Atmospheric Ozonolysisstudy of Methyl Acrylate and Methyl 3-Methyl Acrylate

Atmospheric OzonolysisStudy of Methyl Acrylate and Methyl 3-Methyl acrylate

Yanhui Sun, Haijie Cao, Dandan Han, Jing Li, Maoxia He*

Environment Research Institute, ShandongUniversity, Jinan 250100 P. R. China

*Corresponding author. E-mail:.cn

Fax: 86-531-8836 9788

INDEX

Figs. (a) and (b): The optimized geometries of relevant reactants, products and intermediatesat B3LYP/6–31G+(d,p) level(Pages 2-4).

Tables S1(a) andS1(b): The zero point energy (ZPE) corrections and relative energies for all species (Pages 5-7).

Tables S2(a) andS2(b): The moments of inertia and vibrationalfrequencies of reactants, products, intermediates and transition states(Pages 8-9).

Tables S3(a) andS3(b): Overall and site-specific rate constants and branching rations for the main channels (R1 and R2)at different temperatures (200K-400K) (MA+O3)(Pages 10-11).

Tables S4(a) and S4(b):Overall and site-specific rate constants and branching rations for the main channels (R1 and R2)at different pressures (0.01-10000 Torr)(M3MA+O3)(Pages 12-13).

IM1a IM2a IM3a

IM4a IM5a IM6a

IM7a R P1a

P2a P3a P4a

P5a

Fig. (a).B3LYP/6-31G+(d,p) optimized geometries of relevant reactants, products and intermediatesof MA with O3.Distances are in angstroms.

IM1b IM2b IM3b

R P1b P2b

Fig. (b).B3LYP/6-31G+(d,p) optimized geometries of relevant reactants, products and intermediates of M3MA with O3. Distances are in angstroms.

Table S1(a).Zero-point energy, total energy, single-point energy and Zero-point corrected relative energies of reactants, products, intermediates and transition states calculated at different levels of theory (unit in kcal/mol).(MA+O3)

ZPE / B3LYP(HF) / ΔE / 6-31G(d) / 6-311++G(d,p) / ΔE / CCSD(T) / ΔE / CCSD+CF
R / 0.01 / -306.49 / -305.54 / -305.72 / -305.61
O3 / 0.01 / -225.42 / -224.87 / -224.99 / -224.88
R+ O3 / 0.10 / -531.91 / -530.40 / -530.71 / -530.48
TS1a / 0.10 / -531.91 / 1.63 / -530.41 / -530.72 / 1.39 / -530.48 / 4.35 / 5.75
IM1a / 0.11 / -532.00 / -48.88 / -530.48 / -530.78 / 5.46 / -530.57 / -49.32 / -43.86
TS2a / 0.11 / -531.97 / 16.78 / -530.46 / -530.77 / -5.64 / -530.53 / 19.28 / 13.63
P1a / 0.07 / -342.40 / -341.41 / -341.61 / -341.47
IM2a / 0.03 / -189.59 / -189.04 / -189.15 / -189.08
P1a+M2a / 0.10 / -531.99 / -1.15 / -530.45 / -530.76 / -7.23 / -530.55 / 5.72 / -1.51
TS3a / 0.11 / -531.96 / 17.88 / -530.46 / -530.77 / 1.67 / -530.53 / 21.12 / 22.79
P2a / 0.03 / -114.51 / -114.17 / -114.24 / -114.19
IM3a / 0.07 / -417.48 / -416.29 / -416.52 / -416.36
P2a+IM3a / 0.10 / -531.99 / -2.60 / -530.46 / -530.77 / -6.73 / -530.55 / 4.79 / -1.94
NO / 0.00 / -129.89 / -129.53 / -129.60 / -129.55
NO+IM3a / 0.08 / -547.37 / -545.82 / -546.13 / -545.91
TS4a / 0.08 / -547.36 / 4.94 / -545.79 / -546.09 / 4.94 / -545.91 / 1.01 / 5.95
NO2 / 0.01 / -205.07 / -204.55 / -204.65 / -204.57
P1a+NO2 / 0.08 / -547.47 / -62.23 / -545.96 / -546.26 / 4.03 / -546.03 / -76.03 / -72.00
H2O / 0.02 / -76.42 / -76.20 / -76.27 / -76.21
IM3a+H2O / 0.10 / -493.90 / -492.48 / -492.80 / -492.57
IM4a / 0.10 / -493.93 / -15.12 / -492.50 / -492.81 / 1.76 / -492.58 / -6.99 / -5.22
TS5a / 0.10 / -493.91 / 11.05 / -492.48 / -492.79 / 1.74 / -492.57 / 11.30 / 13.04
IM5a / 0.10 / -493.98 / -31.40 / -492.57 / -492.88 / 2.20 / -492.65 / -38.51 / -36.30
TS6a / 0.09 / -493.90 / 47.67 / -492.48 / -492.80 / -4.61 / -492.56 / 50.07 / 45.46
H2O / 0.02 / -76.42 / -76.20 / -76.27 / -76.21
P3a / 0.08 / -417.65 / -416.48 / -416.72 / -416.54
P3a+ H2O / 0.10 / -494.07 / -59.67 / -492.67 / -493.00 / -9.12 / -492.74 / -62.62 / -71.74
TS7a / 0.09 / -493.89 / 17.19 / -492.46 / -492.77 / -2.93 / -492.54 / 24.03 / 21.10
P4a / 0.06 / -341.75 / -340.77 / -340.96 / -340.83
OH / 0.01 / -75.73 / -75.52 / -75.58 / -75.54
H2O / 0.02 / -76.42 / -76.20 / -76.27 / -76.21
P4a+OH+H2O / 0.09 / -493.90 / 13.21 / -492.49 / -492.82 / -9.94 / -492.57 / -0.09 / -10.03
TS8a / 0.09 / -493.88 / 28.94 / -492.44 / -492.75 / -0.76 / -492.53 / 30.07 / 29.31
H2O2 / 0.03 / -151.56 / -151.13 / -151.24 / -151.15
P1a / 0.07 / -342.40 / -341.41 / -341.61 / -341.47
P1a+ H2O2 / 0.10 / -493.95 / -18.15 / -492.54 / -492.85 / 0.77 / -492.62 / -22.74 / -21.97
TS9a / 0.07 / -417.44 / 21.20 / -416.25 / -416.48 / 0.40 / -416.33 / 18.80 / 19.20
IM6a / 0.08 / -417.51 / -17.79 / -416.34 / -416.57 / 1.78 / -416.40 / -24.68 / -22.89
TS10a / 0.07 / -417.37 / 82.47 / -416.19 / -416.43 / -4.64 / -416.26 / 87.63 / 82.98
CO2 / 0.01 / -188.58 / -188.09 / -188.19 / -188.11
P5a / 0.06 / -229.08 / -228.40 / -228.54 / -228.44
CO2+P5a / 0.07 / -417.66 / -96.70 / -416.49 / -416.73 / -2.41 / -416.54 / -90.88 / -93.30
TS11a / 0.07 / -417.42 / 33.89 / -416.23 / -416.47 / -2.36 / -416.30 / 36.06 / 33.70
IM7a / 0.07 / -417.47 / 5.17 / -416.28 / -416.54 / -11.11 / -416.35 / 3.89 / -7.22
P4a / 0.06 / -341.75 / -340.77 / -340.96 / -340.83
OH / 0.01 / -75.73 / -75.52 / -75.58 / -75.54
P4a+OH / 0.07 / -417.48 / -7.07 / -416.29 / -416.54 / 2.93 / -416.36 / -10.97 / -8.04

Table S1(b).Zero-point energy, total energy, single-point energy and Zero-point corrected relative energies of reactants, products, intermediates and transition states calculated at different levels of theory (unit in kcal/mol).(M3MA+O3)

ZPE / B3LYP(HF) / ΔE / 6-31G(d) / 6-311++G(d,p) / ΔE / CCSD(T) / ΔE / CCSD+CF
R / 0.12 / -345.82 / -344.71 / -344.92 / -344.79
R+ O3 / 0.13 / -571.24 / -569.57 / -569.91 / -569.67
TS1b / 0.13 / -571.23 / 2.12 / -569.58 / -569.92 / 1.24 / -569.67 / 3.91 / 5.15
IM1b / 0.14 / -571.32 / -48.59 / -569.65 / -569.98 / 4.69 / -569.76 / -50.69 / -46.00
TS2b / 0.13 / -571.29 / 14.83 / -569.64 / -569.98 / -4.66 / -569.73 / 17.00 / 12.34
P1b / 0.07 / -342.40 / -341.41 / -341.61 / -341.47
IM2b / 0.06 / -228.93 / -228.22 / -228.36 / -228.28
P1b+M2b / 0.13 / -571.32 / -6.15 / -569.63 / -569.97 / -6.50 / -569.74 / 4.65 / -1.85
TS3b / 0.13 / -571.29 / 17.76 / -569.64 / -569.98 / -4.80 / -569.72 / 19.90 / 15.10
P2b / 0.06 / -153.85 / -153.35 / -153.45 / -153.39
IM3b / 0.07 / -417.48 / -416.29 / -416.52 / -416.36
P2b+IM3b / 0.13 / -571.33 / -7.72 / -569.63 / -569.97 / -5.71 / -569.75 / 2.69 / -3.03

Table S2(a). Moments of inertia and harmonic vibrational frequencies of reactants, products, intermediates and transition states calculated at B3LYP/6-31+G(d, p) level of theory.(MA+O3)

moments of inertia / harmonic vibrational frequencies
MA / 176,784, 949 / 98,136,201,220,336,473,528,666,826,868,1005,1023,1025,1084,1174,1204,1232,1331,1441,1476,1488,1501,1699,1781,3063,3141,3165,3174,3205,3260
O3 / 16,134,150 / 733,1219,1257
IM1a / 519,1614,1904 / 31,75,119,157,181,298,309,389,491,573,693,715,748,799,859,911,944,1004,1041,1051,1087,1173,1209,1218,1252,1311,1336,1366,1477,1490,1498,1514,1788,3071,3085,3091,3153,3156,3188
TS1a / 568,1881,2107 / 201i,52,76,91,132,181,213,230,333,351,444,482,645,670,732,819,871,983,1004,1018,1080,1107,1135,1174,1205,1239,1301,1437,1476,1488,1499,1590,1782,3067,3147,3181,3184,3229,3288
TS2a / 515,1832,1921 / 405i,41,89,115,131,201,232,279,333,421,487,561,591,717,755,859,905,964,1008,1055,1125,1174,1194,1216,1235,1277,1342,1473,1483,1489,1499,1501,1826,2979,3068,3135,3149,3181 3265
TS3a / 506,1925,2158 / 433i,43,104,121,127,182,209,304,316,406,441,515,556,744,770,859,955,1001,1024,1138,1149,1173,1205,1222,1238,1267,1395,1412,1477,1488,1498,1556,1811,2952,3029,3073,3156,3191,3191

Table S2(b). Moments of inertia and harmonic vibrational frequencies of reactants, products, intermediates and transition states calculated at B3LYP/6-31+G(d, p) level of theory.(M3MA+O3)

moments of inertia / harmonic vibrational frequencies
M3MA / 199,1467,1644 / 84,126,151,158,211,246,308,385,447,703,728,862,915,947,1004,1049,1078,1128,1174,1203,1222,1325,1346,1416,1473,1482,1487,1489,1501,1716,1775,3028,3062,3078,3120,3139,3167,3172,3195
O3 / 16,134,150 / 733,1219,1257
IM1b / 781,1854,2378 / 21,57,118,139,185,224,244,271,317,370,455,481,614,677,720,735,776,877,893,915,935,1035,1049,1095,1119,1159,1173,1210,1248,1318,1326,1356,1391,1420,1476,1490,1494,1498,1503,1784,3056,3064,3070,3088,3135,3139,3152,3187
TS1b / 840,2165,2499 / 213i,55,77,89,124,134,147,175,208,227,308,374,379,459,483,719,732,734,864,922,948,971,1045,1051,1096,1119,1132,1174,1205,1231,1292,1339,1414,1473,1481,1488,1492,1500,1598,1777,3031,3066,3099,3140,3145,3179,3202,3218
TS2b / 797,1911,2259 / 409i,50,79,102,130,191,195,224,242,323,346,354,416,506,574,621,728,764,875,913,985,999,1020,1115,1147,1159,1174,1196,1216,1277,1342,1393,1430,1463,1474,1486,1489,1497,1501,1819,2990,3051,3067,3123,3147,3150,3162,3180
TS3b / 773,2100,2341 / 451i,48,88,108,134,166,173,195,272,307,322,409,447,476,572,595,740,777,862,944,957,1015,1035,1117,1128,1138,1173,1206,1237,1251,1309,1404,1407,1448,1477,1481,1489,1499,1500,1808,2955,3051,3072,3120,3147,3155,3183,3189

Table S3(a). Rate constants of ka1, ka2,ka3, ka and branching rations of R1a and R2a (MA+O3). All the data are obtained at atmospheric pressure.

T / ka1 / ka2 / ka3 / ka / ka1/ka / ka2/ka
200 / 2.95×10-21 / 1.29×10-23 / 7.36×10-23 / 3.04×10-21 / 0.972 / 0.004
220 / 1.51×10-20 / 6.96×10-23 / 3.33×10-22 / 1.55×10-20 / 0.974 / 0.005
240 / 5.96×10-20 / 2.92×10-22 / 1.18×10-21 / 6.11×10-20 / 0.976 / 0.005
260 / 1.94×10-19 / 1.01×10-21 / 3.43×10-21 / 1.98×10-19 / 0.978 / 0.005
273 / 3.83×10-19 / 2.07×10-21 / 6.33×10-21 / 3.92×10-19 / 0.979 / 0.005
280 / 5.40×10-19 / 2.98×10-21 / 8.60×10-21 / 5.52×10-19 / 0.979 / 0.005
291 / 8.98×10-19 / 5.12×10-21 / 1.35×10-20 / 9.16×10-19 / 0.980 / 0.006
294 / 1.03×10-18 / 5.90×10-21 / 1.52×10-20 / 1.05×10-18 / 0.980 / 0.006
298 / 1.22×10-18 / 7.11×10-21 / 1.77×10-20 / 1.24×10-18 / 0.980 / 0.006
320 / 2.95×10-18 / 1.84×10-20 / 3.83×10-20 / 3.00×10-18 / 0.981 / 0.006
340 / 6.01×10-18 / 4.01×10-20 / 7.07×10-20 / 6.12×10-18 / 0.982 / 0.007
360 / 1.14×10-17 / 8.15×10-20 / 1.22×10-19 / 1.16×10-17 / 0.983 / 0.007
380 / 2.05×10-17 / 1.56×10-19 / 1.98×10-19 / 2.08×10-17 / 0.983 / 0.007
400 / 3.48×10-17 / 2.84×10-19 / 3.07×10-19 / 3.54×10-17 / 0.983 / 0.008

Table S3(b). Rate constants of kb1, kb2,kb3, kb and branching rations of R1b and R2b (M3MA+O3). All the data are obtained at atmospheric pressure.

T / kb1 / kb2 / kb3 / kb / kb1/kb / kb2/kb
200 / 2.28×10-20 / 5.77×10-21 / 1.14×10-21 / 2.97×10-20 / 0.767 / 0.194
220 / 9.67×10-20 / 2.48×10-20 / 4.29×10-21 / 1.26×10-19 / 0.768 / 0.198
240 / 3.28×10-19 / 8.57×10-20 / 1.30×10-20 / 4.27×10-19 / 0.769 / 0.201
260 / 9.39×10-19 / 2.49×10-19 / 3.32×10-20 / 1.22×10-18 / 0.769 / 0.204
273 / 1.72×10-18 / 4.61×10-19 / 5.68×10-20 / 2.24×10-18 / 0.769 / 0.206
280 / 2.34×10-18 / 6.30×10-19 / 7.43×10-20 / 3.05×10-18 / 0.769 / 0.207
291 / 3.69×10-18 / 1.00×10-18 / 1.10×10-19 / 4.80×10-18 / 0.769 / 0.209
294 / 4.15×10-18 / 1.13×10-18 / 1.22×10-19 / 5.41×10-18 / 0.768 / 0.209
298 / 4.85×10-18 / 1.32×10-18 / 1.40×10-19 / 6.31×10-18 / 0.768 / 0.210
320 / 1.07×10-17 / 2.98×10-18 / 2.75×10-19 / 1.39×10-17 / 0.767 / 0.213
340 / 2.03×10-17 / 5.74×10-18 / 4.72×10-19 / 2.65×10-17 / 0.765 / 0.217
360 / 3.62×10-17 / 1.01×10-17 / 7.62×10-19 / 4.73×10-17 / 0.764 / 0.220
380 / 6.11×10-17 / 1.79×10-17 / 1.17×10-18 / 8.02×10-17 / 0.762 / 0.223
400 / 9.88×10-17 / 2.95×10-17 / 1.71×10-18 / 1.30×10-16 / 0.760 / 0.227

Table S4(a). Rate constants of ka1, ka2,ka3, ka and branching rations of R1a and R2aforozonolysis ofMAat different pressures and at 291, 298 and 305 K.

T / P / ka / ka1 / ka2 / ka3 / ka1/ka / ka2/ka
291 / 0.01 / 9.16×10-19 / 9.11×10-19 / 5.20×10-21 / 1.81×10-25 / 0.994 / 0.006
0.10 / 9.16×10-19 / 9.11×10-19 / 5.19×10-21 / 1.81×10-24 / 0.994 / 0.006
1.00 / 9.16×10-19 / 9.11×10-19 / 5.19×10-21 / 1.81×10-23 / 0.994 / 0.006
10 / 9.16×10-19 / 9.11×10-19 / 5.19×10-21 / 1.80×10-22 / 0.994 / 0.006
100 / 9.16×10-19 / 9.09×10-19 / 5.19×10-21 / 1.80×10-21 / 0.992 / 0.006
1000 / 9.16×10-19 / 8.94×10-19 / 5.10×10-21 / 1.77×10-20 / 0.975 / 0.006
10000 / 9.16×10-19 / 7.62×10-19 / 4.38×10-21 / 1.50×10-19 / 0.832 / 0.005
298 / 0.01 / 1.24×10-18 / 1.24×10-18 / 7.21×10-21 / 2.36×10-28 / 0.994 / 0.006
0.10 / 1.24×10-18 / 1.24×10-18 / 7.21×10-21 / 2.36×10-24 / 0.994 / 0.006
1.00 / 1.24×10-18 / 1.24×10-18 / 7.21×10-21 / 2.36×10-23 / 0.994 / 0.006
10 / 1.24×10-18 / 1.24×10-18 / 7.20×10-21 / 2.36×10-22 / 0.994 / 0.006
100 / 1.24×10-18 / 1.23×10-18 / 7.19×10-21 / 2.36×10-21 / 0.992 / 0.006
1000 / 1.24×10-18 / 1.21×10-18 / 7.08×10-21 / 2.32×10-20 / 0.976 / 0.006
10000 / 1.24×10-18 / 1.04×10-18 / 6.11×10-21 / 1.97×10-19 / 0.836 / 0.005
305 / 0.01 / 1.67×10-18 / 1.66×10-18 / 9.87×10-21 / 3.06×10-25 / 0.994 / 0.006
0.10 / 1.67×10-18 / 1.66×10-18 / 9.87×10-21 / 3.06×10-24 / 0.994 / 0.006
1.00 / 1.67×10-18 / 1.66×10-18 / 9.87×10-21 / 3.06×10-23 / 0.994 / 0.006
10 / 1.67×10-18 / 1.66×10-18 / 9.87×10-21 / 3.06×10-22 / 0.994 / 0.006
100 / 1.67×10-18 / 1.65×10-18 / 9.85×10-21 / 3.05×10-21 / 0.992 / 0.006
1000 / 1.67×10-18 / 1.63×10-18 / 9.70×10-21 / 3.00×10-20 / 0.976 / 0.006
10000 / 1.67×10-18 / 1.40×10-18 / 8.42×10-21 / 2.57×10-19 / 0.841 / 0.005

Table S4(b). Rate constants of kb1, kb2,kb3, kb and branching rations of R1b and R2bforozonolysis ofM3MA at different pressures and at 291, 298 and 305 K.

T / P / kb / kb1 / kb2 / kb3 / kb1/kb / kb2/kb
291 / 0.01 / 4.80×10-18 / 3.77×10-18 / 1.03×10-18 / 1.49×10-24 / 0.786 / 0.214
0.10 / 4.80×10-18 / 3.77×10-18 / 1.03×10-18 / 1.49×10-23 / 0.786 / 0.214
1.00 / 4.80×10-18 / 3.77×10-18 / 1.03×10-18 / 1.49×10-22 / 0.786 / 0.214
10 / 4.80×10-18 / 3.77×10-18 / 1.02×10-18 / 1.49×10-21 / 0.786 / 0.214
100 / 4.80×10-18 / 3.76×10-18 / 1.02×10-18 / 1.48×10-20 / 0.784 / 0.213
1000 / 4.80×10-18 / 3.66×10-18 / 9.95×10-19 / 1.44×10-19 / 0.763 / 0.207
10000 / 4.80×10-18 / 2.89×10-18 / 7.86×10-19 / 1.13×10-18 / 0.601 / 0.164
298 / 0.01 / 6.31×10-18 / 4.96×10-18 / 1.35×10-18 / 1.88×10-24 / 0.785 / 0.215
0.10 / 6.31×10-18 / 4.96×10-18 / 1.35×10-18 / 1.88×10-23 / 0.785 / 0.215
1.00 / 6.31×10-18 / 4.96×10-18 / 1.35×10-18 / 1.88×10-22 / 0.785 / 0.215
10 / 6.31×10-18 / 4.96×10-18 / 1.35×10-18 / 1.88×10-21 / 0.785 / 0.215
100 / 6.31×10-18 / 4.94×10-18 / 1.35×10-18 / 1.88×10-20 / 0.783 / 0.214
1000 / 6.31×10-18 / 4.81×10-18 / 1.32×10-18 / 1.83×10-19 / 0.763 / 0.208
10000 / 6.31×10-18 / 3.82×10-18 / 1.05×10-18 / 1.44×10-18 / 0.606 / 0.166
305 / 0.01 / 8.21×10-18 / 6.44×10-18 / 1.77×10-18 / 2.36×10-24 / 0.784 / 0.216
0.10 / 8.21×10-18 / 6.44×10-18 / 1.77×10-18 / 2.36×10-23 / 0.784 / 0.216
1.00 / 8.21×10-18 / 6.44×10-18 / 1.77×10-18 / 2.36×10-22 / 0.784 / 0.216
10 / 8.21×10-18 / 6.44×10-18 / 1.77×10-18 / 2.36×10-21 / 0.784 / 0.215
100 / 8.21×10-18 / 6.42×10-18 / 1.77×10-18 / 2.35×10-20 / 0.782 / 0.215
1000 / 8.21×10-18 / 6.26×10-18 / 1.72×10-18 / 2.29×10-19 / 0.762 / 0.210
10000 / 8.21×10-18 / 5.01×10-18 / 1.38×10-18 / 1.82×10-18 / 0.610 / 0.168

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