Supplementary Information for

Direct ab-initio Dynamics Calculations of Thermal Rate Constants for the CH4 + O2(3)  CH3 + HO2 reaction

Tam V.-T. Mai,1 Minh v. Duong,1 Xuan T. Le,1Lam K. Huynh1,2,* andArtur Ratkiewicz3

1Institute for Computational Science and Technology, Ho Chi Minh City, Vietnam

2International University, Vietnam National University - HCMC, Vietnam

3Chemistry Institute, University of Bialystok, Hurtowa 1, 15-399Bialystok, Poland

Submitted to Structural Chemistry

Table of content

Table S1: Harmonic vibrational frequencies (in cm-1) for the transition state (TS), reactants, products, and complex

Table S2: The optimized geometries of all species calculated at CCSD(T)/aug-cc-pVTZ//BH&HLYP/aug-cc-pVDZ level of theory.

Table S1: Harmonic vibrational frequencies (in cm-1) for the transition state (TS), reactants, products, and complex.

Species / Sym / Type / Frequency
BHHLYP
/aug-cc-pVDZ / QCISD
/aug-cc-pVDZ / Expt.
TS / a’ / Rxn coordinate / 1819i / 1876i
a’’ / CH3 torsion / 31 / 31
a’ / C-H-O bend / 152 / 140
a’’ / CH2 wag / 380 / 357
a’ / CH3 wag / 492 / 482
a’ / C-H bend / 578 / 564
a’’ / Asym C-H-O bend / 974 / 954
a’ / CH3 umbrella motion / 1115 / 1059
a’ / H-C-H bend / 1415 / 1240
a’’ / Asym H-C-H bend / 1437 / 1412
a’ / C-H bend, O-O str / 1437 / 1413
a’ / C-H-O bend / 1540 / 1499
a’ / C-H sym str / 3156 / 3077
a’’ / Asym C-H str / 3330 / 3244
a’’ / Asym C-H str / 3331 / 3249
CH4 / t2 / H-C-H bend / 1353 / 1330 / 1367a
e / H-C-H bend / 1574 / 1544 / 1583a
a1 / C-H str / 3112 / 3028 / 3026a
t2 / C-H str / 3232 / 3153 / 3157a
O2 / O-O str / 1811 / 1625 / 1580b
CH3 / a2” / Out of plane bend / 548 / 495
e’ / C-H str / 1432 / 1413
a1’ / C-H str / 3190 / 3116
e’ / C-H str / 3383 / 3304
HO2 / a’ / O-O str / 1253 / 1068
a’ / bend / 1516 / 1438
a’ / O-H str / 3816 / 3656
Complex / a’’ / CH3 torsion / 52 / 56
a’ / CH3 displacement / 63 / 75
a’ / CH3 wag / 139 / 136
a’’ / CH2 wag / 156 / 139
a’ / CH3 wag / 241 / 235
a’’ / Asym C-H-O bend / 444 / 409
a’ / CH3 umbrella motion / 683 / 636
a’ / O-O str, O-O-H bend / 1267 / 1076
a’ / H-C-H bend / 1433 / 1411
a’’ / Asym H-C-H bend / 1435 / 1415
a’ / C-H-O bend / 1551 / 1477
a’’ / C-H sym. str. / 3176 / 3100
a’’ / Asym. C-H str / 3366 / 3286
a’’ / Asym C-H str / 3373 / 3292
a’ / H-O str / 3578 / 3496
a Experimental data from ref. [1]; b Experimental data from ref. [2]

Table S2: The optimized geometries of all species calculated at CCSD(T)/aug-cc-pVTZ//BH&HLYP/aug-cc-pVDZ level of theory.

Species / Cartesian coordinates (Å) / Energy (hartree) / Rotational constant (GHZ)
CH4 (Td) / C 0.000000000 0.000000000 0.000000000
H 0.628897000 0.628897000 0.628897000
H -0.628897000 -0.628897000 0.628897000
H -0.628897000 0.628897000 -0.628897000
H 0.628897000 -0.628897000 -0.628897000 / -40.4409292 / 158.4830352 158.4830352 158.4830352
3O2 (D∞h) / O 0.000000000 0.000000000 0.591736000
O 0.000000000 0.000000000 -0.591736000 / -150.1397469 / 0.0000000 45.1179696 45.1179696
TS (Cs)
(cis conformer) / C -1.768258000 0.129361000 0.000000000
H -2.139892000 -0.300048000 -0.923086000
H -2.139860000 -0.300003000 0.923120000
H -0.346456000 -0.322223000 -0.000005000
H -1.563711000 1.194339000 -0.000029000
O 0.705887000 -0.600456000 0.000000000
O 1.394046000 0.469427000 0.000000000 / -190.4911089 / 39.0891609 5.6575706 5.1140516
Complex (Cs) / C -2.036016000 0.115236000 0.000011000
H -2.389711000 -0.298863000 -0.933803000
H -2.389711000 -0.298670000 0.933911000
H -0.037962000 -0.568327000 0.000067000
H -1.495149000 1.052516000 -0.000086000
H 0.932738000 -0.646792000 0.000068000
H 1.383341000 0.574532000 -0.000088000 / -190.4958848 / 32.5846694 4.6374539 4.1776612
CH3 (D3h) / C 0.000000000 0.000000000 0.000001000
H 0.000000000 1.080030000 -0.000001000
H 0.935334000 -0.540015000 -0.000001000
H -0.935334000 -0.540015000 -0.000001000 / -39.7636604 / 286.5952971 286.5952971 143.2976485
HO2 (Cs) / O 0.054552000 0.706394000 0.000000000
O 0.054552000 -0.598658000 0.000000000
H -0.872824000 -0.861888000 0.000000000 / -150.725791 / 639.8456336 34.8759527 33.0732357

References:

1.Gray DL, Robiette AG (1979) Mol Phys 37:1901-1920.

2.Huber KP, Herzberg G (1979) Molecular spectra and molecular Structure, Van Nostrand Reinhold company

1