S14
Theoretical Study of the Complex Reaction of O(3P) with Cis-2-Butene
Boulanouar Messaoudi,a,b Sidi Mohamed Mekellechea and Nelaine Mora-Diezb*
aLaboratoire de Thermodynamique Appliquée et Modélisation Moléculaire, Département de
Chimie, Faculté des Sciences, Université de Tlemcen, BP 119, Tlemcen, 13000, Algeria.
bDepartment of Chemistry, Thompson Rivers University, Kamloops, BC, V2C 0C8, Canada.
* Corresponding authors:
and
Pages Contents
S2 SCHEME S1: Schematic representation of the different channels studied for the reaction of cis-2-butene with O(3P)
S3-4 TABLE S1: Relatives enthalpies and Gibbs free energies at the MP2/6-311G(d,p), PMP2/6-11G(d,p)//MP2/6-311G(d,p), CCSD(T)/6-311G(d,p)//MP2/6-311G(d,p), CBS-4M and CBS-QB3 levels of theory for a selection of stationary points.
S5-6 TABLE S2: Energies, various (MP2) thermal corrections, enthalpies and Gibbs free energies (in a.u. at 298.15 K) of the stationary points along the cis-2-butene + O(3P) addition and H-abstraction channels calculated at different levels of theory.
S7-15 CBS-QB3 Cartesian coordinates of the optimized stationary points (reactants, intermediates, transition states, products and the addition reactant complexes) calculated.
S14
SCHEME S1
TABLE S1. Enthalpy and Gibbs free energy change (relative to the isolated reactants, in kcal/mol at 298.15 K) of important stationary points along the cis-2-butene + O(3P) addition and H-abstraction channels calculated at different levels of theory.
MP2 / PMP2a / CBS-4M / CBS-QB3 / MP2 / PMP2a / CBS-4M / CBS-QB3
cis-2-butene + O(3P) / 0.00 / 0.00 / 0.00 / 0.00 / 0.00 / 0.00 / 0.00 / 0.00
CH3CHCOH + CH3 (P1) / -18.56 / -25.51 / -26.46 / -30.40 / -21.60 / -28.54 / -29.36 / -33.32
CH3CHCOCH3 + H (P2) / -16.18 / -20.99 / -21.59 / -23.69 / -15.46 / -20.27 / -21.34 / -23.36
CH3CHO + CH3CH (P3) / -12.18 / -12.66 / -12.07 / -13.03 / -15.23 / -15.71 / -15.31 / -16.33
CH3CO + CH3CH2 (P4) / -30.13 / -32.04 / -31.29 / -32.29 / -33.75 / -35.67 / -35.26 / -36.34
CH3CH2CO + CH3 (P5) / -30.40 / -32.15 / -30.40 / -31.31 / -33.43 / -35.17 / -33.55 / -34.50
CH3COCH2 + CH3 (P6) / -21.77 / -27.53 / -28.67 / -31.72 / -24.86 / -30.61 / -32.42 / -35.15
CH3CHCHCH2 + OHb (P7) / -3.68 / -12.62 / -17.54 / -16.50 / -4.15 / -13.10 / -18.24 / -18.69
CH3CHCCH3 + OHb (P8) / 17.09 / 11.57 / 5.28 / 5.02 / 15.23 / 9.72 / 2.72 / 2.69
3IM1 / -19.41 / -20.81 / -23.95 / -27.24 / -10.83 / -12.23 / -16.38 / -19.33
3IM2 / -14.81 / -11.86
3IM3 / -32.06 / -31.71
3IM4 / -34.51 / -26.24
3TS1 / 11.95 / 4.73 / -6.86 / -2.24 / DH≠expc
[-0.83,-2.61] / 20.17 / 12.94 / 0.93 / 5.66
3TS2 / -4.66 / -12.16 / -16.10 / -19.55 / 3.31 / -4.19 / -8.58 / -12.00
3TS3 / -2.92 / -9.82 / -12.37 / -15.47 / 5.97 / -0.94 / -3.96 / -7.37
3TS4 / 2.40 / -3.70 / -7.36 / -9.79 / 10.19 / 4.10 / -1.16 / -3.11
3TS5 / -11.55 / -6.15
3TS6 / -13.92 / -17.54 / -23.17 / -23.92 / -5.51 / -9.13 / -15.63 / -16.25
3TS7 / -20.85 / -13.26
3TS8 / 15.48 / 8.67 / 2.01 / -2.21 / 23.07 / 16.25 / 9.04 / 4.82
3TS9b / 16.51 / 10.08 / -2.63 / 3.20 / 24.10 / 17.67 / 4.35 / 10.53
3TS10b / 19.17 / 13.41 / 4.03 / 5.12 / 26.72 / 20.96 / 10.23 / 12.06
a Using MP2/6-311G(d,p) geometries and frequency corrections; b Hydrogen-abstraction products (P7 and P8) and TSs (TS9 and TS10);
c DH≠exp=Ea exp-2RT, for bimolecular gas-phase reactions (Ref. 38): -0.83 kcal/mol (Ref. 23a); Ea exp= +0.36 kcal/mol; -1.42 kcal/mol (Ref. 26 and 27); Ea exp= -0.23 kcal/mol; -1.45 kcal/mol (Ref. 25); Ea exp= -0.27 kcal/mol; -1.46 kcal/mol (Ref. 28); Ea exp= -0.28 kcal/mol; -1.48 kcal/mol (Ref. 30); Ea exp= -0.30 kcal/mol; -1.51 kcal/mol (Ref. 23b and 24); Ea exp= -0.32 kcal/mol; -2.61 kcal/mol (Ref. 29); Ea exp= -1.42 kcal/mol.
TABLE S2 Energies, various (MP2) thermal corrections, enthalpies and Gibbs free energies (in a.u. at 298.15 K) of important stationary points along the cis-2-butene + O(3P) addition and H-abstraction channels calculated at different levels of theory.
O (3P) / 0.00142 / 0.00236 / -0.01495 / -74.91815 / -74.91945 / -74.99120 / -75.00852 / -74.98527 / -75.00258
Cis-2-Butene / 0.11456 / 0.11550 / 0.08083 / -156.74044 / -156.74044 / -156.91714 / -156.95170 / -156.86734 / -156.90177
CH3CHC(O)H / 0.07745 / 0.07839 / 0.04445 / -191.97564 / -191.98607 / -192.19403 / -192.22762 / -192.16028 / -192.19389
CH3 / 0.03324 / 0.03418 / 0.01130 / -39.70724 / -39.70917 / -39.75648 / -39.77939 / -39.74078 / -39.76356
CH3COCH2 / 0.07699 / 0.07793 / 0.04391 / -191.98029 / -191.98883 / -192.19755 / -192.23249 / -192.16238 / -192.19682
H / 0.00142 / 0.00236 / -0.01065 / -0.49981 / -0.49981 / -0.50099 / -0.51401 / -0.49746 / -0.51047
CH3CHO / 0.05905 / 0.05999 / 0.03144 / -153.44070 / -153.44070 / -153.60603 / -153.63460 / -153.57680 / -153.60538
CH3CH / 0.05195 / 0.05289 / 0.02461 / -78.23231 / -78.23438 / -78.32155 / -78.35002 / -78.29658 / -78.32500
CH3CO / 0.04667 / 0.04762 / 0.01863 / -152.79869 / -152.80094 / -152.96295 / -152.99197 / -152.93746 / -152.96648
C2H5 / 0.06436 / 0.06530 / 0.03653 / -78.90296 / -78.90507 / -78.99526 / -79.02443 / -78.96662 / -78.99578
OH / 0.01114 / 0.01208 / -0.00813 / -75.57290 / -75.57439 / -75.65519 / -75.67544 / -75.64642 / -75.66665
CH3CHCHCH2 / 0.10005 / 0.10100 / 0.06848 / -156.08676 / -156.10083 / -156.28110 / -156.31384 / -156.23249 / -156.26750
CH3CHCCH3 / 0.10258 / 0.10353 / 0.06881 / -156.05620 / -156.06481 / -156.24475 / -156.28045 / -156.19820 / -156.23342
CH3CH2CO / 0.07825 / 0.07920 / 0.04528 / -191.99532 / -191.99746 / -192.20031 / -192.23429 / -192.16174 / -192.19578
CH3CHC(O)CH3 / 0.11015 / 0.11110 / 0.07328 / -231.18015 / -231.18912 / -231.44170 / -231.48020 / -231.39292 / -231.43111
O(3P) + Cis-2-butene / 0.11597 / 0.11786 / 0.06588 / -231.65858 / -231.65988 / -231.90834 / -231.96022 / -231.85261 / -231.90435
CH3CHCOH + CH3 (P1) / 0.11068 / 0.11257 / 0.05575 / -231.68288 / -231.69524 / -231.95051 / -232.00701 / -231.90106 / -231.95745
CH3CHCOCH3 + H (P2) / 0.11157 / 0.11346 / 0.06262 / -231.67996 / -231.68893 / -231.94274 / -231.99422 / -231.89037 / -231.94158
CH3CHO + CH3CH (P3) / 0.11100 / 0.11289 / 0.05604 / -231.67302 / -231.67509 / -231.92758 / -231.98462 / -231.87337 / -231.93037
CH3CO + CH3CH2 (P4) / 0.11103 / 0.11292 / 0.05516 / -231.70165 / -231.70601 / -231.95821 / -232.01641 / -231.90408 / -231.96226
CH3CH2CO + CH3 (P5) / 0.11149 / 0.11338 / 0.05658 / -231.70255 / -231.70663 / -231.95679 / -232.01369 / -231.90252 / -231.95934
CH3COCH2 + CH3 (P6) / 0.11022 / 0.11211 / 0.05521 / -231.68753 / -231.69800 / -231.95403 / -232.01188 / -231.90316 / -231.96038
CH3CHCHCH2 + OH (P7) / 0.11119 / 0.11308 / 0.06034 / -231.65966 / -231.67522 / -231.93629 / -231.98928 / -231.87890 / -231.93414
CH3CHCCH3 + OH (P8) / 0.11372 / 0.11561 / 0.06068 / -231.62910 / -231.63919 / -231.89993 / -231.95589 / -231.84462 / -231.90007
3IM1 / 0.11686 / 0.11780 / 0.07950 / -231.68945 / -231.69299 / -231.94650 / -231.98630 / -231.89602 / -231.93516
3IM2 / -231.87622 / -231.92326
3IM3 / -231.90370 / -231.95489
3IM4 / 0.11863 / 0.11958 / 0.08132 / -231,70612 / -231,70930 / -231,78994 / -231.95749 / -231.99626 / -231.90762
3TS1 / 0.11706 / 0.11800 / 0.07911 / -231.63968 / -231.65249 / -231.91928 / -231.95874 / -231.85618 / -231.89533 / 2.231 / 2.005
3TS2 / 0.11388 / 0.11482 / 0.07555 / -231.66297 / -231.67622 / -231.93399 / -231.97390 / -231.88377 / -231.92348 / 2.176 / 2.006
3TS3 / 0.11015 / 0.11110 / 0.07328 / -231.65647 / -231.66877 / -231.92805 / -231.96653 / -231.87726 / -231.91609 / 2.169 / 2.004
3TS4 / 0.11441 / 0.11536 / 0.07580 / -231.65226 / -231.66327 / -231.92008 / -231.96207 / -231.86822 / -231.90931 / 2.154 / 2.004
3TS5 / 0.10989 / 0.11084 / 0.06805 / -231,66213 / -231,66746 / -231,74895 / -231.92825 / -231.97123 / -231.87102 / -231.91415 / 2.052
3TS6 / 0.11629 / 0.11723 / 0.07866 / -231.68013 / -231.68721 / -231.94526 / -231.98512 / -231.89073 / -231.93025 / 2.073 / 2.002
3TS7 / 0.11384 / 0.11478 / 0.07489 / -231.67653 / -231.68404 / -231.76758 / -231.94074 / -231.98086 / -231.88584 / -231.92549 / 2.221
3TS8 / 0.11384 / 0.11478 / 0.07489 / -231.63083 / -231.64299 / -231.90514 / -231.94582 / -231.85614 / -231.89667 / 2.221 / 2.007
3TS9 / 0.11202 / 0.11296 / 0.07309 / -231.62738 / -231.63893 / -231.91253 / -231.95328 / -231.84752 / -231.88758 / 2.167 / 2.009
3TS10 / 0.11188 / 0.11282 / 0.07288 / -231.62299 / -231.63348 / -231.90191 / -231.94391 / -231.84445 / -231.88513 / 2.136 / 2.007
S14
CBS-QB3 Cartesian coordinates of the optimized stationary points (reactants. intermediates. transition states, products, and addition reactant complexes) calculated.
Cis-2-Butene
C -1.58957000 -0.52188900 -0.00000100
H -2.24482500 -0.50376700 0.87819300
H -1.05837000 -1.47458400 -0.00013000
H -2.24499700 -0.50362400 -0.87806300
C -0.66713300 0.66362100 0.00000000
H -1.16456400 1.63158700 0.00000500
C 0.66713500 0.66362200 -0.00000200
H 1.16456400 1.63158800 0.00000000
C 1.58957000 -0.52189000 0.00000000
H 2.24494600 -0.50367600 -0.87810000
H 2.24487500 -0.50372100 0.87815500
H 1.05836600 -1.47458300 -0.00004300
3IM1
C -0.78858700 1.34870500 -0.06623500
H -1.80802000 1.65257500 0.17565800
H -0.62952900 1.49662600 -1.13722500
H -0.09215300 1.98971600 0.48001000
C -0.60211700 -0.13492700 0.29603300
H -0.79161100 -0.22659700 1.40123100
C 0.75409200 -0.71749400 0.00407000
H 0.79728500 -1.80032100 -0.00774900
C 2.00615600 0.08680900 -0.06299100
H 2.30389600 0.47808900 0.92403300
H 2.83851000 -0.51606400 -0.43204700
H 1.90762700 0.95947200 -0.71838900
O -1.59290800 -0.94150700 -0.21384800
3IM2
C -2.59644400 0.54672100 0.00211300
H -2.74963100 1.18149900 0.88163000
H -3.31121500 -0.27599500 0.00358000
H -2.75408400 1.18221600 -0.87609800
C -1.18493300 0.02413700 -0.00157700
H -0.38744000 0.79902000 -0.00319400
C 2.24535600 1.00979200 -0.00191700
H 2.86982200 1.89451400 -0.00436200
C 2.49917000 -0.43234500 0.00248800
H 1.55874300 -0.99575900 0.00050100
H 3.07243800 -0.75279200 -0.88188600
H 3.06611500 -0.74871100 0.89241700
O -0.89295600 -1.14672800 -0.00240300
3IM3
C 1.42164300 0.02096400 -0.08038000
H -3.26735300 1.64674900 0.19986800
C -2.43515000 0.97036700 0.04405700
C 2.83581700 0.55050800 0.00211400
H 2.87439200 1.31846400 0.77788300
H 3.54609800 -0.25280600 0.22148500
H 3.08355400 1.03349200 -0.94562100
H -1.46225900 1.40147600 -0.15629500
C -2.65043400 -0.49952000 -0.03529000
H -3.33575000 -0.85416500 0.74386800
H -3.10562000 -0.79645400 -0.99468500
H -1.71093300 -1.04880700 0.05510600
O 1.04332700 -1.08773300 0.06442300
3IM4
C -0.50834200 0.11511300 -0.22379800
C -1.85779100 -0.57855200 -0.09627800
H -1.79592000 -1.55766200 -0.57512600
H -2.14358500 -0.71417800 0.95785900
H -2.63878400 0.00352200 -0.58834300
C 2.05171100 -0.03537300 -0.17857800
H 2.10109700 -0.00097900 -1.26951200
H 2.17986100 0.98240800 0.19628800
H 2.88947500 -0.63729100 0.18370700
O -0.54475800 1.38252900 0.12808300
C 0.72280500 -0.63548800 0.28911700
H 0.62336200 -1.66632200 -0.06283500
H 0.69226100 -0.66392100 1.39051500
3TS1
C 1.15804300 -1.21132800 -0.24787900
H 2.17872100 -0.90172200 -0.47776400
H 0.62601300 -1.35223300 -1.18919000
H 1.20935600 -2.18134300 0.26040700
C 0.50494100 -0.19408400 0.64199800
H 1.09728800 0.11578300 1.49768600
C -0.80583700 0.18080100 0.63201300
H -1.12965600 0.86078200 1.41503200
C -1.83756600 -0.16812300 -0.39081300
H -2.72090000 -0.60609200 0.08787100
H -2.17772700 0.73628900 -0.90775600
H -1.47590800 -0.87115600 -1.14130100
O 1.03441600 1.56951200 -0.41961300
3TS2
C 1.41842900 1.31086800 0.12004200
H 2.30221200 1.23063900 -0.50185700
H 1.58444500 1.19276000 1.18392800
H 0.70036700 2.07242400 -0.16802500
C 0.37905400 -0.40246100 -0.34178200
H 0.31695500 -0.08609600 -1.39906600
C -0.87128500 -0.38060500 0.38615800
H -0.86880300 -0.85730600 1.36116800
C -2.10304600 0.28390600 -0.11751800
H -2.96768600 -0.38961700 -0.08515500
H -2.37296200 1.15363400 0.49886700
H -1.98444400 0.63220100 -1.14732800
O 1.29387600 -1.22736100 -0.00299200
3TS3
C -0.81422000 1.34395800 -0.06463800
H -1.85087700 1.56631900 0.18378000
H -0.63438400 1.64575400 -1.10252000
H -0.15239100 1.92722300 0.57786400
C -0.58559200 -0.16249000 0.06009600
H -0.87455100 -0.16784400 1.74862200
C 0.75080400 -0.69470700 -0.05571500
H 0.80398600 -1.77785000 -0.08668900
C 2.00725200 0.10027600 -0.00942400
H 2.31291900 0.28524300 1.03310200
H 2.83142200 -0.43157600 -0.48962600
H 1.90389000 1.07992300 -0.48302300
O -1.56118500 -0.95617700 -0.12042800
3TS4
C -1.07228200 1.26941700 -0.19475000
H -1.96132600 1.72250700 0.26049200
H -1.23979700 1.20373700 -1.27072400
H -0.22135900 1.91990800 0.01774300
C -0.90676400 -0.12091500 0.39684700
H -0.45944800 -0.14831300 1.41330200
C 1.07418100 -0.64396700 -0.32262900
H 0.90187400 -1.19481600 -1.23715400
C 2.20657500 0.16815500 0.14108900
H 2.10872800 0.43467100 1.19867500
H 3.14981800 -0.38568300 0.03268400
H 2.31267400 1.10637900 -0.42537200
O -1.55017800 -1.08681600 -0.01412300
3TS5
C 0.98915200 0.16283200 -0.00039600
H -0.09065000 -0.43264500 -0.00114700
C -1.55812600 -0.88590900 -0.00023500
C 2.20425600 -0.73063100 0.00027000
H 2.17159700 -1.38082600 -0.87936400
H 3.12124400 -0.13946100 0.00120300
H 2.17018300 -1.38142000 0.87941000
H -1.79606800 -1.94614600 -0.00018400
C -2.50795900 0.24356300 0.00023500
H -1.97757200 1.20203300 0.00036100
H -3.16453100 0.23307200 -0.88331900
H -3.16417600 0.23263000 0.88404300
O 0.99575400 1.35920400 -0.00003100
3TS6
C -1.16469900 1.23928200 0.12021900
H -2.02632400 1.56477700 -0.46939800
H -0.35545000 1.95162000 -0.02961700
H -1.45701200 1.21253200 1.17700400
C -0.78747400 -0.15493700 -0.39030500
C 2.02677000 0.21314000 -0.30833400
H 3.03790300 0.00324300 0.06989600
H 1.98229800 -0.14975400 -1.33785400
H 1.90448600 1.29868900 -0.31682600
O -1.42604800 -1.15826500 -0.12521500
C 1.01191200 -0.46799000 0.55215000
H 0.79858500 -0.04015500 1.52812500
H 1.00484400 -1.55179800 0.53801600
3TS7
C -0.63425100 -0.16637900 0.14641100
C -1.43718000 1.08480200 -0.11649000
H -0.97508700 1.93180600 0.39220700
H -1.47396300 1.30121000 -1.18958000
H -2.46679300 0.96580500 0.23302600
C 2.30239600 0.23205200 -0.45102600
H 2.18631500 -0.53551900 -1.20668600
H 2.11246400 1.24992500 -0.77109600
H 3.11961900 0.09697900 0.24966400
O -1.11698600 -1.26445800 -0.37686600
C 0.55630800 -0.20299600 0.85857400
H 0.96740700 -1.17252800 1.11387300
H 0.74228800 0.59311600 1.56870000
3TS8
C 1.43707700 1.08490600 -0.11639200
H 2.46638000 0.96639200 0.23420900
H 0.97418600 1.93195200 0.39150900
H 1.47487200 1.30091600 -1.18952600
C 0.63425300 -0.16639500 0.14628700
C -2.30242300 0.23206700 -0.45099400