Supplementary material
MultiSpecies-MultiChannel (MSMC)
An ab initio Parallel Thermodynamic and Kinetic Code for
Complex Chemical Systems
Minh v. Duong,[a] Hieu T. Nguyen,[a] Nghia Truong,[a] Thong Le[a] and Lam K. Huynh[a,b]*
[a] Institute
[b]
for Computational Science and Technology, Ho Chi Minh City, Vietnam
International University, Vietnam National University at Ho Chi Minh City, Vietnam
1
Contents
Text S1: Sum and Density of States (DOS) Treatment................................................................................. 3
External Molecular Rotor ...................................................................................................................... 3
Hindered Internal Rotation ................................................................................................................... 4
Optical Isomer ....................................................................................................................................... 7
Thermodynamic Properties ................................................................................................................... 7
Text S2. Implementation of Microcanonical Rate Coefficients, k(E)........................................................... 9
Rice–Ramsperger–Kassel–Marcus (RRKM)......................................................................................... 9
Inverse Laplace Transform (ILT) .......................................................................................................... 9
Tunneling Correction .......................................................................................................................... 10
Text S3. Collision models ........................................................................................................................... 11
Text S4. Graphical User Interface (GUI) .................................................................................................... 12
Table S1. Comparison of Calculated Thermodynamic Properties[a] of Selected Species with Available
Literature Data (ATcT = Active Thermochemical Tables,25,26 values collected from Burcat’s online
database27). .................................................................................................................................................. 16
Table S2: Geometries, Energies (at 0 K) and Frequencies for all Species for the Thermodynamic Test
Cases Calculated at the Composite Method CBS-QB3. ............................................................................. 19
Table S3: Geometries, Energies (at 0 K) and Frequencies for all Species for the C2H2 + OH Test Case
Calculated at the Composite Method CBS-QB3. ........................................................................................ 27
Table S4: Geometries, Energies (at 0 K) and Frequencies for all Species for the C2H5O Decomposition
Test Case Calculated at the Composite Method CBS-QB3. ....................................................................... 28
Table S5: Thermodynamic Data for Species in the NASA format ............................................................. 31
Table S6: An Example of MSMC Input File (File name: C2H5O.minp) .................................................... 34
References ................................................................................................................................................... 38
2
Text S1: Sum and Density of States (DOS) Treatment
Within MSMC, it is assumed that the rotational DOS is separable from vibrational DOS. The
coupling of rovibrational DOS due to anharmonicity has not been taken into account in this
current version of MSMC. To calculate the rovibrational DOS, we first use Beyer-Swinehart's
algorithm4 to directly count the DOS for harmonic oscillators; the harmonic DOS is then coupled
with the rotational one (including external and hindered internal rotation, if any) using
Stein&Rabinovitch’s algorithm5 to obtain the final rovibrational DOS. We choose the energy-grain
of 1 cm-1 to perform the direct counting, making the error negligible. Explicit treatments for
external and hindered internal rotors are described in detail below.
External Molecular Rotor
External molecular rotors6-10 are treated as rigid 3-D quantum rotors. Such a treatment is
analytically solvable for the spherical and symmetric cases. The rotor types (e.g. spherical,
symmetric, asymmetric, etc.) can be determined according to the three principal moments of
inertia of the considered molecule (assuming I C  I B  I A  0 or A  B  C  0 ). In the case of an
asymmetric top ( I A  I B  I C ). we approximate the top as a quasi-symmetric one (either oblate
or prolate) depending on the magnitudes of the principal moments of inertia. This approximation
is expected to have only a minor effect on the contribution to the partition function but is much
easier to implement and compute when compared to the explicit treatment of an asymmetric
top.11 Details about the properties of different types of rotors treated in MSMC are presented as
follows.
Table 1. Properties of different types of rotors treated in MSMC
Type of rotor
Criteria
I C  I B  I A
Linear
IC  I B  I A  0
with J  0,1,2,...
E ( J )  BJ ( J  1)
CBA
with J  0,1,2,...
IC  I B  I A  0
E( J , K )  BJ ( J  1)  (A B)K2
CB A
J  0,1,2,...;K  0, 1, 2,..,  J
IC  I B  I A  0
E( J , K )  BJ ( J  1)  (C B)K2
CBA
J  0,1,2,...;K  0, 1, 2,..,  J
C  B  A
Spherical top
Prolate symmetric
top
Oblate symmetric
top
where A 
Energy, E
E ( J )  BJ ( J  1)
2
2I A
,B
2
2I B
and C 
Degeneracy, g
g  2J  1
g  (2J  1)2
2(2 J  1),if K  0
g
2 J  1,if K  0
2(2 J  1),if K  0
g
2 J  1,if K  0
2
2IC
are rotational constants
The symmetry number is introduced to take into account the over-counting of forbidden
states, due to the Pauli exclusion principle, when solving the corresponding Schrödinger
equation.12 According to the Pauli principle, the overall molecular wave function must be
3
symmetric or anti-symmetric with respect to the interchange of two identical atoms of the
molecule, depending on whether they are bosons or fermions. A detailed discussion is beyond
the scope of this paper, but can be found in the work of Philip Bunker. 13 In MSMC, the external
symmetry number is pre-determined based on the symmetry point group of the species of
interest14 and this information has to be provided manually by users. The automatic parsing GUI
from the electronic structure calculation results is under construction for different types of
molecules.
Hindered Internal Rotation
The 1-D Schrödinger equation for a hindered internal rotor (HIR) is given as follows
Hˆ  hir  E  hir


1
d2
 2  V ( )   hir  E  hir ,

 2 I red d

(1)
where E is the energy; V   is the hindrance potential which can be directly computed as a
function of torsional angles,  , from ab initio investigations; I red is the reduced moment of
inertia for the considered hindered internal rotation. In MSMC program, the reduced moment of
inertia is approximated by I (3,2) which is computed according to East and Radom1 on the basis of
the original work by Kilpatrick and Pitzer 2. We adopted the notation I (m,n) , where m denotes the
reduction level for a rotor with respect to a fixed reference frame, while n indicates the coupling
reduction. Note that that the couplings among internal rotation modes and between internal and
external rotational modes are assumed negligible, i.e. the total kinetic Hamiltonian is separable.
In order to solve the HIR equation (Eq. (1)), we cast it into a Mathieu-type equation by
representing the potential as a Fourier series
V ( ) 
L
ce 
il
l  L
l
(2)
in which L is the cut-off number depending on the nature of the potential. The default value of L
is 20, which can capture complicated potentials. The task of determining complex coefficients,
cl  , is carried out with the Filon’s quadrature method3 to perform the oscillating integrals. The
detailed derivations can be found in the supplementary document.
V ( ) 
L
ce 
il
l  L
l
(3)
Where cl  are complex coefficients and satisfy c l  c*l . So to fully describe the potential,
we only need to calculate the cl  for l  0 . Let
cl  al  ibl , l  0; al , bl 
Taking the integral
4
(4)
2
 V ( )e d 
im
2
L

 ce e
il
0 l  L
0
im
l
d
(5)
 2 c m  2 (am  ibm ), m  0

Note that
 e
ik
d  2 (k ) and eix  cosx  i sinx . So we have

2
1
am 
2
 V ( ) cos(m )d
0
1
bm  
2
(6)
2
 V ( )sin(m )d , m  0
0
To compute the integrals we use quadrature method, which is as follows. Assume that the potential
are scanned at N  2K  1 points and labelled as 0,1, 2,..., N  1 . Then
2

(7)
i  ih, h 
 , i  0,1, 2,...N  1;V (i)  V (i )
N 1
K
We then divide the whole range into 3-point segments namely (0 ,1 , 2 ), ( 2 ,3 , 4 ) and so
on. On each 3-point segment, we assume the potential is a quadrature
Vk ( )  Ak  2  Bk   Ck , k  1, 2,3,...K ; h    h
(8)
and
V (2k  2)  Vk (  h)  Ak h 2  Bk h  Ck
V (2k  1)  Vk (  0)  Ck
(9)
V (2k )  Vk (  h)  Ak h  Bk h  Ck
2
so
V (2k )  V (2k  2)  2V (2k  1)
2h 2
V (2k )  V (2k  2)
Bk 
2h
Ck  V (2k  1)
Then the integrals for am and bm are given by
Ak 
1
am 
2
h
K
  V ( ) cos[m(
k
k 1  h
1
bm  
2
K
2k
  )]d
(11)
h
  V ( )sin[m(
k 1  h
k
Then
5
(10)
2k
  )]d 
1
am 
2
K
h
  V ( ) cos(m
k 1  h
k
2k
) cos(m )  sin(m 2 k )sin(m )  d
1 K
 cos(m2k ) I (m, k )  sin(m2k ) J (m, k )
2 k 1
1 K
bm  
 sin(m2k ) I (m, k )  cos(m2k ) J (m, k )
2 k 1

(12)
where
h
I (m, k )   Vk ( ) cos(m )d 
h
(13)
h
J (m, k )   Vk ( ) sin(m )d 
h
Substituting Vk ( )  Ak   Bk   Ck and taking the elementary integrals gives
2
4 A h cos(mh)
sin(mh)
 2 Ak (m 2 h 2  2)  Ck m 2   k 2
3
m
m
2B
J (m, k )  2k sin(mh)  mh cos(mh)  , m  0
(14)
m
2
I (0, k )  Ak h3  2Ck h
3
J (0, k )  0
The wave function was expanded as harmonic series, solution for the Schrödinger equation
I (m, k ) 
without a potential, m 
1
eim , and by plugging it into eq. (1), we obtain the matrix elements
2
for the Hamiltonian
H mn  m H n 
1
2

L

1 2
 im 
e


cl eil  ein d
  2I red  2 l
 L

,
(15)
1

m2 mn  cmn
2 I red
where
m and n
are integers.
Since cm  n  cn  m ,  H mn  is a complex Hermitian matrix. Thus we use the LAPACK
subroutine Zheev for diagonalization to obtain its eigenvalue spectrum, which are the energy levels
of the hindered internal rotor. The obtained energy levels are used for computing the hindrance
partition function. The obtained energy levels are expected to resemble the harmonic oscillator
spectrum at energies below the hindrance barrier; for the higher energy levels, the hindered internal
*
rotor converges to the free one, which is given by E (n)  Breduced n2 ; g  gfree rotor ; n  0, 1, 2, etc. ,
 int
where  int is internal symmetry number (not to be confused with external symmetry number).
6
Optical Isomer
For optical isomers that are not associated with a hindered internal rotation, the number of
optical isomers is included in the rate coefficient expression as a multiplier and must be manually
provided in the input file. If optical isomers are associated with a hindered internal rotation, the
hindered internal rotation should be explicitly treated and the number of optical isomers is set
equal to 1.
Thermodynamic Properties
Heat of Formation
The well-defined atomization method,15-17 which is based on the decomposition of a species into its atoms,
is one of the most common methods for calculating heats of formation H f with the advantage of being
directly used for all species including transition states. Therefore, to be consistent, especially for the
purpose of determining kinetics, this method was implemented in the code using the procedure proposed
by Curtiss and co-workers.17 Bond additivity (BAC)18,19 correction terms were included to reduce the
systematic errors of atomization energies. Calculation of H f using other methods such as isodesmic
reactions have not been implemented in the code yet.
Other Thermodynamic Properties
Standard statistical mechanics methods were used to calculate thermodynamic properties such as
entropies and heat capacities as a function of temperature for a species of interest. Specifically,
thermodynamic properties of a molecule can be computed by adding up the contributions from the
following components including electronic, translational, external rotational, vibration, and hindered
internal rotation (if any). We briefly present the formulation to illustrate the implementation in MSMC.
These contributions can be calculated from the corresponding partition function and its derivatives with
respect to temperature. The partition function can be calculated as follows
Q(T )   g i e  Ei / kbT ,
(16)
i 0
where Ei denotes the ith energy level, g i is the degeneracy, T is the temperature, and k B is Boltzmann’s
constant. The contributions to other thermodynamic properties such as internal energy U , heat capacity
C p and entropy S can be calculated in terms of the partition function using the following equations
 U  k BT 2
 Cp 
U
T
 ln Q
T
P
(17)
N ,V
  ln Q
 2 ln Q 
 k BT  2
T

T 2  N , P
 T
(18)
 ln Q 

(19)

T  N ,V

Since all the partition functions are calculated numerically by direct counting, their derivatives with
respect to temperature are computed by means of the finite difference method with appropriate
precision.
 S  k B  ln Q  T
7
8
Text S2. Implementation of Microcanonical Rate Coefficients, k(E)
Rice–Ramsperger–Kassel–Marcus (RRKM)
For a unimolecular reaction with a well-defined intrinsic transition state, the microcanonical rate
coefficients for a particular energy grain, k ( E ) , can be expressed within the well-known RRKM
framework
k (E) 
W ( E  Eo ) 
h ( E )
(20)
where W (E  Eo ) is the rovibrational sum of states of the transition state,  ( E ) is the density of
rovibrational states of the reactant and h is Planck’s constant. Details about the methodology can
be found elsewhere.8,10
Inverse Laplace Transform (ILT)
In case the reaction takes place over a loose transition state, micro-canonical rate coefficients
cannot be calculated by the RRKM theory. Thus we have to do reverse-engineering to obtain the
energy dependent rate coefficients by performing an inverse Laplace transform on the
phenomenological rate coefficients which can be derived from special treatments such as flexible
transition state theory20-22 or from experiments.
Assume that the high-pressure phenomenological rate coefficient k  (T ) is of the following
form
n
 T   E / RT
k (T )  A 
e a or
 T 
 ref 

k (  )  Ao   n e  Eo  ,

(21)
1
, Ao  A Tref n , E0  Ea / R
T
where A is the pre-exponential factor, Tref is the reference temperature in K, E a is the activation
energy and n is a fitting number.

The relationship between canonical high-pressure rate coefficient, k  ( ) , and microcanonical
rate coefficient, k ( E ) , of a unimolecular reaction can be expressed as
k  ( ) 

1
k ( E )  ( E )e  E dE

Q(  ) 0
(22)
or

k  (  )Q(  )   k ( E )  ( E )e   E dE
(23)
0
 L [k ( E )   ( E )]
9
So
k ( E )  ( E )  LE1[k  (  )  Q(  )]
(24)
 LE1[k  (  )]  LE1[Q(  )]
where  denotes the convolution. We have
LE1[Q(  )]   ( E )
(25)
LE1[k  (  )]  Ao LE1[   n  e  Eo  ]
A
( E  Eo ) n 1 H ( E  Eo )
 ( n)
where H and  are the Heaviside step function and Euler gamma function, respectively. Then
k ( E ) is given by the convolution integral
E
k (E) 
Ao
 ( E  x)( x  Eo ) n 1 H ( x  Eo )dx
 ( E )(n) 0
(26)
where x is dummy integral variable.
Tunneling Correction
A tunneling correction is included using the asymmetric Eckart potential in which the 1-D
tunneling transmission probability is calculated as follows (Eq. 8, Miller 1979)23
P( E ) 
sinh(a)sinh(b)
sinh  (a  b) / 2   cosh 2 (c)
2
(27)
where
E  Vo
4
a    0.5
;
h
Vo  V10.5
b
E  V1
4
 0.5
;

h
Vo  V10.5
c  2
VoV 1
 h 
 2

(28)
1
;
16
E is the energy relative to the top of the energy barrier in the reaction coordinate;   is the
imaginary frequency at the top of the barrier, and Vo , V1 are the classical barrier height with
respect to the reactants and products, respectively.
10
Text S3. Collision models
There are several collision models including empirical ones (e.g., exponential, biexponential,
Weilbull, Lorentzian Step-Ladder, etc.) but only the simple and popular exponential-down model
was implemented in the current version of MSMC. Other models will be implemented in the future.
Within the single exponential-down model, the collision probability P ( E , E ') is expressed as
P( E , E ') 
 E ' E
1
exp  
 E
CN ( E ')
down


 , E '  E (29)

where CN ( E ') is the normalization constant that guarantees
 P( E, E ')dE  1 ;
Edown is the
averaged energy transferred in a deactivating collision, which depends on the nature of the
colliding gas as a function of temperature, or in some cases, of temperature and energy.
Collision frequency/rate  I can be calculated using Lennard-Jones potential parameters as
I  hard  sphere  , where hard  sphere is the hard-sphere collision rate derived from the elementary
gas-phase kinetic theory and  , a correction arising from the use of a realistic (e.g., Lennard
Jones) rather than a hard-sphere interaction, is a dimensionless collision integral which was
calculated by the expression proposed by Reid and coworkers.24 A discussion about this
expression/formulation can be found elsewhere.8
11
Text S4. Graphical User Interface (GUI)
Screenshots of the MSMC-GUI can be viewed in Figures 1-4. The following section will present
some main features of the MSMC-GUI. Detailed description about the GUI can be found in the
Manual within the GUI under the Help section.
Taking its main advantage from the Java programming language that is system-independent,
the MSMC-GUI consists of a unique jar file that can be executed in any computer having JRE
installed. Note that the engine run in Unix/Linux environment. Its program interface is divided
into 2 main groups: General Parameters and Other Parameters. The General Parameters group
involves general information about the calculations such as temperature, pressure, electronic
structure method, etc. Those parameters can be entered directly into the input fields while the
Other Parameters group containing reactants’ or products’ information that can be parsed directly
from the Gaussian output files. Users can also easily modify the imported information by clicking
on the Edit button. Note that the MSMC-GUI is just the user interface, users must install the
computing engine into a Linux machine and provide accessing information via the Setup Server
form under the menu Action (cf. Figure 3). After all the necessary parameters have been provided,
and users can save these parameters into a MSMC file format in local disk or can directly invoke
the calculation on the setup server and wait for the results. Upon clicking on the Submit button,
the MSMC-GUI automatically connects to the provided server, uploads the input file, invokes
computation and finally downloads the result files in a transparent manner. Information about
running status and all result files will be listed in the Result tab (cf. Figure 4).
Figure 1. Screenshot of the main MSMC-GUI
12
Figure 2. Screenshot of the MSMC-GUI for setting up and testing the server connection for calculations.
13
Figure 3. Screenshots of the MSMC-GUI for monitoring calculations and examining/analyzing results.
14
Figure 4. Screenshots of the post-processing MSMC-GUI: plots of rate coefficients as a function of
temperature (top) and normalized species concentration as a function of time (bottom).
15
Table S1. Comparison of Calculated Thermodynamic Properties[a] of
Selected Species with Available Literature Data (ATcT = Active
Thermochemical Tables,25,26 values collected from Burcat’s online
database27).
16
Species
Method
H 298
f
CP300
S 298
CP400
(kcal/mol)
CP500
CP600
CP800
CP1000
CP1500
(cal/mol-K)
Alkanes
CH4
C2H6
C3H8
CH3
C2H5
n-C3H7
i-C3H7
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
-18.1
-17.8
-20.2
-20.0
-25.0
-25.0
35.3
35.1
29.1
28.6
24.8
24.2
21.4
21.5
44.5
44.5
55.7
54.8
65.6
64.6
46.5
46.4
62.3
58.1
71.3
69.4
70.1
69.3
8.5
8.5
11.7
12.6
16.3
17.7
9.4
9.2
11.7
12.2
16.3
17.1
15.6
15.7
9.6
9.7
14.7
15.6
21.2
22.3
10.1
10.0
14.0
14.6
20.4
21.1
19.5
19.5
10.9
11.0
17.7
18.6
25.7
26.8
10.9
10.8
16.4
17.1
24.3
25.0
23.4
23.4
12.3
12.5
20.5
21.4
29.7
30.9
11.5
11.5
18.5
19.4
27.7
28.3
26.9
26.9
14.8
15.0
25.1
25.8
36.1
37.0
12.8
12.9
22.0
23.0
33.1
33.5
32.5
32.5
16.9
17.2
28.6
29.3
41.0
41.8
14.0
14.1
24.8
25.8
37.2
37.6
36.8
36.9
20.4
20.6
34.4
34.7
48.6
49.0
16.2
16.2
29.4
30.2
43.8
43.9
43.7
43.6
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
12.9
12.5
5.4
4.8
-3.4
-4.2
46.1
45.6
52.3
52.4
64.6
63.7
71.4
68.7
58.0
58.2
10.1
10.3
14.5
15.5
19.6
20.7
13.9
14.1
12.4
12.6
18.3
19.2
25.0
26.2
16.9
17.1
14.7
14.9
21.8
22.7
29.8
31.3
19.5
19.8
16.6
17.0
25.0
25.9
34.0
35.7
21.6
22.0
19.7
20.1
30.0
30.8
40.8
42.2
25.0
25.4
22.1
22.5
33.8
34.6
45.9
47.2
27.6
28.0
26.0
26.2
39.8
40.3
53.9
54.7
31.7
31.9
10.3
10.5
14.3
14.6
18.4
19.6
18.2
18.7
11.8
12.0
17.1
17.3
23.0
24.0
22.1
22.6
12.8
13.1
19.5
19.7
26.9
27.8
25.7
26.3
13.7
13.9
21.5
21.8
30.2
31.1
29.0
29.7
14.9
15.2
24.8
25.1
35.5
36.2
34.5
35.1
15.9
16.2
27.4
27.7
39.4
40.1
38.6
39.3
17.7
18.1
31.6
31.7
45.6
46.0
45.2
45.6
13.1
13.4
16.8
17.4
20.7
19.9
25.2
17.8
18.0
23.2
23.7
28.8
28.0
34.9
22.0
22.3
29.1
29.8
36.3
35.7
43.9
25.5
26.1
34.1
35.0
42.6
42.5
51.5
30.9
31.3
41.7
42.5
52.5
52.3
63.5
34.7
35.3
47.2
48.0
59.6
59.6
72.2
40.9
41.1
55.8
56.1
70.5
69.9
85.4
Alkenes
CH2=CH2
(ethene)
CH3CH=CH2
(propylene)
C4H8
(isobutene)
CH2=C=CH2
(allene)
Alkynes
MSMC
55.7
47.8
ATcT
54.5
48.0
MSMC
45.3
59.1
CHC CH3
(propyne)
ATcT
44.3
59.3
MSMC
41.0
69.9
CHCCH2CH3
(1-butyne)
ATcT
39.5
69.6
MSMC
35.7
70.5
CH3CCCH3
(2-butyne)
ATcT
35.0
69.8
Cyclo-alkane, cycle-alkene, acromatics and others
MSMC
13.6
60.2
C3H6
(cyclopropane)
ATcT
12.7
56.8
MSMC
7.2
63.0
C4H8
(cyclobutane)
ATcT
6.8
61.9
MSMC
-17.2
72.3
C5H10
(cyclopentane)
ATcT
-18.4
70.0
C6H12
MSMC
-28.6
74.8
CHCH
(ethyne)
17
(cyclohexane)
C3H4
(cyclopropene)
C4H6
(cyclobutene)
C6H6
(benzene)
Other compounds
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
-29.5
68.8
67.8
39.8
37.4
20.2
19.8
71.1
59.4
58.2
62.6
62.6
64.1
64.3
25.4
12.3
12.7
15.4
15.4
19.3
19.7
35.3
15.8
16.1
20.8
20.8
26.4
26.7
45.0
18.8
19.2
25.7
25.9
32.6
33.0
53.5
21.2
21.8
29.7
30.2
37.5
38.2
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
MSMC
ATcT
-26.9
-26.4
-95.9
-94.0
-58.2
-57.8
-33.8
-32.4
-27.5
-26.1
-22.2
-23.0
8.9
8.9
2.1
2.9
9.6
10.1
94.7
93.5
102.5
102.5
0.75
0.93
47.2
47.2
51.1
51.1
45.1
45.1
55.5
56.0
52.2
52.3
75.0
75.3
43.8
43.9
54.6
54.8
53.6
53.6
46.7
46.5
45.2
45.2
0.83
1.42
7.0
7.0
8.9
8.9
8.0
8.0
10.3
10.2
8.4
8.5
24.5
24.8
7.0
7.1
8.2
8.3
8.2
8.3
8.3
8.4
8.1
8.1
0.37
0.53
7.0
7.0
9.8
9.9
8.1
8.2
11.1
11.1
9.3
9.4
32.2
32.3
7.0
7.1
8.7
8.9
8.7
8.8
8.6
8.7
8.3
8.3
0.34
0.49
7.1
7.1
10.6
10.7
8.4
8.4
11.9
12.0
10.3
10.4
38.5
38.6
7.0
7.1
9.2
9.5
9.2
9.3
9.0
9.1
8.6
8.7
0.40
0.56
7.2
7.2
11.2
11.3
8.6
8.7
12.6
12.8
11.3
11.5
43.4
43.8
7.0
7.1
9.7
10.0
9.7
9.8
9.3
9.4
9.0
9.0
0.49
0.69
66.2
24.9
25.3
35.7
36.1
44.8
45.4
75.2
27.6
28.0
40.0
40.5
49.9
50.5
87.2
31.7
31.9
46.6
46.7
57.4
57.6
7.6
7.9
8.3
7.6
7.9
8.4
12.2 12.9 13.8
CO2
12.3 13.0 13.9
9.1
9.7 11.0
H2O
9.2
9.9 11.3
13.8
14.7
16.2
H2O2
14.0 14.9 16.6
13.2 14.6 16.9
H2CO
13.4 14.8 16.9
50.5 55.3 62.4
Phenol
50.7 55.6 62.5
7.1
7.2
7.7
OH
7.1
7.3
7.9
10.5 11.1 12.1
HO2
10.8 11.4 12.5
10.6 11.3 12.5
HCO
10.8 11.7 12.9
3
9.8
10.4 11.7
CH2
9.9
10.6 11.8
1
9.7
10.5 11.8
CH2
9.8
10.6 11.9
[b]
0.46
0.49 0.32
MAD
[c]
RMS errors
0.69 0.73 0.46
298
[a] Electronic structure calculations were calculated at the composite CBS-QB3. H f was calculated
CO
by atomization method (See main text for more information). [b] Mean absolute deviations
(MADs) . [c] Root mean square error (RMS).
18
Table S2: Geometries, Energies (at 0 K) and Frequencies for all Species for
the Thermodynamic Test Cases Calculated at the Composite Method CBSQB3.
Species
CH4
C2H6
C3H8
n-C4H10
i-C4H10
Energy
(hartree)
-40.409988
-79.630575
-118.855864
-158.081489
-158.084511
Cartesian coordinates
(in Å)
6
1
1
1
1
6
1
1
1
6
1
1
1
6
1
1
1
6
1
1
6
1
1
1
6
1
1
1
6
1
1
6
1
1
6
1
1
1
6
1
1
1
6
1
6
1
1
0.000000000
0.629587000
-0.629587000
-0.629587000
0.629587000
0.000000000
0.000000000
-0.882102000
0.882102000
0.000000000
0.000000000
-0.882102000
0.882102000
0.000000000
-0.882911000
0.882911000
0.000000000
0.000000000
0.875588000
-0.875588000
0.000000000
0.882911000
0.000000000
-0.882911000
1.962203000
2.109853000
2.109853000
2.748402000
0.568589000
0.464001000
0.464003000
-0.568589000
-0.464003000
-0.464000000
-1.962203000
-2.109847000
-2.748403000
-2.109860000
0.000000000
-0.884111000
0.000000000
0.884111000
0.000000000
0.000000000
-1.265802000
-1.316556000
-1.286073000
0.000000000
0.629587000
-0.629587000
0.629587000
-0.629587000
0.000000000
1.018564000
-0.509282000
-0.509282000
0.000000000
-1.018564000
0.509282000
0.509282000
1.277083000
1.322089000
1.322089000
2.173904000
0.000000000
0.000000000
0.000000000
-1.277083000
-1.322089000
-2.173904000
-1.322089000
-0.120891000
-0.750899000
-0.750906000
0.639395000
0.513777000
1.165707000
1.165706000
-0.513777000
-1.165703000
-1.165711000
0.120891000
0.750921000
-0.639394000
0.750884000
1.461622000
1.995471000
1.520227000
1.995471000
0.000000000
0.000000000
-0.730811000
-0.760114000
-1.763398000
19
0.000000000
0.629587000
0.629587000
-0.629587000
-0.629587000
0.765307000
1.163709000
1.163709000
1.163709000
-0.765307000
-1.163709000
-1.163709000
-1.163709000
-0.259633000
-0.905443000
-0.905443000
0.366448000
0.585756000
1.244968000
1.244968000
-0.259633000
-0.905443000
0.366448000
-0.905443000
0.000001000
0.883010000
-0.883003000
-0.000002000
-0.000001000
0.876215000
-0.876218000
-0.000001000
-0.876220000
0.876213000
0.000001000
-0.882993000
-0.000021000
0.883020000
-0.095688000
0.265476000
-1.189849000
0.265476000
0.371574000
1.469626000
-0.095688000
-1.189849000
0.265476000
Frequencies
(cm-1)
1341.2120, 1341.2120, 1341.2120,
1561.0735, 1561.0735, 3028.4612,
3134.8422, 3134.8422, 3134.8422
308.8665, 827.9580, 827.9584,
997.0186, 1219.1563, 1219.1579,
1409.2702, 1425.2815, 1505.0816,
1505.0821, 1507.7574, 1507.7590,
3024.5679, 3025.1795, 3070.6842,
3070.6843, 3096.0218, 3096.0235
219.3190, 269.3752, 366.3376,
755.0908, 870.5538, 914.6182,
933.0298, 1057.1314, 1175.4568,
1213.4906, 1319.0377, 1369.3548,
1406.3647, 1422.7910, 1491.5497,
1494.1528, 1499.4080, 1509.0364,
1515.3801, 3013.9861, 3014.6985,
3018.5640, 3034.3975, 3071.6451,
3081.2045, 3083.4091, 3084.0758
120.6651, 232.6528, 261.5735,
265.4259, 425.4802, 737.4166,
815.0138, 841.5991, 965.2034,
981.8607, 1015.8514, 1063.3775,
1168.5518, 1208.7207, 1292.3859,
1325.3924, 1334.7162 , 1395.5873,
1413.6339, 1416.1611, 1488.6051,
1493.4011, 1501.8937, 1503.2700,
1507.5064, 1513.6934, 2998.7631,
3006.6415, 3016.2280, 3017.6895,
3018.2985, 3039.5949, 3076.5270,
3080.7282, 3082.7433, 3083.6405
213.4496, 260.6448, 260.6448,
365.5853, 365.5857, 435.7216,
795.4523, 924.7046, 924.7081,
955.7655, 971.0344, 971.0365,
1191.5838, 1191.5838, 1209.6846,
1359.9794, 1359.9862, 1401.1864,
1401.1865, 1430.1799, 1484.2479,
1490.4530, 1490.4532, 1509.6045,
1509.6048, 1516.8631, 2993.7972,
Species
CH3
C2H5
n-C3H7
i-C3H7
Energy
(hartree)
-39.744799
-78.971552
-118.196326
-118.201395
n-C4H9
-157.422060
i-C4H9
-157.426623
Cartesian coordinates
(in Å)
1
6
1
1
1
6
1
1
1
6
1
1
1
6
1
1
6
1
1
6
6
1
1
1
1
1
6
6
1
1
1
6
1
1
1
1
6
1
1
1
6
1
1
6
1
1
6
1
1
6
1
1
-2.170184000
1.265802000
1.286073000
1.316556000
2.170184000
0.000000000
0.000000000
0.935848000
-0.935848000
-0.010058000
-0.505828000
1.012945000
-0.505828000
-0.010058000
0.059700000
0.059700000
0.143577000
-0.007993000
0.995418000
-0.665180000
-0.690687000
-0.273499000
-1.689856000
-1.272974000
-1.131961000
0.321758000
0.038078000
0.031602000
1.032000000
-0.302405000
-0.642203000
-1.148685000
0.797915000
-0.923460000
-1.511500000
-2.002872000
-1.890698000
-2.036327000
-2.020162000
-2.688472000
-0.509218000
-0.416294000
-0.404244000
0.644975000
0.524342000
0.549517000
1.998379000
2.163468000
2.867540000
-1.937317000
-2.108722000
-2.001894000
-0.232072000
-0.730811000
-1.763398000
-0.760114000
-0.232072000
0.000000000
1.080624000
-0.540312000
-0.540312000
-0.693275000
-1.101699000
-1.105682000
-1.101699000
0.794440000
1.351043000
1.351043000
-0.137591000
0.169461000
0.274349000
-1.234663000
-1.214379000
-2.212551000
-1.197409000
-2.049479000
-0.285715000
-1.288630000
0.027038000
0.003077000
-0.171258000
0.994960000
-0.728706000
0.483912000
-0.564618000
0.598433000
1.448846000
-0.211109000
-0.132322000
-0.852787000
-0.668792000
0.611833000
0.521428000
1.075761000
1.260903000
-0.488705000
-1.059516000
-1.238061000
0.130857000
1.127590000
-0.444478000
0.168478000
0.911642000
0.681385000
20
0.265476000
-0.095688000
0.265476000
-1.189849000
0.265476000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.886142000
0.000000000
-0.886142000
0.000000000
0.926370000
-0.926370000
0.140043000
1.167797000
-0.389371000
-0.461144000
-1.995335000
-0.128877000
-0.070210000
-2.393602000
-2.367087000
-2.403547000
-0.012989000
1.477196000
-0.421754000
-0.402513000
-0.442025000
2.249879000
1.994019000
3.313166000
1.873560000
2.176201000
0.016848000
-0.794168000
0.962148000
-0.054419000
-0.064561000
-1.004882000
0.738220000
0.035516000
0.974653000
-0.761549000
-0.010730000
0.382885000
-0.305326000
-0.081078000
0.703478000
-1.044643000
Frequencies
(cm-1)
3010.9864, 3010.9864, 3018.5833,
3070.2704, 3070.2704, 3078.5920,
3080.6295, 3083.2782, 3083.2782
506.7550, 1403.4716, 1403.4733,
3102.7007, 3281.7014, 3281.7028
109.4027, 477.4344, 813.2858,
980.0282, 1061.9599, 1191.6149,
1400.8645, 1465.0228, 1482.6419
113.8178, 247.3979, 370.7253,
483.2107, 754.6977, 880.2816,
921.9308, 1051.2847, 1082.9220,
1171.4850, 1268.1215, 1360.1241,
1409.0433, 1462.8397, 1467.8485,
1499.1229, 1505.7389, 2918.2869,
3010.4980, 3024.2725, 3086.0064,
3092.0819, 3130.3219, 3231.4565
103.8056, 117.9535, 354.4831,
396.7801, 883.3783, 939.5231,
944.8406, 1028.4288, 1146.3223,
1177.6318, 1367.4550, 1408.7742,
1413.5035, 1469.4355, 1478.0784,
1480.5942, 1491.7677, 2931.7834,
2936.2031, 3011.3943, 3012.8920,
3081.7646, 3082.7435, 3162.4607
93.3217, 129.9187, 237.0666,
262.8111, 426.4700, 482.3292,
731.0407, 821.4718, 865.9713,
966.4428, 1030.0350, 1074.2112,
1090.8251, 1166.7111, 1248.3922,
1314.4130, 1326.7810, 1390.6131,
1414.5949, 1460.7886, 1467.1451,
1494.5478, 1500.8552, 1509.4192,
2908.2002, 3002.6321, 3015.1924,
3019.8985, 3044.2559, 3080.9386,
3086.7022, 3130.2811, 3231.0017
58.9787, 106.3268, 234.8233,
260.6940, 390.4039, 429.6108,
769.4556, 846.7913, 974.2017,
Species
C2H4
CH3CHCH2
(propylene)
C4H8
(isobutene)
CH2=C=CH2
(allene)
(CH2CH)2
(butadiene)
Energy
(hartree)
-78.416642
-117.646233
-156.877859
-116.420303
-155.666929
Cartesian coordinates
(in Å)
1
6
1
1
6
1
6
1
1
1
6
1
1
6
1
1
6
1
1
6
1
1
1
6
1
6
1
1
6
6
1
1
1
6
1
1
1
6
6
1
1
6
1
1
6
1
1
6
1
6
1
6
-2.749839000
-0.570782000
-0.565229000
-0.437514000
0.581167000
0.407161000
1.985313000
2.083187000
2.680062000
2.342500000
0.000000000
-0.000034000
0.000034000
0.000000000
0.000034000
-0.000034000
1.280408000
1.301573000
2.238883000
-1.233467000
-1.807497000
-1.807209000
-1.181881000
0.134627000
0.166721000
-0.000763000
-0.001498000
-0.001498000
0.000315000
0.000315000
0.000172000
-0.878265000
0.879046000
0.000315000
-0.878265000
0.000172000
0.879046000
0.000001000
-1.302453000
-1.866954000
-1.866927000
1.302452000
1.866931000
1.866949000
-1.844812000
-2.014258000
-2.722211000
-0.608641000
-0.475702000
0.608641000
0.475702000
1.844812000
-0.561111000
-0.505142000
-1.061123000
-1.278078000
0.443263000
1.476873000
-0.042867000
-0.812848000
0.766775000
-0.505907000
0.000000000
0.922578000
-0.922578000
0.000000000
0.922578000
-0.922578000
0.220447000
1.306428000
-0.286244000
0.162344000
-0.153321000
-0.152980000
1.253642000
-0.453702000
-1.542063000
1.457053000
2.025616000
2.025616000
0.124091000
-0.678233000
-0.036164000
-1.331845000
-1.331643000
-0.678233000
-1.331845000
-0.036164000
-1.331643000
0.000006000
-0.000004000
0.655135000
-0.655135000
-0.000002000
0.656210000
-0.656205000
0.109549000
1.181858000
-0.525746000
-0.399286000
-1.479565000
0.399286000
1.479565000
-0.109549000
21
-0.031441000
0.091023000
1.046567000
-0.679539000
0.048889000
0.334314000
-0.067200000
-0.842527000
-0.304758000
0.868743000
0.663495000
1.234560000
1.234560000
-0.663495000
-1.234560000
-1.234560000
-0.000030000
0.000093000
0.000082000
0.000003000
-0.878325000
0.878619000
-0.000203000
-0.000035000
0.000101000
0.000000000
0.923927000
-0.923927000
0.000000000
1.276073000
2.158607000
1.326693000
1.326789000
-1.276073000
-1.326693000
-2.158607000
-1.326789000
-0.000014000
0.000001000
-0.656155000
0.656190000
0.000005000
0.655108000
-0.655092000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
Frequencies
(cm-1)
988.7413, 1024.3461, 1071.3215,
1129.7101, 1179.8739, 1270.2350,
1314.2518, 1402.5947, 1411.8563,
1415.6383, 1469.9197, 1474.8998,
1486.4122, 1499.6171, 1506.2739,
2908.0572, 2934.1897, 2986.3529,
3015.6136, 3024.2314, 3080.7718,
3084.7669, 3091.2161, 3146.0824
834.6255, 972.7569, 973.4373,
1066.4367, 1238.6475, 1379.5299,
1472.1013, 1691.6999, 3121.6181,
3136.7477, 3192.9230, 3221.3735
204.7612, 425.0707, 591.2132,
923.8663, 941.5028, 948.1593,
1029.7583, 1070.9291, 1189.0880,
1327.0447, 1408.2002, 1448.6420,
1480.7343, 1494.8443, 1712.9495,
3012.7570, 3056.4162, 3091.9351,
3120.4259, 3127.5198, 3208.0402
163.4996, 206.4198, 379.1305,
439.5534, 439.8623, 702.6060,
813.7137, 917.3589, 960.2720,
983.1479, 1021.3862, 1082.5241,
1105.7331, 1293.3482, 1409.5695,
1413.1137, 1442.0479, 1472.1567,
1485.4901, 1490.2983, 1502.5193,
1719.5280, 3006.8307, 3012.5901,
3049.9594, 3053.1727, 3102.4670,
3104.2605, 3127.1618, 3206.0228
371.8058, 371.8097, 866.2307,
866.2342, 885.0874, 1017.1739,
1017.1762, 1109.3192, 1422.4941,
1479.5949, 2052.4048, 3117.2845,
3121.3249, 3192.2781, 3192.2838
174.2795, 299.7001, 518.8057,
540.0433, 781.1822, 899.4611,
934.9134, 936.0720, 1001.9023,
1004.4257, 1058.6869, 1227.3242,
1315.0040, 1320.2697, 1415.3498,
1473.2619, 1653.5138, 1706.5055,
3121.5064, 3131.2371, 3134.8672,
3134.9763, 3219.8165, 3220.2418
Species
C2H2
CH3CCH
(propyne)
C4H6
(1-butyne)
C4H6
(2-butyne)
C3H6
(cyclopropane)
C4H8
(cyclobutane)
Energy
(hartree)
-77.187431
-116.421726
-155.646204
-155.654698
-117.632357
-156.859825
Cartesian coordinates
(in Å)
1
1
6
1
6
1
6
1
6
6
1
1
1
6
6
6
1
6
1
1
1
1
1
6
6
6
1
1
1
6
1
1
1
6
6
6
1
1
1
1
1
1
6
6
6
1
1
1
1
1
1
6
2.014258000
2.722211000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.884337000
-0.884337000
0.834003000
-0.542643000
1.959412000
2.955954000
-1.587684000
-1.475927000
-1.476367000
-2.597679000
-0.692461000
-0.692043000
-0.601506000
0.601505000
-2.060298000
-2.455709000
-2.456309000
-2.456865000
2.060298000
2.456297000
2.455742000
2.456846000
-0.547139000
0.859507000
-0.312291000
-0.918091000
-0.918090000
1.441587000
1.441589000
-0.523731000
-0.523732000
0.000000000
-1.084917000
1.084917000
0.000000000
0.000000000
-1.426067000
-1.960723000
1.960723000
1.426067000
0.000000000
-1.181858000
0.525746000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
1.021144000
-0.510572000
-0.510572000
0.157840000
0.646972000
-0.263506000
-0.630932000
-0.482955000
-1.115105000
-1.114856000
-0.065705000
1.288129000
1.288364000
-0.000220000
-0.000325000
0.000131000
-0.070207000
0.916717000
-0.845769000
0.000145000
-0.846585000
0.916083000
-0.068625000
-0.676525000
-0.135530000
0.812091000
-1.134543000
-1.134544000
-0.227770000
-0.227770000
1.362203000
1.362204000
1.084917000
0.000000000
0.000000000
1.960723000
1.426067000
0.000000000
0.000000000
0.000000000
0.000000000
-1.084917000
22
0.000000000
0.000001000
0.599081000
1.661906000
-0.599081000
-1.661906000
1.420165000
2.482190000
0.219257000
-1.238141000
-1.629958000
-1.629958000
-1.629958000
0.000123000
0.000001000
-0.000152000
0.000256000
0.000037000
-0.883226000
0.883513000
-0.000422000
-0.875805000
0.875629000
-0.000837000
0.000694000
0.000142000
1.017946000
-0.447383000
-0.569413000
-0.000060000
-0.568779000
-0.449415000
1.017405000
0.000000000
-0.000001000
0.000001000
-0.909328000
0.909329000
-0.909368000
0.909365000
0.909358000
-0.909356000
0.122814000
-0.122814000
-0.122814000
-0.529321000
1.161263000
-1.161263000
0.529321000
0.529321000
-1.161263000
0.122814000
Frequencies
(cm-1)
642.0191, 642.0191, 772.6880,
772.6880, 2069.6726, 3421.0933,
3523.9759
339.6167, 339.6174, 665.9190,
665.9191, 943.2966, 1056.8865,
1056.8872, 1416.9425, 1479.9116,
1479.9117, 2230.6029, 3025.5280,
3084.3590, 3084.3591, 3479.3991
200.1148, 221.6767, 359.2723,
519.3317, 665.2329, 673.1039,
787.8315, 846.4794, 1020.7847,
1089.2263, 1108.5621, 1288.4097,
1349.2001, 1410.6578, 1479.1108,
1496.5055, 1507.3811, 2222.1486,
3020.7434, 3036.7159, 3045.5592,
3104.6917, 3110.9678, 3478.2220
27.8554, 200.5650, 201.1153,
382.5960, 382.7998, 724.7681,
1044.1110, 1044.3240, 1066.3892,
1066.5725, 1170.9730, 1416.7932,
1420.3609, 1481.8420, 1481.8501,
1482.1528, 1482.1646, 2365.5003,
3019.4230, 3019.7275, 3074.4361,
3074.5802, 3075.3161, 3075.4596
743.6938, 744.2532, 861.8551,
883.7305, 884.8186, 1053.7666,
1055.5470, 1088.4478, 1152.0183,
1211.5245, 1211.6380, 1216.3039,
1473.6895, 1474.4732, 1522.0901,
3119.7037, 3119.9478, 3127.8617,
3194.0004, 3194.1779, 3215.9796
193.0305, 641.1535, 754.2154,
754.2154, 885.3940, 913.2182,
913.2182, 941.9578, 965.9473,
1013.2578, 1167.7178, 1173.6179,
1246.9630, 1246.9630, 1256.8850,
1258.4816, 1287.4556, 1287.4556,
1484.8755, 1484.8755, 1491.3956,
1523.9458, 3041.4926, 3042.5684,
3042.5684, 3048.2491, 3075.8297,
3090.0242, 3090.0242, 3108.4101
Species
C5H8
(spiropentane)
C5H10
(cyclopentane)
C6H12
(cyclohexane)
C3H4
(cyclopropene)
Energy
(hartree)
-194.856213
-196.116379
-235.351637
-116.383557
Cartesian coordinates
(in Å)
1
1
6
6
1
1
1
1
6
6
6
1
1
1
1
6
1
1
6
1
1
6
1
1
6
1
1
6
1
1
6
6
6
6
6
6
1
1
1
1
1
1
1
1
1
1
1
1
6
6
6
1
0.000000000
0.000000000
1.270166000
1.270091000
1.572483000
1.572354000
1.572475000
1.572121000
0.000000000
-1.270197000
-1.270064000
-1.572124000
-1.572405000
-1.572189000
-1.572691000
0.000000000
-0.703897000
0.992516000
-0.325095000
-1.409586000
0.035957000
0.000000000
0.875758000
-0.875758000
0.000000000
-0.992516000
0.703897000
0.325095000
-0.035957000
1.409586000
1.382279000
1.116990000
-0.265121000
-1.382280000
-1.116988000
0.265121000
-0.451077000
1.170578000
1.899685000
1.449248000
2.350627000
-1.449273000
-2.350625000
-1.899682000
-1.170563000
0.278021000
0.451078000
-0.278022000
0.000042000
0.000042000
0.000042000
-0.913066000
-1.426067000
-1.960723000
-0.541057000
0.541110000
-1.541494000
-0.250422000
0.250451000
1.541644000
-0.000080000
-0.541600000
0.541492000
-1.541766000
-0.251610000
1.541833000
0.252174000
1.242663000
2.012274000
1.703805000
0.695764000
0.594908000
1.343179000
0.000000000
0.006014000
-0.006014000
-1.242663000
-1.703805000
-2.012274000
-0.695764000
-1.343179000
-0.594908000
-0.491632000
0.950824000
1.442183000
0.491631000
-0.950827000
-1.442181000
2.453337000
0.995986000
1.617420000
-0.515227000
-0.836295000
0.515223000
0.836291000
-1.617422000
-0.996001000
-1.511153000
-2.453338000
1.511182000
0.863415000
-0.501312000
-0.501312000
1.460177000
23
1.161263000
-0.529321000
0.541219000
-0.541216000
0.250238000
1.541796000
-1.541729000
-0.250284000
-0.000008000
-0.540794000
0.540709000
-0.248575000
-1.541511000
0.249049000
1.541563000
0.372154000
0.697432000
0.362247000
-1.031012000
-1.155897000
-1.834269000
1.307545000
1.961003000
1.961003000
0.372154000
0.362247000
0.697432000
-1.031012000
-1.834269000
-1.155897000
-0.228377000
0.228321000
-0.228318000
0.228367000
-0.228324000
0.228330000
0.148653000
1.324076000
-0.148665000
-1.324033000
0.149284000
1.324023000
-0.149303000
0.148665000
-1.324078000
1.324025000
-0.148630000
-1.324012000
0.000000000
0.645003000
-0.645003000
0.000000000
Frequencies
(cm-1)
292.8185, 306.0670, 306.1024,
600.6486, 791.9908, 792.0035,
839.7439, 885.9769, 886.1242,
895.5313, 1011.5491, 1022.5894,
1050.9478, 1074.2582, 1074.2852,
1075.0874, 1169.8686, 1179.9709,
1180.0214, 1180.1595, 1431.5468,
1461.5736, 1461.5771, 1493.0585,
1573.6982, 3105.8460, 3105.8657,
3108.7895, 3109.8799, 3181.6209,
3182.6113, 3195.7514, 3195.7591
34.1745, 261.1716, 552.6567,
620.3745, 767.9919, 822.1931,
867.7705, 881.4585, 903.1436,
907.8528, 972.4834, 1002.6082,
1040.5346, 1049.0544, 1181.3845,
1206.2973, 1227.7940, 1237.2253,
1285.0097, 1310.7956, 1322.6542,
1341.2594, 1350.7187, 1351.2538,
1488.9822, 1494.8901, 1499.9322,
1500.0193, 1525.3338, 3014.0638,
3020.4098, 3030.4496, 3030.8162,
3047.2129, 3062.1477, 3072.7214,
3075.9177, 3078.1968, 3093.5413
221.8983, 228.4931, 372.9002,
426.8870, 429.5717, 520.2213,
792.6240, 793.4684, 800.2736,
860.8177, 863.6372, 918.0697,
919.0653, 1034.3670, 1035.9067,
1042.4448, 1076.7559, 1094.5824,
1132.5654, 1180.3266, 1285.6476,
1287.3334, 1292.7727, 1293.8189,
1350.4799, 1371.2177, 1377.0854,
1377.6746, 1384.5634, 1385.5749,
1484.4564, 1484.9446, 1489.7538,
1490.2245, 1495.1620, 1510.1220,
2995.5945, 2996.0257, 2997.2921,
3002.8846, 3003.2207, 3006.3197,
3045.1897, 3045.4732, 3047.6601,
3047.8667, 3049.4957, 3056.4065
605.6059, 786.2095, 870.0783,
923.1720, 1014.8137, 1031.9595,
1068.4086, 1110.2192, 1153.6320,
1520.5873, 1733.1554, 3032.7006,
Species
C4H6
(cyclobutene)
C5H8
(cyclopentene)
C6H6
(benzene)
CH3C6H5
(Toluene)
Energy
(hartree)
-155.646796
-194.912308
-231.789736
-271.020471
Cartesian coordinates
(in Å)
1
1
1
6
6
6
6
1
1
1
1
1
1
6
1
1
6
1
6
1
1
6
1
1
6
1
6
6
6
6
6
6
1
1
1
1
1
1
6
1
6
1
6
1
6
1
6
1
6
6
1
1
0.913109000
-0.000396000
-0.000396000
0.000001000
-0.000001000
0.000001000
-0.000001000
0.000459000
-0.000459000
-0.888924000
0.888601000
-0.888601000
0.888924000
-0.066347000
-1.049538000
0.660050000
-0.066347000
-0.102578000
0.257390000
1.323163000
-0.291057000
-0.066347000
-1.049538000
0.660050000
-0.066347000
-0.102578000
-1.290132000
-1.102348000
0.187688000
1.290155000
1.102384000
-0.187747000
-2.293716000
-1.959982000
0.333673000
2.293684000
1.959933000
-0.333593000
1.199390000
1.736012000
-0.193601000
-0.731479000
1.901705000
2.985869000
1.198765000
1.735218000
-0.194007000
-0.732406000
-0.912330000
-2.422428000
-2.828412000
-2.828265000
1.460248000
-1.042587000
-1.042587000
0.668712000
-0.668712000
-0.786796000
0.786796000
1.414557000
-1.414557000
-1.245125000
-1.245610000
1.245610000
1.245125000
-0.326262000
-0.565826000
-0.457862000
1.074158000
1.961448000
-1.207838000
-1.451423000
-2.151826000
-0.326262000
-0.565826000
-0.457862000
1.074158000
1.961448000
-0.528070000
0.853189000
1.381199000
0.528015000
-0.853143000
-1.381191000
-0.938841000
1.516822000
2.455735000
0.938918000
-1.516885000
-2.455746000
-1.202772000
-2.145318000
-1.200216000
-2.143177000
0.000226000
0.000598000
1.203080000
2.145726000
1.200006000
2.142691000
-0.000318000
-0.000131000
0.877123000
-0.891120000
24
0.000000000
1.575278000
-1.575278000
0.814300000
0.814300000
-0.700094000
-0.700094000
1.601088000
1.601088000
-1.143164000
-1.143159000
-1.143159000
-1.143164000
1.235335000
1.662169000
2.043585000
0.665748000
1.287906000
0.000000000
0.000000000
0.000000000
-1.235335000
-1.662169000
-2.043585000
-0.665748000
-1.287906000
-0.000001000
0.000007000
-0.000011000
0.000001000
0.000008000
-0.000005000
0.000002000
0.000014000
0.000001000
0.000002000
0.000004000
-0.000014000
0.002129000
0.001261000
-0.008521000
-0.017444000
0.008288000
0.013139000
0.002079000
0.002012000
-0.008787000
-0.017138000
-0.011500000
0.009133000
-0.500130000
-0.475662000
Frequencies
(cm-1)
3095.8162, 3246.7009, 3293.8644
321.8478, 650.2211, 865.7789,
867.7595, 884.8784, 896.8139,
940.7073, 997.5490, 1039.1659,
1098.2394, 1129.6123, 1168.4155,
1213.0413, 1234.8229, 1317.0367,
1467.9190, 1488.1385, 1634.8764,
3031.3332, 3036.7561, 3067.7418,
3082.2922, 3164.0233, 3195.7811
139.5231, 392.2858, 615.8342,
714.4370, 783.4262, 819.7011,
890.7957, 902.4865, 916.7645,
972.6074, 973.8287, 1035.1867,
1067.9545, 1129.1406, 1153.6259,
1225.4473, 1230.7818, 1308.2821,
1318.2356, 1326.4110, 1378.1449,
1484.6671, 1489.9644, 1509.7240,
1680.1992, 2996.4504, 2997.8327,
3035.2018, 3043.5908, 3055.2441,
3090.9389, 3165.4901, 3190.5044
412.8483, 412.9990, 622.9201,
623.0497, 688.8182, 723.3523,
862.0787, 862.7373, 981.1648,
981.5639, 1012.9824, 1016.5118,
1023.3193, 1059.4882, 1060.1754,
1174.4548, 1197.2456, 1197.4010,
1334.4311, 1381.4611, 1512.1890,
1512.8331, 1636.7196, 1636.9729,
3155.6128, 3165.0158, 3165.4678,
3180.7980, 3181.2702, 3191.6442
29.2734, 208.8416, 343.5263,
414.8012, 476.4613, 529.3747,
637.7413, 713.5210, 744.5274,
799.0889, 854.1689, 910.7506,
975.3207, 999.3188, 1000.2303,
1018.0176, 1051.7935, 1062.7963,
1111.3652, 1181.1717, 1203.3268,
1229.0458, 1328.0821, 1356.2521,
1414.7825, 1470.5161, 1491.2733,
1504.3213, 1530.0654, 1626.9749,
1649.0184, 3020.6910, 3074.9330,
3101.1065, 3151.9788, 3153.6044,
3166.2375, 3174.5448, 3187.3758
Species
m-Xylene
(C8H10)
Energy
(hartree)
-310.251059
3
CH2
-39.069838
1
CH2
-39.057322
H2
-1.166083
O2
-150.164612
N2
-109.398465
CO
-113.182004
CO2
-188.372094
H2O
-76.337482
H2O2
H2CO
-151.378792
-114.344176
NH3
-56.460190
Phenol
-306.939197
Cartesian coordinates
(in Å)
1
6
1
6
1
6
1
6
6
1
6
6
1
1
1
6
1
1
1
6
1
1
6
1
1
1
1
8
8
7
7
6
8
6
8
8
8
1
1
8
1
8
1
6
1
1
8
7
1
1
1
6
-2.801504000
0.006376000
0.009067000
1.209211000
2.148747000
-1.206008000
-2.140892000
-1.226247000
-0.003227000
-0.007081000
1.219395000
2.526123000
2.361215000
3.133469000
3.121108000
-2.528642000
-2.678427000
-2.548016000
-3.381086000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.824523000
0.000000000
-0.824523000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
-0.813692000
0.813692000
1.130788000
0.014231000
1.820441000
2.905172000
1.125188000
1.668994000
1.130750000
1.681751000
-0.264114000
-0.947018000
-2.033782000
-0.275614000
-1.033271000
-2.112462000
-0.777544000
-0.795705000
-1.029122000
-1.542467000
-1.792309000
-0.365079000
0.000000000
0.997024000
-0.997024000
0.000000000
0.860186000
-0.860186000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.756944000
-0.756944000
0.726812000
0.896106000
-0.726812000
-0.896106000
0.000000000
0.938825000
-0.938825000
0.000000000
0.000000000
0.939571000
-0.469786000
-0.469786000
-1.216404000
25
1.037039000
-0.000959000
-0.001007000
-0.004151000
-0.006957000
0.004341000
0.008512000
0.005402000
0.003836000
0.007558000
-0.001154000
0.000108000
-0.011929000
-0.873719000
0.887610000
-0.004325000
-0.959978000
0.779100000
0.152217000
0.103831000
-0.311494000
-0.311494000
0.177272000
-0.531815000
-0.531815000
0.372087000
-0.372087000
0.602838000
-0.602838000
0.547721000
-0.547721000
-0.643922000
0.482942000
0.000000000
1.160399000
-1.160399000
0.118665000
-0.474661000
-0.474661000
-0.052652000
0.421214000
-0.052652000
0.421214000
-0.525958000
-1.118196000
-1.118196000
0.674018000
0.115833000
-0.270276000
-0.270276000
-0.270276000
0.000187000
Frequencies
(cm-1)
22.9752, 40.5187, 198.0070,
221.8530, 274.8307, 405.0628,
443.6389, 523.2974, 529.3380,
543.1025, 711.6499, 736.5749,
784.7861, 896.1194, 903.4813,
919.9836, 982.8758, 999.9728,
1013.9091, 1035.1524, 1061.5558,
1062.4821, 1121.9822, 1179.6310,
1196.4479, 1270.3071, 1322.1998,
1345.6185, 1413.7403, 1416.4216,
1451.4874, 1488.3866, 1489.0174,
1492.4620, 1509.0337, 1526.5268,
1631.0198, 1650.5342, 3022.2533,
3023.0597, 3071.2460, 3071.8405,
3101.2219, 3101.7068, 3143.8070,
3151.5722, 3160.2902, 3178.4563
1056.3192, 3116.6521, 3357.3405
1404.6409, 2885.3058, 2947.0650
4419.2599
1640.9258
2447.5326
2220.5599
666.4978, 666.4978, 1375.6153,
2436.0748
1637.9196, 3812.7536, 3909.9019
345.5417, 943.3105, 1302.5322,
1456.1399, 3783.6027, 3784.8359
1202.2787, 1270.3779, 1539.0456,
1826.8033, 2868.7799, 2918.1862
1071.7409, 1682.0591, 1682.0593,
3460.0346, 3578.9976, 3578.9977
230.9934, 343.8735, 406.1389,
Species
Energy
(hartree)
OH
-75.649720
HO2
-150.741101
HCO
-113.704759
Cartesian coordinates
(in Å)
1
6
1
6
1
6
1
6
1
6
8
1
8
1
8
1
8
6
1
8
1.648329000
-0.262528000
-0.822475000
1.854626000
2.937847000
1.169374000
1.721653000
-0.220218000
-0.765045000
-0.940171000
-2.304300000
-2.677130000
0.000000000
0.000000000
0.055289000
-0.884630000
0.055289000
0.062307000
-0.872303000
0.062307000
-2.169247000
-1.196865000
-2.127937000
-0.027298000
-0.045721000
1.188299000
2.121502000
1.220925000
2.157204000
0.024018000
0.110628000
-0.776871000
0.000000000
0.000000000
-0.609416000
-0.871133000
0.718308000
0.584183000
1.215065000
-0.590020000
26
-0.000320000
0.000222000
0.000238000
-0.000139000
-0.000759000
-0.000123000
0.000624000
0.000058000
0.000868000
-0.000038000
-0.000185000
-0.000176000
0.108357000
-0.866852000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
Frequencies
(cm-1)
421.0333, 515.9324, 536.5598,
633.3490, 698.6951, 760.8089,
819.5118, 830.0126, 884.5615,
961.0585, 983.4677, 1012.4479,
1044.0057, 1093.9214, 1176.9416,
1190.2117, 1198.9817, 1288.2460,
1349.3386, 1370.8758, 1502.5830,
1531.0742, 1638.4870, 1651.1165,
3145.8531, 3166.2551, 3174.8121,
3189.2281, 3196.0964, 3831.9522
3704.7381
1164.9194, 1428.5061, 3606.9913
1111.2434, 1941.6055, 2619.4834
Table S3: Geometries, Energies (at 0 K) and Frequencies for all Species for
the C2H2 + OH Test Case Calculated at the Composite Method CBS-QB3.
Species
CHCHOH
CH2CHO
C2H2OH_CHCHO
H
(TS1)
CHCHOH_C
H2CHO
(TS2)
Energy
(hartree)
-152.887400
-152.932841
-152.835619
-152.831235
Cartesian coordinates
(in Å)
6
1
6
1
8
1
6
1
1
6
1
8
6
1
6
1
8
1
6
1
6
1
8
1
0.111805000
0.104990000
1.227346000
2.288874000
-1.164078000
-1.116145000
1.055667000
2.095014000
0.809252000
0.000000000
0.297374000
-1.191955000
-0.552073000
-0.155373000
-1.254609000
-1.793624000
1.433067000
1.324557000
-0.000975000
0.144525000
-1.105611000
-2.118290000
1.051431000
0.201829000
0.387671000
1.478191000
-0.301791000
-0.133918000
-0.099473000
-1.063769000
-0.528211000
-0.221283000
-1.583503000
0.427899000
1.494278000
0.114047000
0.625809000
1.611040000
-0.360299000
-1.274755000
-0.138053000
-0.824925000
0.533723000
1.611717000
-0.308812000
0.031794000
-0.236426000
-1.101566000
27
-0.000135000
0.000253000
-0.000002000
0.000213000
0.000045000
-0.000002000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.000000000
0.031576000
0.082192000
-0.018812000
-0.082975000
-0.083704000
0.593826000
-0.015560000
-0.017259000
-0.034146000
0.187352000
0.021612000
-0.044752000
Frequencies
(cm-1)
473.9616, 480.2561, 577.0150,
770.9786, 845.0895, 1106.3025,
1249.6166, 1364.8478, 1672.0399,
3099.8113, 3300.4924, 3790.5949
451.0390, 505.2945, 756.6299,
975.3570, 980.0742, 1150.9088,
1396.7912, 1470.4036, 1553.1200,
2927.2254, 3137.8023, 3253.6025
-256.5398, 85.5106, 246.5271,
612.8470, 643.0704, 672.1907,
770.5411, 787.1250, 973.3513,
3416.2442, 3504.4531, 3752.6748
-1961.3341, 293.3987, 816.1764,
911.8011, 1014.0462, 1100.0497,
1168.7527, 1308.1982, 1405.4835,
1168.7527, 1308.1982, 1405.4835,
2007.2122, 3115.2840, 3163.1271
Table S4: Geometries, Energies (at 0 K) and Frequencies for all Species for
the C2H5O Decomposition Test Case Calculated at the Composite Method
CBS-QB3.
Species
C2H5O
CH3CHO
H
C2H5O_CH3+
CH2O
(TS1)
C2H5O_CH3C
HO+H
(TS2)
Energy
(hartree)
-154.105069
-153.582464
-0.499818
-154.079430
-154.073005
Cartesian coordinates
(in Å)
Frequencies
(cm-1)
6
1
1
1
6
1
1
8
6
1
1
1
6
1
8
1
1.043292000
0.926212000
2.058018000
0.926212000
0.000000000
0.127916000
0.127916000
-1.303253000
-1.168836000
-1.707806000
-1.707686000
-1.155415000
0.235610000
0.305111000
1.233144000
0.000000000
-0.602179000
-1.232883000
-0.192545000
-1.232883000
0.511763000
1.192737000
1.192737000
0.101916000
-0.147778000
0.222534000
0.222271000
-1.237493000
0.397203000
1.508704000
-0.276570000
0.000000000
0.000000000
0.884507000
0.000000000
-0.884507000
0.000000000
0.865817000
-0.865817000
0.000000000
-0.000009000
-0.878909000
0.879093000
-0.000118000
-0.000011000
0.000043000
0.000001000
0.000000000
105.7852, 279.7098, 432.4404,
866.3798, 886.8727, 1068.7473,
1098.0429, 1239.3062, 1341.9650,
1388.8334, 1410.0697, 1484.6265,
1496.0527, 2885.7274, 2889.1927,
3029.3194, 3095.5996, 3105.4138
6
1
1
1
6
1
1
8
6
1
1
1
6
1
1
8
0.928049000
0.504229000
1.974722000
0.504229000
0.000000000
0.541597000
0.541597000
-1.204333000
1.188112000
1.539222000
1.205501000
1.868058000
-0.226775000
-0.315815000
-0.315758000
-1.218653000
-1.212477000
-1.583853000
-0.931741000
-1.583853000
0.797328000
1.044363000
1.044363000
0.562701000
-0.166187000
-0.694605000
-0.859216000
0.669830000
0.303485000
1.613884000
1.182392000
-0.342009000
0.000000000
0.923228000
0.000000000
-0.923228000
0.000000000
0.933345000
-0.933345000
0.000000000
0.045173000
-0.849343000
0.886590000
0.222480000
-0.219728000
1.075562000
-0.896339000
0.076048000
-341.2621, 132.7277, 265.8136,
497.5349, 545.1008, 599.0329,
893.3380, 1105.7079, 1249.3354,
1408.8302, 1427.2659, 1489.2175,
1636.0319, 2880.1500, 2925.1872,
3091.1101, 3255.6722, 3268.3694
28
160.1833, 508.1924, 776.7180,
882.5968, 1125.5861, 1135.2928,
1374.6562, 1425.8709, 1460.3871,
1470.9204, 1824.0273, 2856.2355,
3021.5533, 3076.6246, 3136.3551
-
-812.8757, 177.8140, 386.8012,
454.0130, 500.9202, 810.5811,
896.5167, 1097.7412, 1125.1166,
1374.9230, 1401.9274, 1464.3991,
1474.2531, 1694.4588, 2851.4613,
3022.6491, 3089.8835, 3135.1578
Table S5: Geometries, Energies (at 0 K) and Frequencies for all Species for
the C2H5 + O2 Test Case Calculated at the Composite Method CBS-QB3.
Species
CCOO
CC=O
CCOOH
cy(CCO)
CCOO_C2H4
+HO2
CCOO_CCH
O+OH
(TS1)
CCOO_
CCOOH
(TS2)
Energy
(hartree)
-229.190553
-153.582464
-229.163565
-153.539321
-229.140768
-229.124949
-229.133193
Cartesian coordinates
(in Å)
6
6
8
8
1
1
1
1
1
6
6
8
1
1
1
1
6
6
8
8
1
1
1
1
1
6
1
1
6
1
8
1
6
6
8
8
1
1
1
1
1
6
6
8
8
1
1
1
1
1
6
6
8
8
1
1
-1.463617000
-0.499652000
0.800072000
1.454689000
-0.318336000
-2.428795000
-1.620584000
-1.071343000
-0.819420000
1.168836000
-0.235610000
-1.233144000
1.707806000
1.707686000
-0.305111000
1.155415000
-1.495891000
-0.630078000
0.656086000
1.418955000
-2.061001000
-1.597335000
-0.500128000
1.354446000
-1.040495000
0.000000000
0.919128000
-0.920258000
0.000000000
0.920258000
0.000000000
-0.919128000
1.050198000
1.284400000
-1.149159000
-1.262341000
-0.032193000
1.028002000
1.029170000
1.630479000
1.628953000
1.617509000
0.332160000
-0.655290000
-1.519859000
2.133186000
-0.503262000
2.281522000
1.422591000
0.369140000
1.224996000
0.540217000
-0.792403000
-1.140784000
-0.029553000
0.959091000
-0.475370000
0.642379000
0.432553000
-0.566055000
0.716694000
-0.296285000
-0.534118000
-1.430207000
1.609879000
-0.147778000
0.397203000
-0.276570000
0.222534000
0.222271000
1.508704000
-1.237493000
-0.551475000
0.604444000
0.566943000
-0.498188000
-1.084282000
-0.850972000
0.709623000
-1.190795000
1.548570000
0.733842000
1.270080000
1.268691000
-0.733842000
-1.268691000
0.000000000
-1.270080000
0.745474000
-0.619795000
0.616137000
-0.648534000
-0.955050000
1.319683000
1.319835000
-1.089440000
-1.089930000
-0.172376000
0.055231000
0.738679000
-0.486269000
0.783520000
-0.980394000
-0.830920000
-0.607268000
0.318655000
-0.567028000
0.754404000
0.596299000
-0.700113000
-1.137874000
1.628526000
29
-0.091955000
0.255366000
-0.382269000
0.175610000
1.328940000
0.388957000
-1.171200000
0.261262000
-0.135148000
-0.000009000
-0.000011000
0.000001000
-0.878909000
0.879093000
0.000043000
-0.000118000
-0.097864000
0.247322000
-0.387096000
0.240395000
0.655459000
-1.134698000
1.328761000
-0.431491000
-0.141170000
-0.371847000
-0.594414000
-0.593865000
-0.371847000
-0.593865000
0.854841000
-0.594414000
0.000118000
0.000032000
-0.000112000
0.000048000
-0.001049000
0.917349000
-0.917056000
-0.917396000
0.917766000
-0.224173000
0.512514000
-0.186441000
-0.129694000
-0.377302000
0.469226000
0.340270000
-1.206392000
1.573232000
-0.119905000
0.212656000
-0.291970000
0.162117000
0.061460000
-0.293160000
Frequencies
(cm-1)
116.7915, 234.5468, 358.4345,
529.9754, 800.5442, 844.2614,
993.5872, 1097.9489, 1151.1675,
1202.0581, 1308.3070, 1377.5958,
1409.6847, 1482.0252, 1486.8144,
1506.3816, 3040.2811, 3064.7443,
3105.7147, 3112.9228, 3132.6945
160.1833, 508.1924, 776.7180,
882.5968, 1125.5861, 1135.2928,
1374.6562, 1425.8709, 1460.3871,
1470.9204, 1824.0273, 2856.2355,
3021.5533, 3076.6246, 3136.3551
117.3824, 162.7957, 221.0660,
357.3773, 469.2429, 571.5328,
834.2842, 861.6758, 953.3132,
1056.6344, 1136.5401, 1272.8955,
1362.9643, 1370.8436, 1446.5044,
1460.3111, 2982.7459, 3057.0435,
3138.3361, 3248.6642, 3765.4762
818.3726, 843.3580, 889.6657,
1039.1049, 1139.1615, 1141.9109,
1167.6774, 1171.8659, 1300.3290,
1504.0082, 1540.2137, 3077.2326,
3084.8781, 3158.2361, 3173.6983
-1099.1262, 218.6724, 359.1594,
480.1130, 517.8001, 643.2699,
834.1963, 889.1725, 1005.3797,
1040.9016, 1228.5187, 1303.5575,
1315.3738, 1341.4865, 1470.1616,
1570.7688, 1604.7107, 3099.6101,
3158.0062, 3177.1480, 3246.1353
-1842.4558, 133.3782, 206.2576,
416.8852, 656.5526, 780.5559,
797.0365, 912.3736, 1057.9303,
1113.5882, 1118.1073, 1162.4026,
1355.4106, 1407.9920, 1473.7655,
1479.3115, 1947.0655, 3013.8935,
3064.8889, 3082.4506, 3119.0744
-2273.9888, 275.5101, 439.9312,
553.9176, 690.6842, 869.2051,
897.8081, 903.1570, 959.7678,
1043.9316, 1112.4091, 1166.1895,
1245.6413, 1343.9535, 1454.1942,
1497.3342, 1728.0249, 3025.7684,
Species
CCOOH_
C2H4+HO2
(TS3)
CCOOH_cy(
CCO)+OH
(TS4)
Energy
(hartree)
-229.137804
-229.141526
Cartesian coordinates
(in Å)
1
1
1
6
6
8
8
1
1
1
1
1
6
6
8
8
1
1
1
1
1
1.948644000
1.471248000
0.524791000
1.622849000
0.921894000
-0.760812000
-1.611066000
1.547245000
2.180432000
0.516665000
-1.672364000
1.134587000
-1.701985000
-0.584645000
0.200206000
1.881068000
-1.977133000
-2.143114000
-0.391918000
2.139780000
-0.558024000
-0.966524000
-0.733950000
0.916074000
0.536865000
-0.551086000
-0.470944000
0.348539000
1.506515000
0.481986000
-0.531994000
1.145659000
-1.537605000
-0.257366000
0.703684000
-0.442599000
0.045844000
-0.731666000
-0.616833000
1.232512000
-0.772738000
1.384855000
30
0.585334000
-1.166961000
1.295645000
-0.115422000
0.362595000
-0.485304000
0.254571000
0.362749000
-1.042483000
1.366644000
-0.291736000
-0.032352000
0.056511000
0.021740000
-0.141987000
-0.003536000
0.987860000
-0.862443000
0.958825000
0.443761000
-0.833319000
Frequencies
(cm-1)
3084.1658, 3099.2958, 3192.1739
-537.2979, 96.5583, 229.6776,
313.0231, 422.0756, 474.5590,
816.8560, 822.2708, 918.1757,
1031.6991, 1083.2572, 1239.0800,
1259.2651, 1382.9124, 1464.6052,
1545.1332, 3137.3725, 3142.1358,
3215.7015, 3241.0711, 3728.0034
-737.4492, 85.0359, 123.0790,
257.1079, 390.9873, 495.9172,
763.2849, 836.4830, 937.3066,
1002.5935, 1166.1663, 1168.5617,
1200.6425, 1313.8595, 1467.7256,
1535.6212, 3029.5544, 3083.5689,
3164.9885, 3281.0621, 3788.8377
Table S6: Thermodynamic Data for Species in the NASA format
31
32
33
Table S7: An Example of MSMC Input File (File name: C2H5O.minp)
<Description>
C2H5O decomposition, tunneling & HIR included
</Description>
OpticalIsomer=1
EnergyLevel=(-39.774369, 2)
Coordinates
C
0.000000000 0.000000000 0.000000000
H
0.000000000 1.080624000 0.000000000
H
0.935848000 -0.540312000 0.000000000
H
-0.935848000 -0.540312000 0.000000000
FREQUENCY
506.7550
1403.4716
1403.4733
3102.7007
3281.7014
3281.7028
Scale=0.99
</R1>
<Temperature>//Unit: K
300 400 500 600 700 800 900 1000 1500 2000
</Temperature>
<Pressure>//Unit: torr
760E-2 760E-1 760E+0 760E+1 760E+2
</Pressure>
<NASAfit>
ON
</NASAfit>
<R2>
NAME CH2O
Symmetry=2
Parity
Undefined
Optical_Isomer=1
EnergyLevel=(-114.370661, 1)
Coordinates
C
0.000000000 0.000000000 -0.525958000
H
0.000000000 0.938825000 -1.118196000
H
0.000000000 -0.938825000 -1.118196000
O
0.000000000 0.000000000 0.674018000
Frequency
1202.2787
1270.3779
1539.0456
1826.8033
2868.7799
2918.1863
Scale=0.99
</R2>
<ELMT> // Electronic structure calculation method
CBS-QB3
</ELMT>
<Kinetics>
ON
</Kinetics>
<Initiation>
CH3
</Initiation>
<BoltzmannReactant>
ON
</BoltzmannReactant>
<ArrheniusFitting>
modified
</ArrheniusFitting>
<IM1>
Name C2H5O
Symmetry=1
Parity
Undefined
OpticalIsomer=1
LJPARAmeter=(EPSILON=362.6, SIGMA=4.53)
TRANSferEnergy 100
EnergyLevel=(-154.169095, 2)
COORDINATES
C
1.043292000 -0.602179000 0.000000000
H
0.926212000 -1.232883000 0.884507000
H
2.058018000 -0.192545000 0.000000000
H
0.926212000 -1.232883000 -0.884507000
C
0.000000000 0.511763000 0.000000000
H
0.127916000 1.192737000 0.865817000
H
0.127916000 1.192737000 -0.865817000
O
-1.303253000 0.101916000 0.000000000
FREQUENCY
105.7852
279.7098
432.4404
866.3798
886.8727
1068.7473
1098.0429
1239.3062
1341.9650
1388.8334
1410.0697
1484.6265
1496.0527
2885.7274
2889.1927
3029.3194
3095.5996
3105.4138
Scale=0.99
HinderedRotor=(HinMode=2, HinSym=3, HinAxis=1-5,
HinGroup=2,3,4)
<EnergyStep>//Unit: cm^-1
100.00
</EnergyStep>
<Omega>
Lennard-Jones
</Omega>
<Collider>
He
Epsilon=10.0
Sigma=2.55
</Collider>
<CoreNumber>
4
</CoreNumber>
<GridResolution>
low
</GridResolution>
//-----------------------------------------------------------------------------//
<R1>
NAME CH3
Symmetry=6
PARITY Undefined
34
HindrancePotential
theta dE0 [kcal/mol]
0
0.00000
10
0.08636
20
0.44991
30
1.02544
40
1.68472
50
2.24466
60
2.50955
70
2.28815
80
1.73017
90
1.05329
100 0.45553
110 0.08110
120 -0.00690
130 0.07116
140 0.43204
150 1.02004
160 1.69724
170 2.26380
180 2.51272
190 2.26439
200 1.69867
210 1.02422
220 0.43542
230 0.07882
240 -0.00578
250 0.08352
260 0.45861
270 1.05767
280 1.73515
290 2.29035
300 2.51095
310 2.24693
320 1.68385
330 1.02409
340 0.44640
350 0.08334
360 -0.00543
</IM1>
<TS-R-IM1>
NAME TS1
EnergyLevel=(-154.14019, 2)
Symmetry=1
Parity
Undefined
OpticalIsomer=1
Tunneling=Eckart
Coordinates
C
0.928049000 -1.212477000
H
0.504229000 -1.583853000
H
1.974722000 -0.931741000
H
0.504229000 -1.583853000
C
0.000000000 0.797328000
H
0.541597000 1.044363000
H
0.541597000 1.044363000
O
-1.204333000 0.562701000
FREQUENCY
-341.2621
132.7277
497.5349
545.1008
893.3380
1105.7079
1408.8302
1427.2659
1636.0319
2880.1500
2925.1872
3091.1101
3255.6722
3268.3694
Scale=0.99
HinderedRotor=(HinMode=1, HinSym=3, HinAxis=1-5,
HinGroup=2,3,4)
HindrancePotential
theta dE0 [kcal/mol]
0
0.00000
10
0.05021
20
0.19709
30
0.40721
40
0.63324
50
0.80804
60
0.87700
70
0.81622
80
0.64598
90
0.42293
100 0.20892
110 0.05628
120 -0.00050
130 0.04884
140 0.19775
150 0.41180
160 0.63849
170 0.81284
180 0.87667
190 0.81258
200 0.63968
210 0.41411
220 0.19834
230 0.04977
240 -0.00029
250 0.05547
260 0.20906
270 0.42263
280 0.64740
290 0.81574
300 0.87382
310 0.80623
320 0.63334
330 0.40819
340 0.19684
350 0.05023
360 -0.00081
</TS-R-IM1>
<TS-IM1-P1>
NAME TS2
EnergyLevel=(-154.129865, 2)
Symmetry=1
Parity
Undefined
OpticalIsomer=2
Tunneling=Eckart
Coordinates
C
1.188112000 -0.166187000
H
1.539222000 -0.694605000
H
1.205501000 -0.859216000
H
1.868058000 0.669830000
C
-0.226775000 0.303485000
H
-0.315815000 1.613884000
H
-0.315758000 1.182392000
O
-1.218653000 -0.342009000
0.000000000
0.923228000
0.000000000
-0.923228000
0.000000000
0.933345000
-0.933345000
0.000000000
265.8136
599.0329
1249.3354
1489.2175
35
0.045173000
-0.849343000
0.886590000
0.222480000
-0.219728000
1.075562000
-0.896339000
0.076048000
FREQUENCY
-812.8757
177.8140
386.8012
454.0130
500.9202
810.5811
896.5167
1097.7412
1125.1166
1374.9230
1401.9274
1464.3991
1474.2531
1694.4588
2851.4613
3022.6491
3089.8835
3135.1578
Scale=0.99
HinderedRotor=(HinMode=1, HinSym=3, HinAxis=1-5,
HinGroup=2,3,4)
HindrancePotential
Ttheta dE0 [kcal/mol]
0
0.0000
10
0.1348
20
0.4593
30
0.8737
40
1.2448
50
1.4588
60
1.4609
70
1.2711
80
0.9514
90
0.5859
100
0.2591
110
0.0488
120
0.0094
130
0.1586
140
0.4674
150
0.8577
160
1.2207
170
1.4470
180
1.4695
190
1.2866
200
0.9561
210
0.5694
220
0.2296
230
0.0290
240
0.0225
250
0.2073
260
0.5342
270
0.9153
280
1.2502
290
1.4516
300
1.4734
310
1.3200
320
1.0322
330
0.6752
340
0.3298
350
0.0807
360
0.0029
</TS-IM1-P1>
<Outlet1>
Name H
Symmetry=1
Parity
Undefined
OpticalIsomer=1
EnergyLevel=(-0.499818, 2)
COORDINATES
H
0.000000000 0.000000000
FREQUENCY
0.00
Scale=0.99
</Outlet1>
<Outlet2>
Name CH3CHO
Symmetry=1
Parity
Undefined
OpticalIsomer=1
EnergyLevel=(-153.637676, 1)
COORDINATES
C
-1.168836000 -0.147778000 -0.000009000
H
-1.707806000 0.222534000 -0.878909000
H
-1.707686000 0.222271000 0.879093000
H
-1.155415000 -1.237493000 -0.000118000
C
0.235610000 0.397203000 -0.000011000
H
0.305111000 1.508704000 0.000043000
O
1.233144000 -0.276570000 0.000001000
FREQUENCY
160.1833
508.1924
776.7180
882.5968
1125.5861
1135.2928
1374.6562
1425.8709
1460.3871
1470.9204
1824.0273
2856.2355
3021.5533
3076.6246
3136.3551
Scale=0.99
HinderedRotor=(HinMode=1, HinSym=3, HinAxis=1-5,
HinGroup=2,3,4)
HindrancePotential
Theta dE0 [kcal/mol]
0
0.00000
10
0.07500
20
0.28044
30
0.56453
40
0.85044
50
1.05124
60
1.10809
70
1.00940
80
0.78880
90
0.51663
100
0.26165
110
0.07953
120
0.00281
130
0.04571
140
0.20704
150
0.46249
160
0.76104
170
1.01096
180
1.11027
190
1.01211
200
0.76117
210
0.46231
220
0.20552
230
0.04412
240
0.00223
250
0.08005
260
0.26291
270
0.51792
280
0.79106
290
1.00889
300
1.10832
310
1.04986
320
0.84802
330
0.56558
340
0.28175
0.000000000
36
350
0.07682
360
0.00226
</Outlet2>
Components 1 2
</Product1>
//----------------------------------------------------------------------------------//
<Product1>
Name CH3CHO+H
37
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38