Supplementary material for an article to be published In J. Mol. Model.
Thermochemical and Kinetics Studies of the CH3SH + S (3P) Hydrogen Abstraction and Insertion
Reactions
Daniely V. V. Cardosoa, Leonardo A. Cunhaa, Rene F. K. Spadaa,b, Luiz F. A. Ferrãoa, Orlando RobertoNetoc, Francisco B. C. Machadoa*
a
Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos, 12.228-900 São
Paulo, Brazil.
b
Departamento de Física, Instituto Tecnológico de Aeronáutica, São José dos Campos, 12.228-900 São
Paulo, Brazil.
c
Divisão de Aerotermodinâmica e Hipersônica, Instituto de Estudos Avançados, São José dos Campos,
12.228-001 São Paulo, Brazil.
Correspondence to: Francisco B. C. Machado (e-mail: fmachado@ita.br)
Units:
1 kcal/mol = 4.184 kJ/mol
1 cm-1 = 0.0119627 kJ/mol
1 Angstrom (Å) = 10-10 m
1 Bohr (a0) = 5.2917721092(17) 10-11 m
Contents:
Table S-1 Bond lengths (Å) and angles (in deg) of CH3SH
Table S-2 Bond lengths (Å) and angles (in deg) of CH3S
Table S-3 Bond lengths (Å) and angles (in deg) of CH2SH
Table S-4 Bond lengths (Å) and angles (in deg) of CH3
Table S-5 Bond length (Å) of SH
Table S-6 Bond lengths (Å) and angles (in deg) of HS2
Table S-7 Bond lengths (Å) and angles (in deg) of TS1
Table S-8 Bond lengths (Å) and angles (in deg) of TS2
Table S-9 Bond lengths (Å) and angles (in deg) of TS3
In this work we denote maDdZ as the combination of maug-cc-pVDZ (C and H) and maug-ccpV(D+d)Z (S), while aXdZ denotes the combination of aug-cc-pVXZ (C and H) and aug-cc-pV(X+d)Z
(S).
Table S-10 ICVT reaction rate constants (in cm3 molecule1 s1) for R1 using dual-level dynamics
(BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
Table S-11 ICVT reaction rate constants (in cm3 molecule1 s1) for R2 using dual-level dynamics
(BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
Table S-12 ICVT reaction rate constants (in cm3 molecule1 s1) for R3 using dual-level dynamics
(BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
Table S-13 Activation energy (in kcal mol1) for R1 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
Table S-14 Activation energy (in kcal mol1) for R2 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
Table S-15 Activation energy (in kcal mol1) for R3 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
Fig. S-1 Arrhenius plots of the rate constants for the first reaction path calculated with ICVT using
VMEP
G
and Va as explained in Table S-10
Fig. S-2 Arrhenius plots of the rate constants for the second reaction path calculated with ICVT using
VMEP and VaG as explained in Table S-11
Fig. S-3 Arrhenius plots of the rate constants for the third reaction path calculated with ICVT using
VMEP and VaG as explained in Table S-12
Table S-1 Bond lengths (Å) and angles (in deg) of CH3SH
Coordinates
r (1C–2S)
r (2S–3H)
r (1C– 4H)
r (1C–5H)
r (1C–6H)
 (3H, 2S, 1C)
 (4H, 1C, 2S)
 (5H, 1C, 2S)
 (6H, 1C, 2S)
 (5H, 1C, 4H)
 (6H, 1C, 4H)
 (6H, 1C, 5H)
τ (4H,1C,2S,3H)
τ (5H,1C,2S,3H)
τ (6H,1C,2S,3H)
τ (4H,5H,1C,6H)
τ (5H,4H,1C,6H)
a
maDdZ
BB1K
aDdZ
aTdZ
M06-2X
aTdZ
MP2
aTdZ
Theor.a
Exp.b
Exp.c
1.797
1.340
1.092
1.091
1.091
97.3
106.2
111.7
111.7
108.4
108.4
110.2
180.0
62.0
62.0
118.6
119.7
1.799
1.339
1.090
1.089
1.089
97.2
106.3
111.6
111.6
108.5
108.5
110.3
180.0
62.0
62.0
118.7
119.9
1.796
1.332
1.082
1.081
1.081
97.3
106.3
111.4
111.4
108.6
108.6
110.3
180.0
61.8
61.8
118.9
119.9
1.812
1.337
1.087
1.086
1.086
96.8
106.2
111.2
111.2
108.8
108.8
110.4
180.0
61.8
61.8
119.4
120.4
1.812
1.334
1.087
1.086
1.086
96.7
106.1
111.2
111.2
108.9
108.9
110.5
180.0
61.8
61.8
119.5
120.5
1.814
1.340
1.090
1.090
1.090
96.8
106.6
-
1.814
1.335
1.092
96.5
-
1.816
1.327
1.100
1.106
1.100
100.4
108.7
108.5
108.5
110.4
110.5
110.3
-
Chang Y-T, Loew GH (1993) The reaction of atomic oxygen with methanethiol. A theoretical study of
the structures and the potential energy surface. Chem Phys Lett 205:543-549. doi: 10.1016/00092614(93)80010-M
b
Calloman JH, Hirota E, Kuchitsu K, Lafferty WJ, Maki AG, Pote CS (1976) Structure data on free
polyatomic molecules. In: Hellwege KH, Hellwege AM (eds) Landolt-Bornstein: group II: atomic and
molecular physics. Springer, Berlin
c
Herzberg G (1966) Electronic spectra and electronic structure of polyatomic molecules. Van Nostrand-
Reinhold, New York
Table S-2 Bond lengths (Å) and angles (in deg) of CH3S
Coordinates
maDdZ
BB1K
aTdZ
aTdZ
M06-2X
aTdZ
MP2
aTdZ
Theor.a
Exp. b
r (1C–2S)
1.774
1.776
1.773
1.789
1.792
1.800 1.791
r (1C– 3H)
1.098
1.096
1.089
1.093
1.092
1.095 1.090
r (1C– 4H)
1.093
1.090
1.082
1.087
1.087
1.091 1.090
r (1C–5H)
1.093
1.090
1.082
1.087
1.087
1.091 1.090
106.3
106.3
106.2
107.0 110.0
106.3
106.3
 (3H,1C,2S)
111.8
111.6
111.4
109.8
112.0
112.0
 (4H,1C,2S)
111.8
111.6
111.4
109.8
112.0
112.0
 (5H,1C,2S)
107.8
108.1
108.3
108.4
107.7
107.6
 (4H,1C,3H)
107.8
108.1
108.3
108.4
107.7
107.6
 (5H,1C,3H)
110.9
111.0
110.9
111.0
111.0
110.4
 (5H,1C,4H)
τ (4H,5H,1C,2S) 126.0 126.0 125.6 125.1 124.8
τ (3H,4H,1C,2S)
117.4
117.7
117.3
117.3
116.6
τ (3H,5H,1C,2S) 117.3 117.3 117.4
116.6
177.7
τ (3H,1C,5H,4H)
117.5
117.6 117.9
118.3
118.7
τ (5H,3H,1C,4H) 119.6
119.7
119.9
120.2
120.5
a
Chang Y-T, Loew GH (1993) The reaction of atomic oxygen with methanethiol. A theoretical study of
the structures and the potential energy surface. Chem Phys Lett 205:543-549. doi: 10.1016/00092614(93)80010-M
b
Endo Y, Saito S, Hirota E (1985) The microwave-spectrum of the thiomethoxy radical CH3S. J Chem
Phys 85:1770-1777. doi: 10.1063/1.451178
Table S-3 Bond lengths (Å) and angles (in deg) of CH2SH
BB1K
M06-2X
MP2
Coordinates
maDdZ aDdZ aTdZ
aTdZ
aTdZ
r (1C–2S)
1.705 1.705 1.697
1.712
r (2S–3H)
1.340 1.339 1.332
1.336
r (1C– 4H)
1.084 1.080 1.072
1.076
r (1C–5H)
1.083 1.079 1.071
1.075
98.1
98.2
98.2
97.9
 (3H,2S,1C)
116.5 116.9 117.0
116.8
 (4H,1C,2S)
121.7 121.8 121.8
121.5
 (5H,1C,2S)
120.8 121.3 121.2
121.0
 (5H,1C,4H)
τ (4H,1C,2S,3H) 179.7 180.0 180.0 178.1
τ (5H,1C,2S,3H) 11.7
0.0
0.0
10.8
τ (5H,1C,4H,2S) 168.8 180.0 180.0
171.1
τ (4H,1C,5H,2S) 168.2 180.0 180.0
170.7
a
Yi-Zhen T, Ya-Ru P, Jing-Yu S, Hão S, Rong-Shun W
Theor. a
1.710
1.732
1.333
1.348
1.075
1.078
1.074
97.7
98.0
116.8
121.6
121.2
179.4
6.4
173.1
172.7
(2008) DFT and ab initio study on the reaction
mechanism of CH2SH+O2. Theor Chem Accounts 121:201-207. doi: 10.1007/s00214-008-0466-z
Table S-4 Bond lengths (Å) and angles (in deg) of CH3
BB1K
M06-2X MP2
Coordinates
Exp. a
maDZ
aDZ
aTZ
aTZ
aTZ
r (1C – 3H)
1.084
1.081 1.073
1.076
1.075 1.079
r (1C – 4H)
1.084
1.081 1.073
1.077
1.075 1.079
120.0 120.0
120.0
120.0 120.0
120.0
 (3H,1C,2H)
120.0 120.0
120.0
120.0 120.0
 (4H,1C,2H)
120.0
120.0
120.0
120.0
120.0 120.0
 (4H,1C,3H)
120.0
τ (4H,1C,3H,2H) 180.0 179.9 180.0
179.9
180.0
a
Herzberg G (1966) Electronic spectra and electronic structure of polyatomic molecules. Van NostrandReinhold, New York
Table S-5 Bond length (in Å) of SH
Method
1S2H
BB1K/maug-cc-pV(D+d)Z
1.345
BB1K/aug-cc-pV(D+d)Z
1.345
BB1K/aug-cc-pV(T+d)Z
1.336
M06-2X/aug-cc-pV(T+d)Z
1.340
MP2/aug-cc-pV(T+d)Z
1.337
a
Experimental
1.341
NIST Chemistry, Webbook. Available at: http://webbook.nist.gov/chemistry. Accessed 9 May 2013
Table S-6 Bond lengths (Å) and angles (in deg) of HS2
Coordinates
Method
r (1S – 2H) r (1S – 3S)  (3S,1S,2H)
BB1K/maDdZ
BB1K/aDdZ
BB1K/aTdZ
M06-2X/aTZ
MP2/aTdZ
1.352
1.352
1.343
1.348
1.344
1.954
1.955
1.944
1.958
1.955
102.0
101.5
101.8
101.6
105.5
Table S-7 Bond lengths (Å) and angles (in deg) of TS1
BB1K
M06-2X
Coordinates
maDdZ aDdZ aTdZ
aTdZ
MP2
aTdZ
r (1C-2S)
r (2S-3H)
r (1C-4H)
r (1C-5H)
r (1C-6H)
r (7S-3H)
 (3H,2S,1C)
 (4H,1C,2S)
 (5H,1C,2S)
 (6H,1C,2S)
 (7S,3H,2S)
τ (4H,1C,2S,3H)
τ (5H,1C,2S,3H)
τ (6H,1C,2S,3H)
τ (7S,3H,2S,1C)
1.801
1.609
1.091
1.086
1.086
1.492
96.1
105.7
111.1
111.1
166.7
180.0
61.9
61.9
0.0
1.784
1.615
1.096
1.092
1.092
1.513
97.9
105.5
111.8
111.8
168.9
180.0
62.4
62.4
0.0
1.787
1.618
1.093
1.089
1.089
1.506
97.8
105.7
111.6
111.6
167.3
180.0
62.3
62.3
0.0
1.784
1.601
1.086
1.081
1.081
1.512
97.7
105.7
111.5
111.5
167.6
180.0
62.2
62.2
0.0
1.799
1.628
1.091
1.086
1.086
1.503
96.3
106.0
111.1
111.1
167.3
180.0
61.9
61.9
0.0
Table S-8 Bond lengths (Å) and angles (in deg) of TS2
BB1K
Coordinates
maDdZ
aDdZ
r (1C-2S)
r (2S-3H)
r (1C-4H)
r (1C-5H)
r (1C-6H)
r (7S-5H)
 (3H,2S,1C)
 (4H,1C,2S)
 (5H,1C,2S)
 (6H,1C,2S)
 (7S,5H,1C)
τ (4H,1C,2S,3H)
τ (5H,1C,2S,3H)
τ (6H,1C,2S,3H)
τ (7S,5H,1C,2S)
1.722
1.341
1.089
1.551
1.089
1.474
97.8
112.4
111.4
117.9
175.0
170.6
80.3
33.0
163.9
1.723
1.340
1.086
1.542
1.085
1.477
97.8
112.7
110.7
118.0
174.5
170.8
80.5
31.9
165.1
Table S-9 Bond lengths (Å) and angles (in deg) of TS3
BB1K
Coordinates
maDdZ
aDdZ
r (1C-2S)
r (2S-3H)
r (1C-4H)
r (1C-5H)
r (1C-6H)
r (7S-2S)
 (3H,2S,1C)
 (4H,1C,2S)
 (5H,1C,2S)
 (6H,1C,2S)
 (7S,2S,1C)
τ (4H,1C,2S,3H)
τ (5H,1C,2S,3H)
τ (6H,1C,2S,3H)
τ (7S,2S,1C,4H)
2.185
1.340
1.089
1.088
1.089
2.056
88.8
103.1
103.6
103.1
172.8
60.4
179.9
60.1
120.0
2.181
1.340
1.086
1.085
1.086
2.056
88.5
102.6
103.8
102.6
173.5
60.2
180.0
60.1
119.8
aTdZ
M06-2X
aTdZ
MP2
aTdZ
1.719
1.333
1.078
1.522
1.077
1.477
97.7
112.7
109.4
117.6
179.4
171.5
78.8
32.9
20.5
1.728
1.337
1.083
1.561
1.082
1.468
97.5
113.0
109.1
118.0
176.2
172.2
78.6
32.5
140.1
1.731
1.334
1.083
1.500
1.082
1.473
97.2
112.6
109.8
117.6
175.4
170.6
79.8
32.7
162.5
aTdZ
M06-2X
aTdZ
MP2
aTdZ
2.157
1.331
1.076
1.078
1.078
2.047
88.5
104.0
103.1
103.1
173.4
60.0
179.8
60.3
119.7
2.184
1.336
1.083
1.081
1.083
2.068
88.5
102.8
103.7
102.8
173.7
60.2
180.0
60.1
119.8
2.161
1.334
1.082
1.081
1.082
2.050
88.7
103.0
103.6
103.0
173.4
60.2
180.0
60.2
119.8
Table S-10 ICVT calculated reaction rate constants (in cm3 molecule1 s1) of R1 using dual-level
dynamics (BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
T(K)
200
298
299
300
350
400
500
600
800
1000
1200
1500
2000
2500
3000
TST
CH3SH + S
ICVT
3.03E-17
2.14E-15
2.20E-15
2.27E-15
8.41E-15
2.33E-14
1.06E-13
3.13E-13
1.40E-12
3.87E-12
8.20E-12
1.89E-11
4.92E-11
9.57E-11
1.58E-10
1.18E-17
1.24E-15
1.28E-15
1.32E-15
5.42E-15
1.60E-14
7.79E-14
2.38E-13
1.09E-12
3.01E-12
6.37E-12
1.46E-11
3.79E-11
7.35E-11
1.21E-10
 CH3S + SH (R1)
ICVT/ZCT
ICVT/SCT
1.50E-17
1.38E-15
1.42E-15
1.47E-15
5.85E-15
1.70E-14
8.09E-14
2.44E-13
1.10E-12
3.04E-12
6.41E-12
1.47E-11
3.80E-11
7.36E-11
1.21E-10
1.61E-17
1.42E-15
1.47E-15
1.51E-15
5.98E-15
1.73E-14
8.18E-14
2.46E-13
1.11E-12
3.05E-12
6.42E-12
1.47E-11
3.80E-11
7.36E-11
1.21E-10
Table S-11 ICVT calculated reaction rate constants (in cm3 molecule1 s1) of R2 using dual-level
dynamics (BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
T(K)
200
298
299
300
350
400
500
600
800
1000
1200
1500
2000
2500
3000
TST
7.37E-27
5.39E-22
5.83E-22
6.29E-22
1.72E-20
2.14E-19
7.93E-18
9.59E-17
2.53E-15
2.05E-14
8.96E-14
4.30E-13
2.35E-12
7.19E-12
1.60E-11
CH3SH + S
ICVT
5.04E-27
4.21E-22
4.56E-22
4.93E-22
1.40E-20
1.78E-19
6.83E-18
8.42E-17
2.26E-15
1.85E-14
8.12E-14
3.91E-13
2.14E-12
6.55E-12
1.46E-11
 CH2SH + SH (R2)
ICVT/ZCT
1.21E-26
6.13E-22
6.61E-22
7.12E-22
1.83E-20
2.18E-19
7.77E-18
9.20E-17
2.38E-15
1.91E-14
8.30E-14
3.96E-13
2.16E-12
6.58E-12
1.47E-11
ICVT/SCT
3.62E-26
1.08E-21
1.16E-21
1.24E-21
2.79E-20
3.05E-19
9.68E-18
1.07E-16
2.60E-15
2.02E-14
8.64E-14
4.07E-13
2.19E-12
6.64E-12
1.48E-11
Table S-12 ICVT calculated reaction rate constants (in cm3 molecule1 s1) of R3 using dual-level
dynamics (BB1K/maDdZ potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ
thermochemistry data)
T(K)
200
298
299
300
350
400
500
600
800
1000
1200
1500
2000
2500
3000
TST
1.57E-21
1.64E-18
1.73E-18
1.81E-18
1.47E-17
7.31E-17
7.46E-16
3.76E-15
3.20E-14
1.27E-13
3.36E-13
9.55E-13
3.01E-12
6.47E-12
1.14E-11
CH3SH + S
ICVT
1.51E-21
1.62E-18
1.70E-18
1.79E-18
1.45E-17
7.22E-17
7.40E-16
3.74E-15
3.18E-14
1.26E-13
3.35E-13
9.52E-13
3.00E-12
6.35E-12
1.09E-11
 CH3 + HS2 (R3)
ICVT/ZCT
1.97E-21
1.82E-18
1.91E-18
2.01E-18
1.58E-17
7.70E-17
7.71E-16
3.85E-15
3.23E-14
1.28E-13
3.38E-13
9.57E-13
3.01E-12
6.36E-12
1.09E-11
ICVT/SCT
2.63E-21
2.06E-18
2.16E-18
2.27E-18
1.73E-17
8.24E-17
8.05E-16
3.96E-15
3.29E-14
1.29E-13
3.40E-13
9.61E-13
3.01E-12
6.37E-12
1.10E-11
Table S-13 Activation energy (in kcal mol1) for R1 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
CH3SH + S  CH3S + SH (R1)
ICVT ICVT/ZCT ICVT/SCT
5.62
5.47
5.42
T(K)
200 – 300
TST
5.15
300 – 400
5.56
5.95
5.84
5.81
400 – 600
6.19
6.43
6.35
6.33
600 – 1000
7.49
7.56
7.51
7.50
1000 – 1500
9.45
9.43
9.40
9.39
Table S-14 Activation energy (in kcal mol1) for R2 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
T(K)
200 – 300
CH3SH + S  CH2SH + SH (R2)
TST
ICVT ICVT/ZCT
ICVT/SCT
13.54
13.70
13.09
12.45
300 – 400
13.90
14.05
13.65
13.12
400 – 600
14.56
14.68
14.41
13.99
600 – 1000
15.99
16.07
15.90
15.61
1000 – 1500
18.14
18.19
18.08
17.89
Table S-15 Activation energy (in kcal mol1) for R3 using ICVT dual-level dynamics (BB1K/maDdZ
potential surface and high-level corrections from CCSD(T)/CBS//BB1K/aTdZ thermochemistry data)
T(K)
200 – 300
CH3SH + S  CH3 + HS2 (R3)
TST
ICVT ICVT/ZCT ICVT/SCT
8.41
8.44
8.26
8.06
300 – 400
8.82
8.82
8.70
8.57
400 – 600
9.40
9.41
9.33
9.24
600 – 1000
10.48
10.49
10.44
10.38
1000 – 1500
12.04
12.05
12.01
11.98
-22
R1
-24
-28
-1
-1
lnk (cm molecule s )
-26
-30
3
-32
-34
TST
ICVT
ICVT/ZCT
ICVT/SCT
-36
-38
-40
0
1
2
3
4
5
-1
(1000T ) K
Fig. S-1 Arrhenius plots of the rate constants for the first reaction path calculated with ICVT using
VMEP
G
and Va as explained in Table S-10
-20
R2
-25
-35
-1
-1
lnk (cm molecule s )
-30
-40
3
-45
-50
TST
ICVT
ICVT/ZCT
ICVT/SCT
-55
-60
-65
0
1
2
3
4
5
-1
(1000T ) K
Fig. S-2 Arrhenius plots of the rate constants for the second reaction path calculated with ICVT using
VMEP and VaG as explained in Table S-11
R3
-25
3
-1
-1
lnk (cm molecule s )
-30
-35
-40
TST
ICVT
ICVT/ZCT
ICVT/SCT
-45
-50
0
1
2
3
4
5
-1
(1000T ) K
Fig. S-3 Arrhenius plots of the rate constants for the third reaction path calculated with ICVT using
VMEP and VaG as explained in Table S-12