- Energies are printed in hartree, vibrational frequencies in cm^-1. - All single point calculation are frozen core (FC) calculations and performed with an optimised wavefunction (Stable=opt keyword in GAUSSIAN). !! The initial standard guess for the CF3CH2O radical (not used here) shows an severe instability. - Zero Point Energies are listed with a scale factor of 0.985 applied to the B3LYP/cc-pVTZ frequencies - E(HLC) for molecules is calculated from the number of alpha (na) and beta (nb) valence electrons by E(HLC,G3(MP2)) = (-9.279 nb - 4.471 (na - nb) ) / 1000 hartree corresponding to G3(MP2)-theory. - We do not investigate or re-optimise the HLC vor B3LYP/cc-pVTZ geometries and zero point energies for reasons that for the reactions under investigation the HLC terms cancel out in the calculation of energy barriers. Nevertheless, instead of the HLC terms for G3(MP2) also the ones for G3(MP2)//B3LYP (relying on B3LYP/6-31G(d) geometries and zpes) could have been used which are given by E(HLC,G3(MP2)//B3LYP) = (-10.041 nb - 4.995 (na - nb) ) / 1000 hartree +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CF3CF2O -> CF3 + CF2O +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ na= 25 nb= 24 8 CF3CF2O equilibrium (UHF/6-31G(d) opt&freq) E=-647.7549839 hartree C -0.7204654545 -0.0204710965 0.1916608528 C 0.7679763831 0.0668577756 -0.1776741015 F -1.3660604323 1.0127775868 -0.2918630475 F -1.2227739448 -1.117781019 -0.3148780745 F -0.8608005066 -0.0432382403 1.494722773 F 1.3912530284 -1.0012511783 0.290919485 O 1.2830479904 1.1974268959 0.3448804213 F 0.8862208003 0.054188935 -1.4947860114 8 CF3CF2O equilibrium (UB3LYP/6-31G(d) opt&freq) E=-650.5559227 hartree C -0.7326542649 -0.004422825 0.2045904627 C 0.8101444023 0.0858563256 -0.1783736382 F -1.3941634833 1.0383343347 -0.2955652315 F -1.213339429 -1.1301076045 -0.3248071819 F -0.8783056828 -0.0397658549 1.5284595245 F 1.4108163601 -1.0365517958 0.293740298 O 1.2702401794 1.2045446799 0.3527353283 F 0.8942297617 0.0430955381 -1.5328478061 8 CF3CF2O equilibrium (UB3LYP/cc-pVTZ opt&freq) E=-650.8230852 hartree C -0.7381348596 -0.0035891919 0.2066327323 C 0.8174487419 0.0852762993 -0.180782649 F -1.3962499529 1.0351916271 -0.291927623 F -1.2175167241 -1.1246631719 -0.3204352317 F -0.8823286246 -0.0388957714 1.5252323357 F 1.4163651827 -1.0338881306 0.2880853614 O 1.2654346167 1.2001059938 0.3514424953 F 0.902023427 0.0410364918 -1.5305815604 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) 58.0742, 208.1443, 224.9763, 327.1765, 341.3066, 351.3075, 509.8071 515.2936, 582.4703, 599.4298, 669.5702, 773.9657, 916.0875, 1088.5998 1129.5279, 1230.0313, 1242.7020, 1282.4309 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -650.823085245 UB3LYP/6-31G(d,p) = -650.555768926 CCSD(T)/6-31G(d) = -649.03724220 MP2(FC)/6-31G(d) = -648.98274767009 PMP2(FC)/6-31G(d) = -648.98470124 QCISD(T)/6-31G(d) = -649.03967358 MP2(FC)/6-31G(d) = -648.98274766733 PMP2(FC)/6-31G(d) = -648.98470124 MP2/GTMP2Large = -649.69941667245 PMP2/GTMP2Large = -649.70172706 S**2 before annihilation .75918 (MP2/GTMP2Large) Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -649.9810782023601 G3(PMP2,CC) = -649.9814350200002 G3(MP2) = -649.98350958512 G3(PMP2) = -649.9838664000002 E(HLC,G3(MP2)) = -0.227167 E(HLC,G3(MP2)//B3LYP) = -0.245979 E(ZPE) = .027042 (scaled with 0.985) ------------------------------------------------------------------------------- na= 25 nb= 24 8 CF3CF2O TS (UHF/6-31G(d) opt&freq) E=-647.7086439 hartree C .892197 -.013592 .000088 C -1.075112 .162836 -.001298 F 1.359438 .549610 1.066788 F 1.112302 -1.293381 .009319 F 1.359796 .534231 -1.074432 F -1.344252 -.561800 -1.058454 O -1.148848 1.369145 -.010696 F -1.344142 -.545173 1.067092 8 CF3CF2O TS (UB3LYP/6-31G(d) opt&freq) E=-650.5470475 hartree C 0.0332208448 0.0592232187 -0.8936202147 C 0.0401621498 0.0716418643 1.0863903116 F 1.2853204707 0.0613517597 -1.29300194 F -0.5892124456 -1.0513348926 -1.2409066574 F -0.6184850677 1.1283645933 -1.2929731243 F -1.2876045073 -0.078035584 1.271720328 O 0.62549175 1.115604207 1.2992305465 F 0.6050668868 -1.139237449 1.2717763988 8 CF3CF2O TS (UB3LYP/cc-pVTZ opt&freq) E=-650.8177566 hartree C 0.0353991513 0.0630741747 -0.8757094515 C 0.0353705755 0.0630604807 1.0455770639 F 1.2817514511 0.0642621568 -1.2761427483 F -0.5840576523 -1.0425698876 -1.2269300203 F -0.6144810518 1.1266420044 -1.2760295297 F -1.285750762 -0.0791759104 1.271160865 O 0.6216432576 1.1083364566 1.2638774519 F 0.6027864128 -1.1384360949 1.2712497345 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) -395.9198, 45.8026, 168.3345, 187.3800, 267.8300, 281.4636, 407.8865 528.4194, 531.6853, 570.7404, 589.9389, 733.9612, 883.3909, 1013.6927 1123.5085, 1278.8466, 1305.4340, 1571.0457 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -650.817756584 UB3LYP/6-31G(d,p) = -650.547141963 CCSD(T)/6-31G(d) = -649.01968019 MP2(FC)/6-31G(d) = -648.96090424244 PMP2(FC)/6-31G(d) = -648.97220537 QCISD(T)/6-31G(d) = -649.02267865 MP2(FC)/6-31G(d) = -648.96090424244 PMP2(FC)/6-31G(d) = -648.97220537 MP2/GTMP2Large = -649.68156093842 PMP2/GTMP2Large = -649.69322279 S**2 before annihilation .86097 (MP2/GTMP2Large) Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -649.9675038859801 G3(PMP2,CC) = -649.9678646100002 G3(MP2) = -649.9705023459801 G3(PMP2) = -649.9708630700002 E(HLC,G3(MP2)) = -0.227167 E(HLC,G3(MP2)//B3LYP) = -0.245979 E(ZPE) = .025782 (scaled with 0.985) +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CF3CFHO -> CF3 + CFHO +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ na= 22 nb= 21 8 CF3CFHO equilibrium (UHF/6-31G(d) opt&freq) E=-548.8981251 hartree C 0.5850742865 0.0019341488 -0.00534114 C -0.8848065076 -0.0665707196 -0.4047388304 F 1.2378500979 -1.0100540907 -0.5350175017 F 1.1193490648 1.1191631782 -0.4466003837 F 0.7239738741 -0.0443117759 1.3003549943 F -1.4850548161 1.0466954129 0.0561770497 O -1.4499742206 -1.1899927045 0.0713726979 H -0.9668768951 -0.0956734594 -1.4847291884 8 CF3CFHO equilibrium (UB3LYP/6-31G(d) opt&freq) E=-551.3230238 hartree C -0.5982702796 -0.0037159692 -0.0016219605 C 0.9170603889 0.106146034 -0.37831946 F -1.2626196634 1.036482945 -0.5198045686 F -1.1050799999 -1.135227963 -0.5074395001 F -0.7604343571 -0.011776743 1.3245534547 F 1.5212754794 -1.0571833913 0.0513485484 O 1.4482654097 1.2203030571 0.0785898214 H 0.9628629357 0.1323415244 -1.4869914583 8 CF3CFHO equilibrium (UB3LYP/cc-pVTZ opt&freq) E=-551.5517198 hartree C -0.6004209334 -0.0048489387 -0.0026338258 C 0.9203717741 0.1085738038 -0.3751881604 F -1.2648485641 1.0267339317 -0.5272105302 F -1.1052618614 -1.1358030531 -0.4995666405 F -0.7670576882 -0.0047926453 1.3188465066 F 1.5306980759 -1.0508668506 0.0543680775 O 1.4466650335 1.2162813591 0.0788299874 H 0.9652050277 0.1299574915 -1.4816447035 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) 71.6521, 218.3104, 240.3948, 359.0897, 394.2359, 519.7133, 562.6045 596.6825, 680.3454, 805.7104, 1026.4762, 1063.0770, 1132.5131, 1182.7303 1221.3548, 1259.1215, 1276.8083, 2885.2876 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -551.551719752 UB3LYP/6-31G(d,p) = -551.324344637 CCSD(T)/6-31G(d) = -550.01509834 MP2(FC)/6-31G(d) = -549.96033883619 PMP2(FC)/6-31G(d) = -549.96250552 QCISD(T)/6-31G(d) = -550.01713621 MP2(FC)/6-31G(d) = -549.96033883619 PMP2(FC)/6-31G(d) = -549.96250552 MP2/GTMP2Large = -550.57392663596 PMP2/GTMP2Large = -550.57649726 S**2 before annihilation .76091 (MP2/GTMP2Large) Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -550.8280161397702 G3(PMP2,CC) = -550.8284200800001 G3(MP2) = -550.8300540097701 G3(PMP2) = -550.8304579500001 E(HLC,G3(MP2)) = -0.19933 E(HLC,G3(MP2)//B3LYP) = -0.215856 E(ZPE) = .034773 (scaled with 0.985) ------------------------------------------------------------------------------- na= 22 nb= 21 8 CF3CFHO TS (UHF/6-31G(d) opt&freq) E=-548.8502853 hartree C 0.7454428768 0.006174605 0.0037177519 C -1.2313359032 -0.1389868541 -0.4188455745 F 1.3533143149 -0.9913590989 -0.5641798376 F 1.1343297346 1.1369749154 -0.5124386694 F 0.9193654221 -0.0032080814 1.2866201158 F -1.6341604273 1.0097103759 0.1173201807 O -1.4944854729 -1.1916756889 0.1286042475 H -1.0843994562 -0.0387839932 -1.4839631502 8 CF3CFHO TS (UB3LYP/6-31G(d) opt&freq) E=-551.3050117 hartree C 0.766860713 -0.000336691 0.0059655809 C -1.2568550527 -0.1474788647 -0.4152451453 F 1.3463620616 -1.0395951818 -0.5656356179 F 1.180076023 1.1374570203 -0.5290128938 F 0.9222735653 -0.0072793703 1.3119837939 F -1.6101587463 1.0664511721 0.106496903 O -1.567905903 -1.186877027 0.1292493781 H -1.06376287 -0.0313932129 -1.4928073062 8 CF3CFHO TS (UB3LYP/cc-pVTZ opt&freq) E=-551.5374898 hartree C -0.7549121228 -0.0041150175 0.0064719123 C 1.2192038772 0.1532049825 -0.4162330877 F -1.3406211228 1.0450089825 -0.5265930877 F -1.1769311228 -1.1227800175 -0.5493880877 F -0.8892291228 -0.0317520175 1.3089549123 F 1.6187198772 -1.0524400175 0.0991519123 O 1.5341118772 1.1913469825 0.1201709123 H 1.0339078772 0.0323519825 -1.4919310877 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) -364.7897, 42.7183, 146.7115, 175.2228, 259.4537, 342.9142, 524.0024 529.6878, 634.6759, 659.0499, 919.5356, 994.2375, 1076.5209, 1263.5853 1292.9500, 1315.2445, 1602.2288, 2996.3852 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -551.537489828 UB3LYP/6-31G(d,p) = -551.306432534 CCSD(T)/6-31G(d) = -649.01968019 MP2(FC)/6-31G(d) = -648.96090424244 PMP2(FC)/6-31G(d) = -648.97220537 QCISD(T)/6-31G(d) = -649.02267865 MP2(FC)/6-31G(d) = -648.96090424244 PMP2(FC)/6-31G(d) = -648.97220537 MP2/GTMP2Large = -649.68156093842 PMP2/GTMP2Large = -649.69322279 S**2 before annihilation .86097 (MP2/GTMP2Large) Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -550.8072391389201 G3(PMP2,CC) = -550.80754204 G3(MP2) = -550.8099726465201 G3(PMP2) = -550.8102755500002 E(HLC,G3(MP2)) = -0.19933 E(HLC,G3(MP2)//B3LYP) = -0.215856 E(ZPE) = .033155 (scaled with 0.985) +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ CF3CH2O -> CF3 + CH2O +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ na= 19 nb= 18 8 CF3CH2O equilibrium (UHF/6-31G(d) opt&freq) E=-450.0447088 hartree C -0.3366267523 -0.1723844332 -0.0058092517 C 1.1278672062 -0.1004065814 -0.3746000139 F -1.0097994383 0.8530638574 -0.490479157 F -0.8684926311 -1.2800531201 -0.5005596123 F -0.5072168369 -0.1888676395 1.3019526507 H 1.6397059974 -0.97084629 0.0222313545 O 1.732118274 1.0328123466 0.1146357126 H 1.2254852436 -0.1121942757 -1.4550863954 8 CF3CH2O equilibrium (UB3LYP/6-31G(d) opt&freq) E=-452.0868672 hartree C -0.3430806418 -0.1705650898 -0.0029471216 C 1.1383526727 -0.0812719579 -0.3664241485 F -1.0332843625 0.8709334322 -0.49976111 F -0.8690571847 -1.3064032191 -0.5156887262 F -0.5203122626 -0.1924831086 1.3297317688 H 1.6584861947 -0.9812688 0.0100101341 O 1.7661442083 1.0333937367 0.105466428 H 1.2446122419 -0.1232827478 -1.4660513316 8 CF3CH2O equilibrium (UB3LYP/cc-pVTZ opt&freq) E=-452.2742627 hartree C -0.3411296534 -0.1692779184 -0.0027458945 C 1.1406247927 -0.0768481948 -0.364489894 F -1.0355233391 0.8668354808 -0.496856887 F -0.8668739305 -1.3023914627 -0.5139692537 F -0.5243950364 -0.1927574105 1.3260583915 H 1.6557585834 -0.977668397 0.0078802464 O 1.7680678067 1.0291275718 0.1024479438 H 1.2438588823 -0.123774966 -1.4611393235 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) 99.9300, 220.9774, 325.9923, 417.2256, 507.6251, 537.1398, 598.7049 669.3859, 829.9601, 1035.4905, 1090.1797, 1157.6189, 1270.7551, 1275.8938 1337.2935, 1405.2682, 2935.3738, 2959.3106 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -452.274262706 UB3LYP/6-31G(d,p) = -452.089629727 CCSD(T)/6-31G(d) = -450.99260206 MP2(FC)/6-31G(d) = -450.93965453628 PMP2(FC)/6-31G(d) = -450.94159308 QCISD(T)/6-31G(d) = -450.99411488 MP2(FC)/6-31G(d) = -450.93965453734 PMP2(FC)/6-31G(d) = -450.94159308 MP2/GTMP2Large = -451.44658531366 PMP2/GTMP2Large = -451.44896493 Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -451.6710258373802 G3(PMP2,CC) = -451.6714669100001 G3(MP2) = -451.6725386563201 G3(PMP2) = -451.67297973 E(HLC,G3(MP2)) = -0.171493 E(HLC,G3(MP2)//B3LYP) = -0.185733 E(ZPE) = .041905 (scaled with 0.985) ------------------------------------------------------------------------------- na= 19 nb= 18 8 CF3CH2O TS (UHF/6-31G(d) opt&freq) E=-449.9828807 hartree C .548179 -.011759 .000002 C -1.499979 .667805 .000038 F .772074 -.711223 -1.070698 F 1.267651 1.077990 -.000991 F .772647 -.709622 1.071638 H -1.359604 1.220366 .923271 O -2.110168 -.411421 .000015 H -1.359602 1.220418 -.923163 8 CF3CH2O TS (UB3LYP/6-31G(d) opt&freq) E=-452.0488057 hartree C -0.0765333937 -0.1375557219 -0.5698240437 C -0.0847827881 -0.1408328341 1.6862281802 F 1.1770469022 -0.1445693795 -0.9803311677 F -0.7082039085 -1.2511527565 -0.9184977436 F -0.7226021086 0.9346637978 -0.9857188071 H -1.1919082563 -0.1980965144 1.6486442949 O 0.5013243392 0.8923984106 1.9950774379 H 0.4330426675 -1.1212343907 1.653240848 8 CF3CH2O TS (UB3LYP/cc-pVTZ opt&freq) E=-452.240040037 hartree C .576264 -.014486 -.000003 C -1.520380 .659882 .000070 F .769923 -.726291 -1.087019 F 1.313879 1.082620 -.001862 F .770965 -.723283 1.088821 H -1.318298 1.215678 .933617 O -2.173943 -.375169 -.000014 H -1.318363 1.215886 -.933365 UB3LYP/cc-pVTZ vibrational frequencies (unscaled) -230.5008, 52.9219, 122.9098, 156.9861, 284.8374, 504.7399, 520.7934 558.9562, 670.1686, 1006.3512, 1124.9738, 1240.1726, 1256.0490, 1278.3559 1485.5371, 1639.2157, 2880.9863, 2936.6395 Single Point Calculations on UB3LYP/cc-pVTZ geometry UB3LYP/cc-pVTZ = -452.240040037 UB3LYP/6-31G(d,p) = -452.051486725 CCSD(T)/6-31G(d) = -450.94721561 MP2(FC)/6-31G(d) = -450.88694992600 PMP2(FC)/6-31G(d) = -450.90148832 QCISD(T)/6-31G(d) = -450.94939946 MP2(FC)/6-31G(d) = -450.88694992600 PMP2(FC)/6-31G(d) = -450.90148832 MP2/GTMP2Large = -451.39984699581 PMP2/GTMP2Large = -451.41408999 S**2 before annihilation .93453 (MP2/GTMP2Large) Additive G3 single point energies on UB3LYP/cc-pVTZ geometry with E(HLC,G3(MP2)) included and zero point energy excluded: G3(MP2,CC) = -451.6316056798101 G3(PMP2,CC) = -451.63131028 G3(MP2) = -451.6337895298101 G3(PMP2) = -451.6334941300001 E(HLC,G3(MP2)) = -0.171493 E(HLC,G3(MP2)//B3LYP) = -0.185733 E(ZPE) = .039764 (scaled with 0.985) +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++