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. 2012 Dec 14;19(4):1489–1505. doi: 10.1007/s00894-012-1709-4

Table 2.

Molecular properties of the structures taking part in the mechanism of the H/D-abstraction reactions CH3X/CD3X + C1 (X=F, C1 and Br) calculated at the G2 level a)

TS1F MC2F MC1Cl TS1Cl MC2Cl MC1Br TS1Br MC2Br
CX 1.345 1.345 1.779 1.713 1.699 1.950 1.875 1.868
CH1 1.398 2.416 1.088 1.383 2.384 1.087 1.399 3.248
CH2 1.088 1.082 1.088 1.087 1.080 1.086 1.086 1.079
CH3 1.088 1.082 1.088 1.087 1.080 1.086 1.086 1.079
ClH1 1.454 1.286 1.460 1.286 3.432 1.448 1.284
ClX 3.171 2.941
H1CX 107.04 107.96 110.26 108.34 101.13 107.35 106.774 54.89
H1CH2 102.03 96.79 110.13 101.01 95.39 111.54 101.98 113.27
H1CH3 102.03 96.79 108.76 101.01 95.39 111.40 101.98 113.27
CH1Cl 178.94 169.72 175.84 173.38 175.15 141.30
ClXC 92.42 89.73
ClH1CH2 118.78 61.69 59.99 61.23 60.74 73.04
ClH1CH3 −118.78 61.69 −59.99 −61.23 −60.74 −73.04
ClH1CX 0.00 180.00 180.00 180.00 180.00 180.00
ClXCH1 180.00 180.00
ClXCH2 60.34 59.54
ClXCH3 −60.34 −59.54
A 34.324 35.589 14.038 23.816 19.582 9.638 19.827 10.832
B 2.877 1.785 2.283 1.946 1.417 2.228 1.350 1.261
C 2.705 1.721 1.989 1.822 1.334 1.831 1.275 1.139
ν1 1269i 35 29 1379i 31 58 1297i 23
ν2 111 83 46 107 86 70 84 37
ν3 350 117 68 368 121 93 362 77
ν4 474 255 741 435 247 585 416 291
ν5 923 297 1034 833 296 943 673 321
ν6 982 785 1034 924 592 946 892 407
ν7 1127 1137 1394 960 842 1306 898 661
ν8 1156 1139 1466 1072 1013 1435 1016 911
ν9 1194 1445 1467 1159 1422 1437 1096 1358
ν10 1441 2764 2996 1419 2808 2957 1365 2797
ν11 2964 3007 3104 3036 3088 3074 2994 3050
ν12 3088 3151 3105 3152 3226 3080 3114 3197
E0(G2)b) 9.891 −9.841 −9.481 8.121 −16.920 −18.422 8.343 −13.623
DTS1F DMC2F DMC1Cl DTS1Cl DMC2Cl DMC1Br DTS1Br DMC2Br
A 25.923 26.955 11.552 18.282 15.505 7.817 15.318 8.932
B 2.795 1.737 2.165 1.926 1.397 2.164 1.337 1.235
C 2.614 1.671 1.867 1.784 1.305 1.732 1.250 1.102
ν1 948i 34 21 1029i 30 42 975i 16
ν2 107 77 42 104 80 65 82 34
ν3 253 85 67 267 87 93 263 77
ν4 417 184 704 386 176 550 365 207
ν5 683 213 777 687 211 701 614 229
ν6 716 617 777 716 461 704 666 319
ν7 876 870 1055 767 761 988 678 621
ν8 916 989 1061 777 792 1040 719 678
ν9 991 1192 1062 901 1068 1043 854 1009
ν10 1187 1983 2144 1063 2014 2113 1014 2006
ν11 2142 2169 2305 2195 2228 2284 2163 2198
ν12 2306 2357 2306 2350 2411 2289 2322 2391
E0(G2)b) 15.125 −5.979 −10.088 12.949 −13.280 −18.656 13.523 −9.489

a)G2 molecular parameters: geometrical structure optimized at the MP2(full)/6-31G(d) level, (bond lengths in Å, valence and dihedral angles in degrees), rotational constants, ABC in GHz, the vibrational frequencies νi (cm−1) obtained at the MP2/6-31G(d) level and scaled by 0.935, 0.950 and 0.935 for the molecular structures taking part in the reaction mechanism of Cl atom with CH3F/CD3F, CH3Cl/CD3Cl and CH3Br/CD3Br, respectively

b)The total G2-energies in kJ mol−1 at 0 K (ZPE included) calculated toward to the G2-energy of the respective reactants energy