The C4H6+. Potential Energy Surface. 1. The Ring Opening Reaction of Cyclobutene Radical Cation and Related Rearrangements by G. Narahari Sastry, Thomas Bally*, Vojtech Hrouda, and Petr Carsky* SUPPORTING INFORMATION ********************** Total energies, thermal corrections, and cartesian coordinates of all stationary points located in this study, ordered by method (I.: QCISD, II: B3LYP, III:UMP2, all with the 6-31G* basis set) I. QCISD//6-31G* **************** =============================================== 1. CB, C2v ----------------------------------------------- State=2-B1\Energy=-155.123617\S2=0.756\ ZPE=53.30741 Zero-point correction= 0.084951 Thermal correction to Energy= 0.089254 Thermal correction to Enthalpy= 0.090198 Thermal correction to Gibbs Free Energy= 0.058712 X Y Z 6 0.000000 0.783975 -0.693155 6 0.000000 -0.783975 -0.693155 6 0.000000 0.713346 0.798803 6 0.000000 -0.713346 0.798803 1 0.000000 1.453051 1.599475 1 0.000000 -1.453051 1.599475 1 0.886043 1.280927 -1.116681 1 -0.886043 1.280927 -1.116681 1 -0.886043 -1.280927 -1.116681 1 0.886043 -1.280927 -1.116681 =============================================== 2. cis-BD, C2v ----------------------------------------------- State=2-A2\\Energy=-155.1524504\S2=0.935\ ZPE=53.70952 Zero-point correction= 0.085592 Thermal correction to Energy= 0.090416 Thermal correction to Enthalpy= 0.091360 Thermal correction to Gibbs Free Energy= 0.058852 X Y Z C 0.000000 0.708499 0.604440 C 0.000000 -0.708499 0.604440 C 0.000000 1.506330 -0.535364 C 0.000000 -1.506330 -0.535364 H 0.000000 1.204945 1.574459 H 0.000000 -1.204945 1.574459 H 0.000000 1.099981 -1.544392 H 0.000000 2.590274 -0.444522 H 0.000000 -1.099981 -1.544392 H 0.000000 -2.590274 -0.444522 =============================================== 3. trans-BD, C2h ----------------------------------------------- \State=2-BG\Energy=-155.1583491\S2=0.92\ ZPE=53.73631 Zero-point correction= 0.085634 Thermal correction to Energy= 0.090405 Thermal correction to Enthalpy= 0.091349 Thermal correction to Gibbs Free Energy= 0.059123 X Y Z C .000000 .703850 .000000 C .000000 -.703850 .000000 C 1.190065 1.424667 .000000 C -1.190065 -1.424667 .000000 H -.951451 1.237278 .000000 H .951451 -1.237278 .000000 H 2.156404 .921588 .000000 H 1.189538 2.512513 .000000 H -2.156404 -.921588 .000000 H -1.189538 -2.512513 .000000 =============================================== 4. BCB, C2v ----------------------------------------------- State=2-A1\Energy=-155.1239593\S2=0.808 ZPE=53.91392 Zero-point correction= 0.085917 Thermal correction to Energy= 0.089736 Thermal correction to Enthalpy= 0.090680 Thermal correction to Gibbs Free Energy= 0.060449 X Y Z C 0.844950 0.000000 -0.233333 C -0.844950 0.000000 -0.233333 C 0.000000 1.133118 0.245341 C 0.000000 -1.133118 0.245341 H 1.479187 0.000000 -1.117976 H -1.479187 0.000000 -1.117976 H 0.000000 1.246826 1.340866 H 0.000000 2.079404 -0.294939 H 0.000000 -1.246826 1.340866 H 0.000000 -2.079404 -0.294939 =============================================== 5. TS1: CB -> cis-BD, C1 (conrotatory) ----------------------------------------------- \Energy=-155.088707\S2=0.911\ ZPE=52.17585, Frequencies -- -486.9096 Zero-point correction= 0.083148 Thermal correction to Energy= 0.087370 Thermal correction to Enthalpy= 0.088314 Thermal correction to Gibbs Free Energy= 0.056367 X Y Z C -1.128222 -0.559023 -0.086099 C -0.634392 0.751635 0.047429 C 0.747969 0.722803 -0.142101 C 1.021021 -0.690852 0.137803 H -2.011281 -0.910175 0.450063 H -0.830193 -1.179086 -0.934044 H -1.207158 1.586393 0.454548 H 1.466240 1.530275 -0.269745 H 1.407386 -1.379906 -0.620587 H 1.136755 -0.994879 1.177579 =============================================== 6. TS2: CB -> trans-BD, C1 (conrotatory) corresponds to Q1 in Figure 10 ----------------------------------------------- \Energy=-155.0905136\S2=0.764\ ZPE=53.08851, Frequencies -- -139.7706 Zero-point correction= 0.084602 Thermal correction to Energy= 0.088561 Thermal correction to Enthalpy= 0.089505 Thermal correction to Gibbs Free Energy= 0.058238 X Y Z C -0.206130 -0.746993 0.257472 C 1.124595 -0.409409 -0.219277 C -1.229077 0.042035 -0.260982 C 0.488214 0.849831 0.234395 H -1.236070 0.362857 -1.299878 H -2.137697 0.202648 0.318908 H -0.318457 -1.173078 1.257627 H 1.709193 -0.630344 -1.104295 H 0.572594 1.187969 1.266102 H 0.344827 1.637165 -0.508107 =============================================== 7. TS3: BCB -> cis-BD, C1 corresponds to Q2 in Figure 10 ----------------------------------------------- Energy=-155.0907083\S2=0.815 ZPE= 52.85319 Frequencies -- -136.9491 Zero-point correction= 0.084227 Thermal correction to Energy= 0.088246 Thermal correction to Enthalpy= 0.089191 Thermal correction to Gibbs Free Energy= 0.057757 X Y Z C 0.327108 -0.114416 0.542201 C -0.806527 0.804546 -0.266372 C 1.457387 -0.043529 -0.222276 C -1.046405 -0.571714 -0.123118 H 1.417453 -0.123164 -1.308833 H 2.436752 0.116115 0.229495 H 0.353806 -0.012326 1.623700 H -1.124829 1.721660 0.220543 H -1.756323 -0.916860 0.632469 H -0.916237 -1.234748 -0.979989 =============================================== 8. TS0: CB(2A1) -> CB(2B1), C2v ----------------------------------------------- State= 2-A1\QCISD=-155.0827801\S2=0.758\ C2V symmetry, ZPE=51.16133 Frequencies -- -1572.9038 Zero-point correction= 0.081531 Thermal correction to Energy= 0.086044 Thermal correction to Enthalpy= 0.086989 Thermal correction to Gibbs Free Energy= 0.055425 X Y Z C 0.000000 1.011796 -0.657856 C 0.000000 0.670355 0.782100 C 0.000000 -0.670355 0.782100 C 0.000000 -1.011796 -0.657856 H 0.000000 -1.378462 1.610831 H 0.000000 1.378462 1.610831 H -0.929243 1.262627 -1.178150 H 0.929243 1.262627 -1.178150 H 0.929243 -1.262627 -1.178150 H -0.929243 -1.262627 -1.178150 =============================================== 9. SP2-1: CB-(2A1) -> cis-BD, C2 (conrotatory) ----------------------------------------------- \QCISD=-155.0807437\S2=0.768\ ZPE = 51.01256 .086283 Zero-point correction= .081294 Thermal correction to Energy= .085339 Thermal correction to Enthalpy= .086283 Thermal correction to Gibbs Free Energy= .055405 X Y Z C .024068 1.096009 -.644150 C -.024068 .671588 .762464 C .024068 -.671588 .762464 C -.024068 -1.096009 -.644150 H .090240 -1.354979 1.609301 H -.090240 1.354979 1.609301 H -.814499 1.609389 -1.123424 H .967350 1.088835 -1.195762 H .814499 -1.609389 -1.123424 H -.967350 -1.088835 -1.195762 =============================================== 10. SP2-2: -CB -> trans-BD, C2 (conrotatory) ----------------------------------------------- 2B symmetry--conrotatory State=2-B\QCISD=-155.0793107\S2=0.913\ ZPE= 51.45381 Frequencies -- -2240.1911 ; -338.7790 Zero-point correction= 0.081997 Thermal correction to Energy= 0.085801 Thermal correction to Enthalpy= 0.086745 Thermal correction to Gibbs Free Energy= 0.056280 X Y Z C 0.198765 1.089573 -0.583349 C -0.198765 0.701534 0.712031 C 0.198765 -0.701534 0.712031 C -0.198765 -1.089573 -0.583349 H 0.944081 -1.190862 1.338274 H -0.944081 1.190862 1.338274 H -0.377001 1.809137 -1.171570 H 1.205591 0.872481 -0.938793 H 0.377001 -1.809137 -1.171570 H -1.205591 -0.872481 -0.938793 =============================================== 11. SP2-3: BCB <->cis-BD, C2 ----------------------------------------------- \State=2-A\HF=-154.519898\\QCISD=-155.0424815 ZPE = 50.42081, Thermal correction = 0.085541 Frequencies -- -1157.6466 -495.5885 Zero-point correction= 0.080351 Thermal correction to Energy= 0.084597 Thermal correction to Enthalpy= 0.085541 Thermal correction to Gibbs Free Energy= 0.054338 X Y Z 6 0.691980 1.070601 0.474241 6 0.691980 0.030553 -0.524960 6 -0.691980 -0.030553 -0.524960 6 -0.691980 -1.070601 0.474241 1 -1.418545 0.141853 -1.318621 1 1.418545 -0.141853 -1.318621 1 0.252775 1.012417 1.462460 1 1.144240 2.012179 0.160474 1 -0.252775 -1.012417 1.462460 1 -1.144240 -2.012179 0.160474 =============================================== 12. TS4: CB -> BCB (hydrogen shift) ----------------------------------------------- \QCISD=-155.0610133\S2=0.786 ZPE= 51.92043, Thermal correction = 0.087426 Frequencies -- -1352.9436 Zero-point correction= 0.082740 Thermal correction to Energy= 0.086482 Thermal correction to Enthalpy= 0.087426 Thermal correction to Gibbs Free Energy= 0.056643 X Y Z 6 -0.076423 -0.775748 0.216005 6 1.153955 -0.073900 -0.244436 6 0.054997 0.815207 0.275709 6 -1.179058 -0.102995 -0.345596 1 -0.152280 -1.387996 1.111026 1 2.027924 -0.167954 0.397296 1 1.366355 -0.030979 -1.312276 1 -0.059291 1.470384 1.133498 1 -2.200314 -0.052716 0.027237 1 -0.703218 0.993882 -0.766874 =============================================== 13. TS5: cis-BD -> trans-BD ----------------------------------------------- \QCISD=-155.1135995\ ZPE = 51.28313, Thermal correction = 0.087403 Frequencies -- -1146.9689, S2 = .781 Zero-point correction= 0.081725 Thermal correction to Energy= 0.086459 Thermal correction to Enthalpy= 0.087403 Thermal correction to Gibbs Free Energy= 0.054429 X Y Z 6 1.687106 -0.376494 -0.154664 6 0.685824 0.394426 0.294215 6 -0.657216 0.464015 -0.283774 6 -1.706803 -0.387545 0.138756 1 2.655148 -0.349756 0.336554 1 1.580678 -1.041422 -1.008985 1 0.819770 1.069041 1.152110 1 -0.881714 1.215835 -1.047851 1 -1.600539 -0.989926 1.041092 1 -2.626807 -0.470184 -0.440123 ----------------------------------------------- II. B3LYP/6-31G* **************** ========================================================== 1. CB, C2V ---------------------------------------------------------- State=2-B1\Energy=-155.6417279\S2=0.753 ; Zero-point correction= .083616 Thermal correction to Energy= .087959 Thermal correction to Enthalpy= .088903 Thermal correction to Gibbs Free Energy= .057421 X Y Z C .000000 .786450 -.689624 C .000000 -.786450 -.689624 C .000000 .713553 .796089 C .000000 -.713553 .796089 H .000000 1.453711 1.594347 H .000000 -1.453711 1.594347 H .882191 1.287886 -1.116569 H -.882191 1.287886 -1.116569 H -.882191 -1.287886 -1.116569 H .882191 -1.287886 -1.116569 ========================================================== 2. cis-BD, C2V ---------------------------------------------------------- State=2-A2\Energy=-155.6751498\S2=0.771 ; Zero-point correction= .084909 Thermal correction to Energy= .089766 Thermal correction to Enthalpy= .090710 Thermal correction to Gibbs Free Energy= .058165 X Y Z C .000000 .000000 .000000 C .000000 .000000 1.419400 C 1.130363 .000000 -.806185 C 1.130363 .000000 2.225585 H -.971159 .000000 -.490061 H -.971159 .000000 1.909461 H 2.141605 .000000 -.409128 H 1.030713 .000000 -1.888206 H 2.141605 .000000 1.828528 H 1.030713 .000000 3.307606 ========================================================== 3. trans-BD, C2h ---------------------------------------------------------- State=2-BG\Energy=-155.6809888\S2=0.771 Zero-point correction= .084921 Thermal correction to Energy= .089730 Thermal correction to Enthalpy= .090674 Thermal correction to Gibbs Free Energy= .058396 X Y Z C .000000 .705300 .000000 C .000000 -.705300 .000000 C 1.182319 1.435253 .000000 C -1.182319 -1.435253 .000000 H -.951394 1.233943 .000000 H .951394 -1.233943 .000000 H 2.151419 .941133 .000000 H 1.173913 2.521721 .000000 H -2.151419 -.941133 .000000 H -1.173913 -2.521721 .000000 ========================================================== 4. BCB, C2v ---------------------------------------------------------- State=2-A1\Energy=-155.6379199\S2=0.761 Zero-point correction= .084660 Thermal correction to Energy= .088534 Thermal correction to Enthalpy= .089478 Thermal correction to Gibbs Free Energy= .059170 X Y Z C .849200 .000000 -.227198 C -.849200 .000000 -.227198 C .000000 1.133809 .238965 C .000000 -1.133809 .238965 H 1.499094 .000000 -1.098523 H -1.499094 .000000 -1.098523 H .000000 1.267815 1.333089 H .000000 2.077467 -.305171 H .000000 -1.267815 1.333089 H .000000 -2.077467 -.305171 ========================================================== 5. TS1: CB -> cis-BD, C1 ---------------------------------------------------------- Energy=-155.6116345\S2=0.767 V(imag) -499.1688 Zero-point correction= .082337 Thermal correction to Energy= .086526 Thermal correction to Enthalpy= .087470 Thermal correction to Gibbs Free Energy= .055665 X Y Z 6 -1.123910 -0.583893 -0.066711 6 -0.653046 0.743167 0.025947 6 0.723924 0.736812 -0.121541 6 1.052547 -0.671188 0.118970 1 -1.985226 -0.942099 0.497614 1 -0.827669 -1.224047 -0.898618 1 -1.252071 1.581234 0.381715 1 1.422576 1.567053 -0.197608 1 1.432624 -1.330219 -0.667295 1 1.212679 -1.001314 1.144199 ========================================================== 6. TS2: TS-CB -> trans-BD, C1 symmetry corresponds to B1 in Figure 10 ---------------------------------------------------------- Energy=-155.6063886\S2=0.754\V(imag)= -330.9815 Zero-point correction= 0.081572 Thermal correction to En 0.086391 Thermal correction to Enthalpy= 0.087335 Thermal correction to Gibbs Free Energy= 0.054085 X Y Z 6 -0.343586 -0.717324 0.225981 6 1.008201 -0.513723 -0.265161 6 -1.300026 0.176722 -0.219706 6 0.751242 0.818195 0.215474 1 -1.229062 0.654386 -1.192050 1 -2.219965 0.329951 0.342139 1 -0.510446 -1.268470 1.156560 1 1.748832 -1.038683 -0.851154 1 0.842967 1.069885 1.272794 1 0.672693 1.669713 -0.467821 ========================================================== 7. TS3: BCB <-> cis-BD, C1 corresponds to B2 in Figure 10 ---------------------------------------------------------- Energy=-155.6065445\S2=0.756 V(imag) = -130.5708 Zero-point correction= .082956 Thermal correction to Energy= .087077 Thermal correction to Enthalpy= .088022 Thermal correction to Gibbs Free Energy= .056431 X Y Z 6 .331716 -.158659 .532057 6 -.805956 .820232 -.225379 6 1.460217 -.032571 -.225697 6 -1.055017 -.557324 -.145392 1 1.425850 -.053912 -1.313535 1 2.435467 .115324 .236615 1 .362734 -.113075 1.616129 1 -1.091587 1.731285 .289854 1 -1.767574 -.931459 .594562 1 -.950652 -1.178236 -1.037158 ========================================================== 8. TS0: CB(2A1) -> CB(2B1), C2v ---------------------------------------------------------- C2V symmetry, State=2-A1\Energy=-155.6017011\S2=0.752, V(imag) -1726.7323 Zero-point correction= 0.080399 Thermal correction to Energy= 0.085077 Thermal correction to Enthalpy= 0.086022 Thermal correction to Gibbs Free Energy= 0.054145 X Y Z 6 0.000000 1.036512 -0.651810 6 0.000000 0.668408 0.774029 6 0.000000 -0.668408 0.774029 6 0.000000 -1.036512 -0.651810 1 0.000000 -1.362042 1.614889 1 0.000000 1.362042 1.614889 1 -0.928300 1.284000 -1.174102 1 0.928300 1.284000 -1.174102 1 0.928300 -1.284000 -1.174102 1 -0.928300 -1.284000 -1.174102 ========================================================== 9. SP2-1: CB(2A1) -> cis-BD, C2 symmetry ---------------------------------------------------------- State=2-A\Energy=-155.6012288\S2=0.754 V(imag) -1229.0939; -328.1724 Zero-point correction= 0.080115 Thermal correction to Energy= 0.084245 Thermal correction to Enthalpy= 0.085189 Thermal correction to Gibbs Free Energy= 0.054190 X Y Z 6 0.010455 1.083682 -0.644666 6 -0.010455 0.668896 0.763938 6 0.010455 -0.668896 0.763938 6 -0.010455 -1.083682 -0.644666 1 0.052238 -1.350121 1.613761 1 -0.052238 1.350121 1.613761 1 -0.871298 1.508907 -1.131655 1 0.949942 1.157199 -1.197739 1 0.871298 -1.508907 -1.131655 1 -0.949942 -1.157199 -1.197739 ========================================================== 10. SP2-2: CB -> trans-BD, C2 symmetry ---------------------------------------------------------- State=2-B\Energy=-155.6013852\S2=0.769, ZPE= 51.00517 V(imag) = -618.7056 -449.1708 Zero-point correction= 0.081282 Thermal correction to Energy= 0.085109 Thermal correction to Enthalpy= 0.086053 Thermal correction to Gibbs Free Energy= 0.055548 X Y Z 6 0.190200 1.081199 -0.587121 6 -0.190200 0.701552 0.715155 6 0.190200 -0.701552 0.715155 6 -0.190200 -1.081199 -0.587121 1 0.912185 -1.204982 1.355570 1 -0.912185 1.204982 1.355570 1 -0.392919 1.797647 -1.171229 1 1.194976 0.878517 -0.952545 1 0.392919 -1.797647 -1.171229 1 -1.194976 -0.878517 -0.952545 ========================================================== 11. SP2-3: BCB -> cis-BD ---------------------------------------------------------- State=2-A\HF=-155.565196\S2=0.779\ V(imag) = -1206.2215 -381.7908 Zero-point correction= 0.079220 (Hartree/Particle) Thermal correction to Energy= 0.083589 Thermal correction to Enthalpy= 0.084533 Thermal correction to Gibbs Free Energy= 0.053096 X Y Z C 0.691319 1.086530 0.475179 C 0.691319 0.051088 -0.523191 C -0.691319 -0.051088 -0.523191 C -0.691319 -1.086530 0.475179 H -1.410738 0.104896 -1.325734 H 1.410738 -0.104896 -1.325734 H 0.261387 1.029377 1.465997 H 1.102921 2.041866 0.147806 H -0.261387 -1.029377 1.465997 H -1.102921 -2.041866 0.147806 ========================================================== 12. TS4: CB -> BCB, C1 ---------------------------------------------------------- \HF=-155.5770223\S2=0.757\ V(imag) = -1346.0288 Zero-point correction= .081411 Thermal correction to Energy= .085234 Thermal correction to Enthalpy= .086178 Thermal correction to Gibbs Free Energy= .055272 X Y Z 6 -.088716 -.776161 .215192 6 1.154246 -.085312 -.241816 6 .071196 .827224 .266569 6 -1.187346 -.100757 -.339943 1 -.163723 -1.388059 1.109631 1 2.024079 -.191167 .401796 1 1.373888 -.052647 -1.307895 1 -.033052 1.475716 1.129442 1 -2.206902 -.035957 .032944 1 -.690570 1.002156 -.765932 ---------------------------------------------------------- III. UMP2=FULL/6-31G* ********************* ========================================================== 1. CB, C2v ---------------------------------------------------------- \State=2-B1\\MP2=-155.094519\ ZPE= 53.72838 \S2=0.756\ Zero-point correction= 0.085622 Thermal correction to Energy= 0.089913 Thermal correction to Enthalpy= 0.090858 Thermal correction to Gibbs Free Energy= 0.059364 X Y Z C .000000 .780719 -.689033 C .000000 -.780719 -.689033 C .000000 .713366 .794022 C .000000 -.713366 .794022 H .000000 1.451675 1.593123 H .000000 -1.451675 1.593123 H .884599 1.276043 -1.111529 H -.884599 1.276043 -1.111529 H -.884599 -1.276043 -1.111529 H .884599 -1.276043 -1.111529 ========================================================== 2. cis-BD ---------------------------------------------------------- \MP2=-155.1181845\S2=0.926\ ZPE=54.46876 Zero-point correction= .086801 Thermal correction to Energy= .091579 Thermal correction to Enthalpy= .092523 Thermal correction to Gibbs Free Energy= .060075 X Y Z C 1.374044 .794538 .000000 C .000000 .928922 .000000 C -.916803 -.149555 .000000 C -.562956 -1.484039 .000000 H 1.876867 -.166353 .000000 H 2.009008 1.673967 .000000 H -.413778 1.934087 .000000 H -1.975473 .096998 .000000 H .466356 -1.825591 .000000 H -1.328688 -2.252302 .000000 ========================================================== 3. trans-BD ---------------------------------------------------------- \State=2-BG\ MP2=-155.1248965\S2=0.913\ ZPE=54.46204 Zero-point correction= .086791 Thermal correction to Energy= .091500 Thermal correction to Enthalpy= .092444 Thermal correction to Gibbs Free Energy= .060322 X Y Z C .603620 1.742559 .000000 C .603620 .359959 .000000 C -.603620 -.359959 .000000 C -.603620 -1.742559 .000000 H -.325454 2.305082 .000000 H 1.530246 2.306804 .000000 H 1.549455 -.177558 .000000 H -1.549455 .177558 .000000 H .325454 -2.305082 .000000 H -1.530246 -2.306804 .000000 ========================================================== 4.BCB, ---------------------------------------------------------- MP2=-155.0976021\S2=0.806\ZPE= 54.22420 Zero-point correction= 0.086420 Thermal correction to Energy= 0.090267 Thermal correction to Enthalpy= 0.091211 Thermal correction to Gibbs Free Energy= 0.060949 X Y Z C .836874 .000000 -.237207 C -.836874 .000000 -.237207 C .000000 1.126237 .246063 C .000000 -1.126237 .246063 H 1.480392 .000000 -1.112364 H -1.480392 .000000 -1.112364 H .000000 1.225262 1.342123 H .000000 2.076141 -.282895 H .000000 -1.225262 1.342123 H .000000 -2.076141 -.282895 ========================================================== 5. U1 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.0678808\\S2=0.763 Zero-point correction= .085719 Thermal correction to Energy= .090232 Thermal correction to Enthalpy= .091176 Thermal correction to Gibbs Free Energy= .058899 X Y Z C 1.177300 -.011127 -.270327 C .117500 -.792483 .217611 C -1.166816 -.310855 -.196839 C -.321419 .855873 .260971 H 2.088024 .070046 .318073 H 1.234100 .272915 -1.315738 H .212462 -1.245325 1.206632 H -1.795809 -.381750 -1.072893 H -.226281 1.635378 -.495241 H -.351891 1.200290 1.290669 ========================================================== 6. U2 (cf. Figure 10): ---------------------------------------------------------- MP2=-155.0669461\S2=0.766\ ZPE=53.86756 Zero-point correction= .085843 Thermal correction to Energy= .090330 Thermal correction to Enthalpy= .091274 Thermal correction to Gibbs Free Energy= .058987 X Y Z C -.344156 -.303346 .436471 C .916182 -.596290 -.475320 C -1.476829 .117357 -.185376 C .995641 .670673 .097366 H -1.443862 .592868 -1.163099 H -2.454218 -.018929 .271859 H -.359898 -.772427 1.414544 H 1.442955 -1.530096 -.319241 H 1.548085 .838807 1.023168 H .721910 1.559406 -.466076 ========================================================== 7. U3 (cf. Figure 10): --------------------------------------------------------- \MP2=-155.067459\S2=0.793\ Zero-point correction= .085486 Thermal correction to Energy= .090134 Thermal correction to Enthalpy= .091078 Thermal correction to Gibbs Free Energy= .058388 X Y Z C -1.449911 .005852 .245498 C -.336898 -.190411 -.506367 C .876808 .790117 -.171701 C 1.058209 -.512871 .287466 H -2.445421 -.156097 -.162500 H -1.388592 .340102 1.279296 H -.384854 -.531682 -1.535209 H .763065 1.776492 .257989 H .957429 -.751953 1.346500 H 1.609128 -1.232991 -.315450 ========================================================== 8. U4 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.0676215\S2=0.766\ ZPE=53.08900 V(imag) = -367.1907 Zero-point correction= 0.084603 Thermal correction to Energy= 0.088759 Thermal correction to Enthalpy= 0.089703 Thermal correction to Gibbs Free Energy= 0.058097 X Y Z C -0.103953 -0.823802 0.181138 C 1.155580 -0.276807 -0.197963 C -1.167639 -0.011674 -0.259669 C 0.289360 0.867082 0.260459 H -1.245984 0.289071 -1.298906 H -2.074707 0.036000 0.337479 H -0.196163 -1.342142 1.140028 H 1.959992 -0.369259 -0.910364 H 0.309138 1.184692 1.299798 H 0.207633 1.672838 -0.471826 ========================================================== 9. U5 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.0612703\S2=0.767\ ZPE=53.19266 V(imag) = -420.6774 Zero-point correction= .084768 Thermal correction to Energy= .088970 Thermal correction to Enthalpy= .089914 Thermal correction to Gibbs Free Energy= .058080 X Y Z C 1.345996 .329369 -.202206 C .481136 -.623124 .257113 C -.882897 -.616902 -.284996 C -1.036751 .685322 .213784 H 2.323007 .460036 .255901 H 1.136843 .909310 -1.095728 H .713224 -1.230994 1.132944 H -1.372415 -1.208722 -1.046145 H -1.165539 1.556628 -.435566 H -1.080024 .865756 1.286420 ========================================================== 10. U6 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.0662188\ S2=0.795\ ZPE=53.95831 V(imag) = -195.3992 Zero-point correction= 0.085988 Thermal correction to Energy= 0.089849 Thermal correction to Enthalpy= 0.090794 Thermal correction to Gibbs Free Energy= 0.059616 X Y Z C -0.314207 -0.493006 0.339035 C 0.976527 -0.515203 -0.460444 C -1.420774 0.103104 -0.183553 C 0.856785 0.745721 0.159984 H -1.392004 0.599699 -1.150499 H -2.372664 0.093961 0.343766 H -0.341226 -0.985147 1.307172 H 1.693738 -1.320713 -0.373637 H 1.275908 0.945720 1.147045 H 0.546258 1.622792 -0.403975 ========================================================== 11. U7 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.0645372\ S2=0.806\ ZPE=53.73543 V(imag) = -246.0198 Zero-point correction= 0.085633 Thermal correction to Energy= 0.089533 Thermal correction to Enthalpy= 0.090477 Thermal correction to Gibbs Free Energy= 0.059251 X Y Z C 0.312440 -0.209033 0.535644 C -0.727546 0.839043 -0.191622 C 1.423252 -0.041315 -0.228689 C -1.064682 -0.523307 -0.172157 H 1.367362 -0.017583 -1.315150 H 2.405296 0.097072 0.220225 H 0.349168 -0.215122 1.619356 H -1.002342 1.733792 0.354262 H -1.806302 -0.876140 0.544250 H -0.973969 -1.114349 -1.082001 ========================================================== 12. U8 (cf. Figure 10): ---------------------------------------------------------- \MP2=-155.059872\S2=0.974\ ZPE= 53.43665 V(imag) = -626.4641 Zero-point correction= 0.085157 Thermal correction to Energy= 0.089353 Thermal correction to Enthalpy= 0.090297 Thermal correction to Gibbs Free Energy= 0.058462 X Y Z C -0.384592 -0.553766 0.223505 C 0.944280 -0.526103 -0.437327 C -1.461174 0.203555 -0.120428 C 0.994400 0.726383 0.166835 H -1.436872 0.932637 -0.923955 H -2.405779 0.071734 0.396899 H -0.470724 -1.270048 1.038299 H 1.645575 -1.340439 -0.299946 H 1.590154 0.907300 1.064769 H 0.520164 1.598402 -0.271572 ========================================================== 13. TS0, C2v ---------------------------------------------------------- \MP2=-155.0537126\ \State=2-A1\ \S2=0.758 ZPE=51.56262 V(imag)= -1003.232 Zero-point correction= 0.082170 Thermal correction to Energy= 0.086708 Thermal correction to Enthalpy= 0.087652 Thermal correction to Gibbs Free Energy= 0.056048 X Y Z C 0.000000 1.005684 -0.653756 C 0.000000 0.670826 0.777887 C 0.000000 -0.670826 0.777887 C 0.000000 -1.005684 -0.653756 H 0.000000 -1.375127 1.607570 H 0.000000 1.375127 1.607570 H -0.926800 1.251400 -1.176180 H 0.926800 1.251400 -1.176180 H 0.926800 -1.251400 -1.176180 H -0.926800 -1.251400 -1.176180 ========================================================== 14: C2 symmetric TS for the CB -> cis-1,3-BD rearrangement, (second order saddle at B3LYP and QCISD levels) ---------------------------------------------------------- \State=2-A\MP2=-155.0523644\S2=0.765\ ZPE=57.0712 V(imag)= -383.0106 Zero-point correction= 0.090949 Thermal correction to Energy= 0.094972 Thermal correction to Enthalpy= 0.095916 Thermal correction to Gibbs Free Energy= 0.065094 X Y Z C -0.020794 1.073608 -0.643202 C 0.020794 0.671948 0.762953 C -0.020794 -0.671948 0.762953 C 0.020794 -1.073608 -0.643202 H -0.080966 -1.356641 1.606733 H 0.080966 1.356641 1.606733 H -0.961942 1.074085 -1.195152 H 0.824198 1.564293 -1.130091 H 0.961942 -1.074085 -1.195152 H -0.824198 -1.564293 -1.130091 ========================================================== 15. C2 symmetric TS for the CB -> trans-BD rearrangement (second order saddle at B3LYP and QCISD levels) ---------------------------------------------------------- \State=2-B\MP2=-155.0470586\S2=0.893\ ZPE=59.25489 V(imag)= -538.1735 Zero-point correction= 0.094429 Thermal correction to Energy= 0.098384 Thermal correction to Enthalpy= 0.099328 Thermal correction to Gibbs Free Energy= 0.068616 X Y Z C 0.205910 1.091979 -0.573408 C -0.205910 0.690407 0.697931 C 0.205910 -0.690407 0.697931 C -0.205910 -1.091979 -0.573408 H 0.940401 -1.180623 1.333386 H -0.940401 1.180623 1.333386 H -0.353830 1.831968 -1.148049 H 1.203368 0.850921 -0.932475 H 0.353830 -1.831968 -1.148049 H -1.203368 -0.850921 -0.932475 ========================================================== 16. TS4: BCB -> cis-BD, C1 ---------------------------------------------------------- Energy=-155.0676215\S2=0.766\ V(imag)= -367.1907 Zero-point correction= 0.084603 Thermal correction to Energy= 0.088759 Thermal correction to Enthalpy= 0.089703 Thermal correction to Gibbs Free Energy= 0.058097 X Y Z C -0.103953 -0.823802 0.181138 C 1.155580 -0.276807 -0.197963 C -1.167639 -0.011674 -0.259669 C 0.289360 0.867082 0.260459 H -1.245984 0.289071 -1.298906 H -2.074707 0.036000 0.337479 H -0.196163 -1.342142 1.140028 H 1.959992 -0.369259 -0.910364 H 0.309138 1.184692 1.299798 H 0.207633 1.672838 -0.471826 ========================================================== 17. TS5: cis-BD -> trans-BD ---------------------------------------------------------- MP2=-155.0808725\\S2=0.761\ ZPE=55.56511, V(imag)= -346.1488 Zero-point correction= 0.088549 Thermal correction to Energy= 0.093163 Thermal correction to Enthalpy= 0.094108 Thermal correction to Gibbs Free Energy= 0.061298 X Y Z C -1.707405 -0.387762 0.111733 C -0.641272 0.471548 -0.262467 C 0.684316 0.358522 0.326401 C 1.678893 -0.344106 -0.181295 H -2.656928 -0.360515 -0.415158 H -1.579644 -1.091117 0.929944 H -0.857670 1.259841 -0.986165 H 0.789202 0.912372 1.265634 H 1.587566 -0.921017 -1.095633 H 2.630280 -0.388779 0.335143 *** END ***