H
O
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
1
1
1
4
5
5
5
1
2
3
1
1
1
1.37943643
1.63381486
0.97110774
1.82751617
1.08910258
1.08946410
1.08768664
121.02632479
106.63963115
88.19592811
110.67989306
107.30333460
108.45346004
65.33490846
-106.22097855
100.64185973
-139.64326280
-20.84057573
Reaction 22 (H Abstraction)
A1
A2
A3
A4
A5
A6
1
2
3
3
3
D1
D2
D3
D4
D5
02
S
H
O
C
H
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
1
2
1
4
4
4
3
8
8
8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
1.43101528
1.42943649
1.82665054
1.09027225
1.08934430
1.08905715
1.39039535
1.09774314
1.09804405
1.10288802
147.24147867
90.43986584
107.24961938
109.65411538
111.11258757
114.73209711
112.69488768
113.46561240
105.52853797
-110.85287194
-158.84730031
1
3
1
1
1
2
3
3
3
D3
D4
D5
D6
D7
D8
-40.54998379
81.38174328
77.66926435
-84.68870487
41.53949818
158.96508598
Reaction 24 (H Abstraction)
02
O
C
H
C
H
H
H
S
H
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1
2
2
4
4
1
1
8
B1
B2
B3
B4
B5
B6
B7
B8
1
1
2
2
2
2
1
A1
A2
A3
A4
A5
A6
A7
3
1
1
4
4
2
D1
D2
D3
D4
D5
D6
1.28060775
1.09559864
1.37925396
1.08251751
1.08163638
1.22143397
2.83117292
1.34507960
117.84640957
122.54386553
119.94923259
120.61927724
112.22266191
111.69234761
92.95539430
-179.46547483
-1.06199791
178.08430852
175.02194777
172.66353081
-179.84752636
B1
B2
B3
B4
B5
B6
B7
B8
1
2
2
4
4
1
1
8
9
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
1.28491958
1.09663464
1.37437818
1.08262122
1.08180233
1.26284684
2.81465728
1.82624029
1.09127989
1.08912279
1.09124032
117.82005017
122.94965093
120.00783517
120.65147434
113.04802727
114.53109459
95.39492480
109.68263562
109.16683134
110.26094767
-178.60784817
-2.05041693
175.85509051
165.84180440
159.42702735
176.87518894
37.66252812
157.32635512
-82.24690021
Reaction 26 (H Abstraction)
02
C
H
H
H
C
O
H
S
H
Reaction 25 (H Abstraction)
02
O
C
H
C
H
H
H
S
C
H
H
H
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
1
1
2
2
2
2
1
8
8
8
A1
A2 3
A3 1
A4 1
A5 4
A6 4
A7 2
A8 1
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1
1
1
1
5
5
5
8
B1
B2
B3
B4
B5
B6
B7
B8
2
3
3
1
1
1
5
A1
A2
A3
A4
A5
A6
A7
2
4
3
6
6
1
D1
D2
D3
D4
D5
D6
A1
A2 2
A3 3
D1
D2
1.09285983
1.09177381
1.09286280
1.50423273
1.17923542
1.49504170
3.01734628
1.34472608
110.72431231
110.72368344
110.73083347
129.99429303
110.02014193
109.77322479
90.37034567
-118.94433484
-120.52670408
0.01019044
-180.00000000
-179.99732858
180.00000000
Reaction 27 (H Abstraction)
02
C
H
O
C
H
1
1
1
4
B1
B2 2
B3 3
B4 1
H
H
C
H
C
H
H
H
S
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
A12
A13
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
4
4
1
8
8
10
10
10
8
14
B5 1
B6 1
B7 3
B8 1
B9 1
B10 8
B11 8
B12 8
B13 1
B14 8
A4 3
A5 3
A6 4
A7 3
A8 3
A9 1
A10 1
A11 1
A12 3
A13 1
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
1.34171929
1.19385319
1.51057403
1.09362979
1.09210639
1.09421092
2.75270230
1.09111763
1.51095650
1.09401673
1.09600393
1.09408952
1.79452206
1.34617689
119.07340671
126.21592316
109.08571573
110.88150509
109.03270637
115.72880817
105.18404283
101.72964551
111.19055477
111.77846363
110.27580831
109.54340958
97.14726411
-179.84664905
-122.75984401
-0.78827826
120.79788576
-179.91975435
-127.84617836
-8.12062755
59.50970943
-179.98737720
-59.58764149
117.31818985
-66.27100694
1
1
1
1
3
1
7
7
7
10
10
B1
B2 2
B3 3
B4 3
B5 1
B6 5
B7 1
B8 1
B9 1
B10 7
B11 7
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
A1
A2
A3
A4
A5
10
1
14
14
14
B12
B13
B14
B15
B16
7
5
1
1
1
A11
A12
A13
A14
A15
1
7
5
5
5
D10
D11
D12
D13
D14
A1
A2 2
A3 2
A4 5
A5 3
A6 5
A7 5
A8 5
A9 1
A10 1
A11 1
A12 7
A13 5
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
1.28401690
1.83743859
1.92413156
1.39200497
1.34804105
1.51779464
1.09792751
1.09247091
1.53310162
1.09082838
1.09285789
1.09327468
2.74027251
1.08651785
1.08698310
1.08663810
100.49672243
91.77540660
113.33847887
96.60383564
109.78511408
Reaction 29 (H Abstraction)
02
C
H
S
H
O
H
C
H
H
C
H
H
H
S
H
Reaction 28 (H Abstraction)
02
C
H
S
H
O
H
C
H
H
C
H
H
H
C
H
H
H
A1
A2 2
A3 2
A4 5
A5 3
A6 5
A7 5
A8 5
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
A1
A2
A3
A4
A5
1
1
1
1
3
1
7
7
7
10
10
10
1
14
B1
B2 2
B3 3
B4 3
B5 1
B6 5
B7 1
B8 1
B9 1
B10 7
B11 7
B12 7
B13 5
B14 1
1.46664595
1.81756148
1.91431315
1.37037129
1.34774920
1.51255380
1.09954733
1.09211904
1.53195056
1.09079246
1.09228251
1.09253470
2.99108689
1.34461806
100.57953240
90.13791541
115.43903131
95.89326267
112.15417435
A6
A7
A8
A9
A10
A11
A12
A13
D1
D2
107.85654583
107.89153849
113.83341103
111.18423436
109.90874824
110.96690942
104.84859840
89.22988791
100.74273525
114.32517105
D2
D3
Reaction 32 (R Addition to Multiple Bond)
02
C
H
O
H
S
C
H
H
H
Reaction 30 (H Abstraction)
02
C
H
S
O
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1
1
1
3
3
6
6
6
B1
B2
B3
B4
B5
B6
B7
B8
2
3
1
1
3
3
3
A1
A2
A3
A4
A5
A6
A7
2
4
4
1
1
1
D1
D2
D3
D4
D5
D6
1.10610232
1.78655887
1.20010636
1.43659437
3.10775670
1.08235535
1.08337107
1.08336976
110.18896318
126.64856393
94.28478093
90.67153687
91.48617080
100.89263206
100.89081839
-180.00000000
0.00000000
0.00000000
0.00693452
119.26389364
-119.24930416
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
1
1
1
4
1
B1
B2
B3
B4
B5
2.05616891
1.08745098
1.32944119
0.97164771
1.64411920
80.92840077
110.46443283
107.81533412
125.62349457
100.47043138
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1
1
3
1
1
6
6
6
B1
B2
B3
B4
B5
B6
B7
B8
2
1
3
3
1
1
1
A1
A2
A3
A4
A5
A6
A7
2
4
5
3
3
3
D1
D2
D3
D4
D5
D6
1.08575744
1.34323684
0.97026639
1.65829303
2.33352562
1.08172270
1.08257750
1.08172037
110.56679198
107.20136517
124.13777696
99.92220580
102.35372855
94.54578138
99.20947367
171.33482287
8.99323752
-110.93215330
-168.89487860
-48.58800636
70.28335675
Reaction 33 (R Addition to Multiple Bond)
Reaction 31 (R Addition to Multiple Bond)
02
C
H
H
O
H
S
177.07429207
5.09247682
2
3
1
4
A1
A2 2
A3 3
A4 5
D1
D2
D3
02
C
H
S
H
O
C
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
1
1
1
1
1
6
6
6
9
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
1.08506964
1.66122722
1.87673168
1.34876450
2.31381675
1.08341740
1.08574359
1.48869298
1.09196020
1.10022364
1.09367189
122.64070970
2
3
3
5
1
1
1
6
6
6
A1
A2 2
A3 2
A4 3
A5 5
A6 5
A7 5
A8 1
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
94.23077058
123.58455281
99.97990035
98.83768467
93.23298522
105.56324380
111.85514965
110.34430339
111.35820683
162.25124736
157.88415191
-112.67002903
172.84388360
-70.67873835
49.38602176
67.93941202
-172.67637487
-54.38036989
A2
D1
Reaction 36 (R Addition to Multiple Bond)
02
C
O
S
C
H
H
H
Reaction 34 (R Addition to Multiple Bond)
02
C
C
H
H
H
S
O
H
H
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1
2
2
2
1
1
7
6
B1
B2
B3
B4
B5
B6
B7
B8
1
1
1
2
2
1
1
A1
A2
A3
A4
A5
A6
A7
3
4
3
6
2
7
D1
D2
D3
D4
D5
D6
1.49372289
1.08729115
1.09434835
1.09450227
1.66539738
1.31581309
0.99834934
1.89962646
111.15231564
109.54287857
109.11148925
124.55420476
114.15714215
105.36913802
84.82063081
120.87976765
117.18804933
-5.27084193
179.04807016
-167.88277996
-20.71672733
B1
B2
B3
A1
1
1
1
B1
B2 2
B3 3
1.78565321
1.16069312
1.59664649
105.13580154
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
D2
D3
D4
A1
A2 2
D1
1
1
1
4
4
4
B1
B2
B3
B4
B5
B6
2
2
1
1
1
A1
A2
A3
A4
A5
3
2
2
2
D1
D2
D3
D4
1.17158053
1.61828392
2.11871837
1.08124638
1.08345031
1.08345031
155.45769884
104.39190869
112.53821962
94.77580593
94.77580593
180.00000000
180.00000000
58.60273649
-58.60273649
Reaction 37 (R Addition to Multiple Bond)
02
C
H
S
H
O
H
C
H
C
H
H
H
Reaction 35 (R Addition to Multiple Bond)
02
C
H
O
S
166.07040528
180.00000000
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
1
1
1
1
3
1
7
7
9
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
1.08737825
2.32711178
1.90259796
1.36468128
1.34423770
1.38917352
1.08578691
1.48898565
1.09654452
1.09588957
1.09194416
90.84821526
86.13139032
104.53407822
89.52893117
117.24339310
116.85291456
123.74474050
110.74728370
111.11958320
2
3
3
1
5
1
1
7
7
7
A1
A2 2
A3 2
A4 5
A5 3
A6 5
A7 5
A8 1
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
111.97287393
95.49214913
117.77567876
-55.41169060
-111.61248856
17.78903281
-167.09299106
125.40734339
-116.10147223
4.50221047
O
H
C
H
H
C
H
H
H
Reaction 38 (Tautomerization)
01
C
H
S
O
H
B1
B2
B3
B4
A1
A2
A3
D1
D2
1
1
1
4
B1
B2 2
B3 3
B4 1
A1
A2 2
A3 3
D1
D2
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
1.09134728
1.69169644
1.25902131
1.36911194
126.21572947
112.29692829
79.53015109
180.00000000
0.00000000
Reaction 39 (Tautomerization)
01
C
S
O
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
1
1
3
1
5
5
5
B1
B2
B3
B4
B5
B6
B7
2
1
3
1
1
1
1.71565296
1.26511572
1.35394941
1.49376307
1.09292322
1.09188644
1.08917340
109.91449838
80.51887430
122.18087363
109.54518382
110.14976965
110.00428002
0.03502534
-179.67609045
116.49499242
-125.73087918
-4.16341740
Reaction 40 (Tautomerization)
01
C
S
1
B1
2
2
3
3
3
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
1
3
1
5
5
5
8
8
8
B2
B3
B4
B5
B6
B7
B8
B9
B10
1.71654565
1.26621316
1.35604563
1.49820162
1.09757901
1.09331079
1.53020946
1.09204080
1.09191253
1.09206599
109.86049245
80.39569257
121.63102006
105.80789959
106.98615181
115.17566972
110.19470349
111.14744209
111.11783259
-0.21602671
178.44187920
-87.70774888
25.35274533
150.40376100
178.83805632
-61.31091815
58.90915053
2
1
3
1
1
1
5
5
5
A1
A2
A3
A4
A5
A6
A7
A8
A9
2
2
3
3
3
1
1
1
D1
D2
D3
D4
D5
D6
D7
D8
D2
D3
D4
D5
D6
Z-Matrices for Molecules
01
S
H
H
B1
B2
A1
01
S
H
C
H
H
H
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
01
S
C
H
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
1
1
B1
B2 2
A1
1.34327993
1.34327993
92.58329996
1
1
3
3
3
B1
B2
B3
B4
B5
2
1
1
1
A1
A2 2
A3 2
A4 2
D1
D2
D3
1.34383796
1.83186600
1.09011110
1.08923069
1.08923069
97.09044649
106.02458786
111.27496891
111.27496891
180.00000000
-61.86427348
61.86427348
1
2
2
1
2
6
6
6
B1
B2
B3
B4
B5
B6
B7
B8
1.84053942
1.09238710
1.09119687
1.34468713
1.52495257
1.09312266
1.09511375
1.09182844
103.76609343
108.65066099
96.83197082
114.35965187
111.21618781
110.30998782
111.06606383
-113.79907940
1
1
2
1
2
2
2
62.42213671
-62.92877011
63.33941833
-177.11626126
-56.84849601
A1
A2
A3
A4
A5
A6
A7
3
4
5
1
1
1
D1
D2
D3
D4
D5
D6
01
C
H
H
H
C
H
H
C
H
H
S
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
01
S
H
C
H
C
H
C
H
H
1
1
1
1
5
5
5
8
8
8
11
B1
B2 2
B3 2
B4 2
B5 1
B6 1
B7 1
B8 5
B9 5
B10 5
B11 8
A1
A2 3
A3 4
A4 2
A5 2
A6 2
A7 1
A8 1
A9 1
A10 5
D1
D2
D3
D4
D5
D6
D7
D8
D9
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1.09296552
1.09427295
1.09423755
1.53302284
1.09555313
1.09395255
1.52840858
1.09215111
1.09345327
1.83917085
1.34460303
107.66141600
107.65336841
110.95296286
109.62637827
110.19348596
112.29767774
111.28472530
110.55368506
114.64658137
96.87039863
115.84020434
121.99793697
57.88209488
-58.80671228
179.43674741
-58.70398120
60.20350086
177.27783367
63.42757476
1
1
3
3
5
5
7
7
B1
B2
B3
B4
B5
B6
B7
B8
2
1
1
3
3
5
5
2
2
1
1
3
3
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
A1
A2
A3
A4
A5
A6
A7
A8
D1
D2
D3
D4
D5
D6
D7
01
C
H
H
S
B1
B2
B3
A1
A2
D1
01
C
H
C
H
S
H
H
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
7
B9 5
A8 3
D7
1.34532355
1.78052170
1.08571181
1.33181721
1.08762779
1.50011270
1.09539567
1.09580977
1.09237416
97.31310735
115.85277913
122.48313340
118.86048255
124.35969445
110.89890200
110.98590451
111.74837446
-46.86082688
138.77175358
-6.10052339
173.34810986
123.63308977
-117.94027294
2.68220294
1
1
1
01
C
C
H
S
H
H
C
H
H
H
B1
B2 2
B3 3
A1
A2 2
D1
1.08986346
1.08985705
1.61084700
115.92565035
122.03997793
180.00000000
1
1
3
3
1
1
B1
B2
B3
B4
B5
B6
1.08911236
1.49291678
1.09300816
1.61980609
1.09733033
1.09697723
111.78326121
114.81232591
126.45725204
109.77445206
109.77061696
-179.94981833
D2
D3
D4
2
1
1
3
3
A1
A2
A3
A4
A5
2
2
5
5
D1
D2
D3
D4
B1
B2
B3
B4
B5
B6
B7
B8
B9
A1
A2
A3
A4
A5
A6
A7
A8
D1
D2
D3
D4
D5
D6
D7
01
C
H
H
C
H
C
H
S
B1
B2
B3
B4
B5
B6
B7
A1
A2
0.08504453
-121.81265346
121.94294055
1
2
2
1
1
1
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
1
1
2
2
2
1
1
1
A1
A2
A3
A4
A5
A6
A7
A8
3
4
4
4
2
2
2
D1
D2
D3
D4
D5
D6
D7
2
3
1
1
4
4
A1
A2
A3
A4
A5
A6
2
3
3
1
1
D1
D2
D3
D4
D5
1.49928079
1.09327780
1.62101959
1.10069884
1.10021014
1.52446846
1.09248638
1.09173182
1.09173185
113.68135958
127.79107438
106.54145479
106.58648058
117.20947132
110.14116314
111.21517133
111.20612761
-179.99577006
-124.75872528
124.70098749
-0.03955432
-179.97522250
-59.74443602
59.81639596
1
1
1
4
4
6
6
B1
B2
B3
B4
B5
B6
B7
1.08537379
1.08343568
1.34113138
1.08544944
1.44806876
1.09276072
1.63104353
116.94777260
121.70641804
A3
A4
A5
A6
D1
D2
D3
D4
D5
01
C
C
C
C
C
C
H
H
H
H
H
C
H
S
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
A12
D1
D2
D3
D4
121.00766131
122.16993040
115.20326215
125.48088108
180.00000000
0.00000000
180.00000000
0.00000000
180.00000000
1
2
3
4
5
1
2
4
5
6
3
12
12
B1
B2 1
B3 2
B4 3
B5 4
B6 2
B7 1
B8 3
B9 4
B10 5
B11 2
B12 3
B13 3
1.38583731
1.40631088
1.40609500
1.38987996
1.39345706
1.08398609
1.08322962
1.08512018
1.08378357
1.08423243
1.45923514
1.09226383
1.63252372
120.31139208
118.85050477
120.73741607
119.74311405
119.88992438
120.99897969
119.21083836
120.07200812
119.96407636
122.56927572
113.69391049
128.27241311
-0.00000000
0.00435527
-0.00380186
-179.99658450
01
C
C
C
C
S
H
H
H
H
A1
A2 1
A3 2
A4 3
A5 3
A6 6
A7 2
A8 3
A9 4
A10 1
A11 2
A12 2
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
01
C
H
H
S
H
O
H
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
D2
D3
D4
1
2
3
4
1
2
3
4
B1
B2
B3
B4
B5
B6
B7
B8
1
2
3
2
1
2
3
A1
A2
A3
A4
A5
A6
A7
1
2
3
5
1
2
D1
D2
D3
D4
D5
D6
2
2
4
4
1
A1
A2
A3
A4
A5
3
3
3
6
D1
D2
D3
D4
1.36629669
1.42594200
1.36629669
1.72748369
1.07892407
1.08214933
1.08214933
1.07892407
112.67431284
112.67431284
111.46777715
128.49773050
123.34875370
123.97693347
128.49773050
0.00000000
0.00000000
180.00000000
180.00000000
180.00000000
180.00000000
1
1
1
1
1
4
B1
B2
B3
B4
B5
B6
1.08805014
1.09631959
1.84497563
1.92992799
1.40086701
1.34441019
108.97259782
109.40309483
96.91328376
114.50396765
96.10911750
-112.84085378
-100.66556114
-123.90770400
62.65185119
01
C
H
S
H
O
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
A1
A2
A3
A4
A5
A6
A7
A8
D1
D2
D3
D4
D5
D6
D7
01
C
H
S
H
O
H
C
H
H
C
H
H
H
B1
B2
1
1
1
1
3
1
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
2
3
3
1
5
1
1
1
A1
A2
A3
A4
A5
A6
A7
A8
2
2
5
3
5
5
5
D1
D2
D3
D4
D5
D6
D7
1.08942056
1.86212814
1.93258637
1.40618355
1.34374699
1.52450124
1.09213032
1.09216321
1.09430327
107.43710284
95.69966608
112.16537584
95.43657376
112.90485694
111.56130222
108.84778614
110.84308365
139.38757587
115.43728334
56.61660460
-122.50257855
-174.28312724
-54.12186971
64.87864161
1
1
1
1
3
1
7
7
7
10
10
10
B1
B2 2
B3 3
B4 3
B5 1
B6 5
B7 1
B8 1
B9 1
B10 7
B11 7
B12 7
1.09048552
1.86078422
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
01
C
C
H
H
H
C
H
H
H
O
H
S
H
A1
A2 2
A3 2
A4 5
A5 3
A6 5
A7 5
A8 5
A9 1
A10 1
A11 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
A1
1.93273142
1.40770086
1.34378990
1.53113914
1.09694377
1.09434082
1.53133853
1.09139945
1.09258576
1.09395990
107.60419848
94.96540335
111.97160606
95.39442757
113.24310404
108.55913773
108.92222458
112.26110141
110.80571403
110.75959819
111.12375186
138.92696503
115.38946402
56.37650528
-122.54880092
63.22114369
178.96904156
-58.65623844
56.43656289
176.81078747
-63.38460230
1
2
2
2
1
6
6
6
1
10
1
12
B1
B2 1
B3 1
B4 1
B5 2
B6 1
B7 1
B8 1
B9 6
B10 1
B11 10
B12 1
1.53155226
1.09213292
1.09325617
1.09262086
1.52413017
1.09114207
1.09006910
1.09393745
1.41363530
0.96410453
1.88012147
1.34385195
111.66641592
A1
A2 3
A3 4
A4 3
A5 2
A6 2
A7 2
A8 2
A9 6
A10 6
A11 10
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
D1
D2
01
C
C
H
C
H
S
H
O
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
110.92539111
108.69601286
112.21955855
110.38629665
110.99918963
109.09823233
106.06456084
107.85672850
110.27459465
95.37272693
120.93715318
118.97780146
1
1
2
4
4
6
4
8
1
2
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
1.32874062
1.08257034
1.49802600
1.09908645
1.86827249
1.34470065
1.40218310
0.96269212
1.08354032
1.08519199
121.18039583
124.22705167
109.62845066
110.97205581
95.49487208
110.23340839
107.84054077
120.94524817
121.15497285
-0.51648923
128.37483887
-120.21786673
55.82968456
2
1
2
2
4
2
4
2
1
01
C
C
C
C
C
C
H
H
H
H
H
C
H
S
H
O
H
A1
A2
A3
A4
A5
A6
A7
A8
A9
3
1
1
2
1
2
4
4
D1
D2
D3
D4
D5
D6
D7
D8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
A11
A12
A13
A14
01
O
H
C
H
O
H
S
H
1
2
3
4
1
1
2
4
5
6
3
12
12
14
12
16
B1
B2 1
B3 2
B4 3
B5 2
B6 6
B7 1
B8 3
B9 4
B10 1
B11 2
B12 3
B13 3
B14 12
B15 3
B16 12
A1
A2 1
A3 2
A4 3
A5 5
A6 6
A7 2
A8 3
A9 2
A10 1
A11 2
A12 2
A13 3
A14 2
A15 3
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
D13
D14
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
1.39399594
1.39607107
1.39818637
1.39030253
1.39194203
1.08437641
1.08184769
1.08511940
1.08420219
1.08415375
1.51035911
1.09699029
1.86888724
1.34448819
1.40568942
0.96297390
120.16622158
119.27166693
120.47648243
120.35772174
120.05967823
120.62856761
119.67029049
119.77928758
120.23801717
120.79933238
109.65327719
112.51388146
95.76510392
109.59381567
1
1
3
3
5
3
7
B1
B2
B3
B4
B5
B6
B7
2
1
1
3
1
3
2
2
1
5
1
B1
B2
B3
B4
B5
B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
01
O
H
C
O
H
S
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
A1
A2
A3
A4
A5
A6
A7
A8
A9
D1
D2
D3
D4
D5
D6
D7
D8
0.96450733
1.40087093
1.09209024
1.39127132
0.96695303
1.84944195
1.34349025
107.18581139
112.43232807
112.92332347
107.16603098
102.98249434
94.45879714
60.00611100
-59.32426671
-61.62227888
-122.76729069
177.78436734
1
1
3
4
3
6
3
8
8
8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
0.96573042
1.39751830
1.40993358
0.96519364
1.86693523
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01
O
H
C
O
H
S
H
C
H
H
C
H
H
H
2
1
3
1
3
1
3
3
3
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A2
A3
A4
A5
A6
A7
A8
A9
2
1
4
1
4
1
1
1
D1
D2
D3
D4
D5
D6
D7
D8
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
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A2
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01
C
C
C
C
S
H
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H
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O
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1
1
3
4
3
6
3
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8
8
11
11
11
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B2 2
B3 1
B4 3
B5 1
B6 3
B7 1
B8 3
B9 3
B10 3
B11 8
B12 8
B13 8
A1
A2 2
A3 1
A4 4
A5 1
A6 4
A7 1
A8 1
A9 1
A10 3
A11 3
A12 3
D1
D2
D3
D4
D5
D6
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D8
D9
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D11
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A2 1
A3 2
A4 3
A5 5
A6 1
A7 2
A8 3
A9 2
D1
D2
D3
D4
D5
D6
D7
D8
0.96569020
1.39907526
1.40973471
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1.87029931
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110.83837669
110.94107916
1
2
3
4
1
2
3
4
1
10
B1
B2 1
B3 2
B4 3
B5 2
B6 1
B7 2
B8 3
B9 2
B10 1
H
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B3
B4
B5
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B11 1
A10 10
D9
1.54347599
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1
2
3
1
1
2
3
4
3
10
4
B1
B2 1
B3 2
B4 2
B5 2
B6 1
B7 2
B8 3
B9 2
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1.33573441
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0.96434332
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
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01
C
H
S
O
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B2
B3
B4
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A2
A3
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D2
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A2 1
A3 3
A4 3
A5 5
A6 1
A7 2
A8 1
A9 2
A10 2
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D2
D3
D4
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D6
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D8
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01
C
H
S
O
H
B1
B2
B3
B4
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A2
A3
D1
D2
1.08892949
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1
1
1
3
B1
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A1
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D1
D2
A1
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D1
D2
1.10576453
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1
1
1
4
B1
B2 2
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1.08921775
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123.57937810
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0.02606869
01
C
O
C
H
H
S
H
H
B1
B2
B3
B4
B5
B6
B7
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A3
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C
C
H
H
H
S
O
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B2
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B6
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A3
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D4
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1
1
3
3
1
6
3
B1
B2
B3
B4
B5
B6
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2
1
1
2
1
1
A1
A2
A3
A4
A5
A6
2
2
3
2
2
D1
D2
D3
D4
D5
1.19774937
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1
2
2
1
1
1
2
B1
B2
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1.49848588
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1
1
2
2
2
1
A1
A2
A3
A4
A5
A6
3
3
3
6
7
D1
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01
C
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C
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1
3
3
1
6
3
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8
8
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1
1
2
1
1
3
3
3
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2
2
3
2
2
1
1
1
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1
2
1
2
2
2
2
2
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A2
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A8
A9
3
4
5
1
1
1
6
6
D1
D2
D3
D4
D5
D6
D7
D8
1.19806571
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1
2
2
1
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6
6
6
1
1
B1
B2
B3
B4
B5
B6
B7
B8
B9
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B2
B3
B4
B5
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01
C
S
O
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1.50664712
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1
2
3
2
5
B1
B2
B3
B4
B5
O
H
B1
B2
B3
B4
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01
C
O
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1
2
1
2
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A2 1
A3 3
A4 1
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1.19656630
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1
1
3
B1
B2 2
B3 1
A1
A2 2
D1
01
C
H
H
S
H
O
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D1
D2
D3
D4
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1
5
B4 3
B5 1
A3 2
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D2
D3
1.56640000
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1
B1
B2 2
A1
1.15621300
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1
1
1
1
1
4
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
1.09019552
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2
2
4
4
1
4
4
4
A1
A2
A3
A4
A5
A6
A7
A8
3
3
3
6
1
1
1
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01
C
H
H
S
O
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01
C
H
H
S
O
C
H
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
-48.93696672
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1
1
1
1
4
5
7
7
7
B1
B2
B3
B4
B5
B6
B7
B8
B9
2
2
4
1
1
5
5
5
A1
A2
A3
A4
A5
A6
A7
A8
3
3
5
4
1
1
1
D1
D2
D3
D4
D5
D6
D7
1.08774372
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1
1
1
1
5
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6
6
4
10
10
10
B1
B2 2
B3 2
B4 4
B5 1
B6 5
B7 5
B8 5
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B10 4
B11 4
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1.09022801
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B7
B8
B9
B10
B11
B12
A1
A2
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A4
A5
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A8
A9
A10
A11
D1
D2
D3
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D8
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01
C
H
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H
H
S
O
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A2 3
A3 3
A4 4
A5 1
A6 1
A7 1
A8 5
A9 1
A10 1
A11 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
B1
B2
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B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
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01
C
H
S
1.09503508
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1
2
3
3
3
1
1
B1
B2
B3
B4
B5
B6
B7
1
2
2
2
3
7
A1
A2
A3
A4
A5
A6
B1
B2 2
A1
1.10928694
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1
1
1
1
1
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D1
D2
D3
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O
C
H
H
H
B1
B2
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A1
A2
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D2
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01
C
C
H
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C
H
H
H
O
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B1
B2
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A2
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D1
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1
4
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5
B3
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3
1
4
4
4
A2
A3
A4
A5
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2
3
1
1
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D1
D2
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1
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B1
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B10
2.75329822
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D4
D5
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01
C
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H
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1
1
1
2
1
1
1
6
10
A1
A2
A3
A4
A5
A6
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3
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2
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D1
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D1
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01
C
H
H
H
C
H
-113.88031869
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1
1
3
4
4
4
1
8
8
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B1
B2
B3
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B5
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B8
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2
1
3
3
3
3
1
1
1
A1
A2
A3
A4
A5
A6
A7
A8
A9
2
1
1
1
4
3
3
3
D1
D2
D3
D4
D5
D6
D7
D8
2
2
2
1
A1
A2 3
A3 4
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D1
D2
D3
1.64248402
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1
1
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B1
B2
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H
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O
C
H
H
H
B1
B2
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B11
B12
B13
A1
A2
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A10
A11
A12
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
5
5
8
9
9
11
11
11
B6 1
B7 1
B8 5
B9 8
B10 8
B11 9
B12 9
B13 9
1.09089522
1.09224963
1.09461446
1.52563704
1.09172195
1.09048584
1.83226268
1.79984659
1.20507184
1.51414242
1.09357624
1.09037606
1.09168131
108.59397833
108.02269372
110.55578824
111.83022151
111.23531962
113.63925323
99.88432959
122.92527716
113.52319123
108.32216926
112.75605582
108.74781639
117.13455537
120.31258919
-179.34406889
-57.69901315
61.95733941
-83.50223357
-1.80796286
177.61896077
-108.90015306
11.76959408
134.09866230
A5 2
A6 2
A7 1
A8 5
A9 5
A10 8
A11 8
A12 8
D4
D5
D6
D7
D8
D9
D10
D11
H
H
S
H
O
Z-Matrices for Radicals
02
S
H
B1
02
S
C
H
H
H
B1
B2
B3
B4
A1
A2
A3
D1
D2
02
S
C
H
H
C
H
H
H
B1
B2
B3
B4
B5
B6
B7
A1
A2
A3
A4
A5
A6
D1
D2
D3
D4
D5
02
C
1
B1
1.34805900
1
2
2
2
B1
B2 1
B3 1
B4 1
A1
A2 3
A3 4
D1
D2
1.80509576
1.09426097
1.09426071
1.08936108
108.46557032
108.46546693
112.72803708
115.62679808
122.18654500
1
2
2
2
5
5
5
B1
B2
B3
B4
B5
B6
B7
1.81255108
1.09664263
1.09673222
1.52576377
1.09500828
1.09200972
1.09200626
105.99738868
105.92913178
115.64533741
110.46961552
110.99351663
110.99466025
111.39208323
124.26821945
-179.90021959
-59.84034334
60.04987358
B1
B2
B3
B4
B5
A1
A2
A3
A4
D1
D2
D3
02
C
H
S
H
O
C
H
H
H
1
1
1
2
2
2
A1
A2
A3
A4
A5
A6
3
4
1
1
1
D1
D2
D3
D4
D5
B1
B2
B3
B4
B5
B6
B7
B8
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
02
O
1
1
1
1
1
B1
B2
B3
B4
B5
2
2
4
4
A1
A2 3
A3 3
A4 3
D1
D2
D3
2
3
3
5
1
1
1
A1
A2
A3
A4
A5
A6
A7
D1
D2
D3
D4
D5
D6
1.09311270
1.10418734
1.80432166
1.93234767
1.40152428
107.00923608
108.65389903
95.89079776
116.85169040
-111.51684524
-104.96425419
-124.91212420
1
1
1
1
1
6
6
6
B1
B2
B3
B4
B5
B6
B7
B8
1.10516701
1.82033617
1.93948424
1.40907052
1.52674909
1.08976380
1.09242484
1.09139813
101.58746116
92.09751648
114.41452446
107.42670124
111.02676659
108.65277919
110.13086487
102.00462725
119.74884160
-126.36444999
-174.35188631
-53.94871313
64.46054301
2
2
3
5
5
5
H
C
S
C
H
H
C
H
H
H
H
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
02
C
S
H
O
H
C
H
H
C
H
H
H
B1
B2
B3
1
1
3
3
5
5
5
8
8
8
3
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
2
1
1
3
3
3
5
5
5
1
A1
A2 2
A3 4
A4 1
A5 1
A6 1
A7 3
A8 3
A9 3
A10 5
D1
D2
D3
D4
D5
D6
D7
D8
D9
0.96287373
1.41030467
1.81965474
1.53363169
1.09255081
1.09509612
1.52994027
1.09245987
1.09101777
1.09425772
1.10622942
108.17732204
114.30372077
107.94996462
108.31165155
106.40379253
113.74442064
110.60354207
110.60075796
111.17425984
110.83139841
-35.44395080
-128.37936412
-172.09316979
-56.81572264
64.22507928
-175.35633369
-55.32572106
65.03202322
-118.56273288
1
1
1
2
1
6
6
6
9
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
1.75965920
1.90549204
1.36854001
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
02
C
H
S
H
O
H
C
H
C
H
H
H
2
2
1
4
1
1
1
6
6
6
A1
A2 3
A3 4
A4 2
A5 4
A6 4
A7 4
A8 1
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
A1
A2
A3
A4
A5
A6
A7
1.36335363
1.49506567
1.09589433
1.09212416
1.54320152
1.09213059
1.09314338
1.09338828
90.82784207
118.27894753
101.06512633
113.81308483
107.77239152
108.72197502
113.74015213
110.57572707
110.56979349
111.10904662
-8.93359654
74.21533050
157.78531283
48.08335058
164.23880239
-73.01006545
57.80350341
177.72340540
-62.54702647
1
1
1
1
3
1
7
7
9
9
9
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
1.09651509
1.92971600
1.92786065
1.40080777
1.34405244
1.46779444
1.08381588
1.48866792
1.09089885
1.10242750
1.09343151
99.79478914
89.95268401
110.59661434
95.13598490
111.00814141
116.17757267
122.85609902
2
3
3
1
5
1
1
7
7
7
A1
A2 2
A3 2
A4 5
A5 3
A6 5
A7 5
A8 1
A9 1
A10 1
D1
D2
D3
D4
D5
D6
D7
D8
D9
A8
A9
A10
D1
D2
D3
D4
D5
D6
D7
D8
D9
02
C
H
O
S
B1
B2
B3
A1
A2
D1
02
C
S
O
C
H
H
H
B1
B2
B3
B4
B5
B6
A1
A2
A3
A4
A5
D1
D2
D3
D4
111.22952465
111.92710770
110.86619833
98.80189333
118.73945357
-65.23718839
-123.74529842
-162.83679645
30.47561147
-33.20694160
86.76406766
-154.68969690
1
1
1
B1
B2 2
B3 3
A1
A2 2
D1
A1
A2
A3
A4
A5
D1
D2
D3
D4
1.10305555
1.20344910
1.77015761
124.75942846
119.12039378
180.00000000
1
1
1
4
4
4
B1
B2
B3
B4
B5
B6
1.76710483
1.21182675
1.50171056
1.09300517
1.09300810
1.09082047
114.19303286
125.24702100
109.80874420
109.80654648
109.53195883
179.99678040
120.78258115
-120.75664928
0.01171873
2
3
1
1
1
2
3
3
3