The Radical Cation of syn-Tricyclooctadiene and its Rearrangement Products ------------------------------------------------------------------------ T. Bally, S. Bernhard, S. Matznger, G. N. Sastry, L. Truttmann, J.-L. Roulin, Z. Zhu, A. Marcinek, J. Adamus, R. Kaminski, J. Gebicki, F. Williams, G.-F. Chen, M. Fuelscher SUPPORTING INFORMATION ====================== A.) B3LYP/6-31G* optimized geometries, energies, and thermal corrections, as well as RCCSD(T)/cc-pVDZ single-point energies (where calculated) of all the stationary points discussed in this paper [The CASSCF/CASPT2 calculations are described under B) at the end of this file] A1. syn-TOD neutral ******************* E(B3LYP/6-31G*) = -309.4994017 Pointgroup: C2v State=1-A1, minimum Progam: Gaussian94 --------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z --------------------------------------------------------- 1 6 0.796995 0.782568 0.658468 2 6 0.796995 -0.782568 0.658468 3 6 -0.796995 -0.782568 0.658468 4 6 -0.796995 0.782568 0.658468 5 6 1.511408 0.672445 -0.671031 6 6 1.511408 -0.672445 -0.671031 7 6 -1.511408 -0.672445 -0.671031 8 6 -1.511408 0.672445 -0.671031 9 1 1.256540 1.355291 1.468611 10 1 1.256540 -1.355291 1.468611 11 1 -1.256540 -1.355291 1.468611 12 1 -1.256540 1.355291 1.468611 13 1 1.834736 1.418903 -1.393230 14 1 1.834736 -1.418903 -1.393230 15 1 -1.834736 -1.418903 -1.393230 16 1 -1.834736 1.418903 -1.393230 --------------------------------------------------------- nuclear repulsion energy 346.0014326717 Hartrees. A2. syn-TOD 2A1 state ********************* E(B3LYP/6-31G*) = -309.199843309 a.u. = 0.7522 E(ROHF/cc-pVDZ) = -307.15887817 a.u. E(RCCSD/cc-pVDZ) = -308.259480336554 a.u. E(RCCSD(T)/cc-pVDZ) = -308.311285278311 a.u. Pointgroup: C2v State: 2-A1, minimum Program: Gaussian94, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.832088 0.787216 0.625685 2 6 0.832088 -0.787216 0.625685 2 6 0.832088 -0.787216 0.625685 3 6 -0.832088 -0.787216 0.625685 4 6 -0.832088 0.787216 0.625685 5 6 1.577387 0.689554 -0.647070 6 6 1.577387 -0.689554 -0.647070 7 6 -1.577387 -0.689554 -0.647070 8 6 -1.577387 0.689554 -0.647070 9 1 1.216745 1.417649 1.428520 10 1 1.216745 -1.417649 1.428520 11 1 -1.216745 -1.417649 1.428520 12 1 -1.216745 1.417649 1.428520 13 1 2.027677 1.431785 -1.300212 14 1 2.027677 -1.431785 -1.300212 15 1 -2.027677 -1.431785 -1.300212 16 1 -2.027677 1.431785 -1.300212 ---------------------------------------------------------- nuclear repulsion energy 342.2759715376 Hartrees. Zero-point correction= 0.129230 Thermal correction to Energy= 0.136133 Thermal correction to Enthalpy= 0.137078 Thermal correction to Gibbs Free Energy= 0.098653 A3. syn-TOD 2B1 (pi) state ************************** E(B3LYP/6-31G*) = -309.185329503 a.u. = 0.7528 E(ROHF/cc-pVDZ) = -307.15728287 a.u. E(RCCSD/cc-pVDZ)= -308.250115959250 a.u. E(RCCSD(T)/cc-pVDZ) = -308.299384791117 a.u. Pointgroup: C2v State: 2-B1, minimum Program: Gaussian92/DFT, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -.787500 .785000 -.710628 2 6 -.787500 -.785000 -.710628 3 6 .787500 -.785000 -.710628 4 6 .787500 .785000 -.710628 5 6 -1.323363 .694200 .707935 6 6 -1.323363 -.694200 .707935 7 6 1.323363 -.694200 .707935 8 6 1.323363 .694200 .707935 9 1 -1.317822 1.371306 -1.462047 10 1 -1.317822 -1.371306 -1.462047 11 1 1.317822 -1.371306 -1.462047 12 1 1.317822 1.371306 -1.462047 13 1 -1.532653 1.432072 1.478202 14 1 -1.532653 -1.432072 1.478202 15 1 1.532653 -1.432072 1.478202 16 1 1.532653 1.432072 1.478202 ---------------------------------------------------------- nuclear repulsion energy 351.0192095162 Hartrees. ZERO-POINT VIBRATIONAL ENERGY 81.74350 (KCAL/MOL) A4. syn-TOD 2B1 (sigma) state in C2v symmetry ********************************************* E(B3LYP/6-31G*) = -309.194483798 a.u. = 0.7517 E(ROHF/cc-pVDZ) = -307.16913667 a.u. E(RCCSD/cc-pVDZ) = -308.265238283593 a.u. E(RCCSD(T)/cc-pVDZ) = -308.314390504327 a.u. Pointgroup: C2v State: 2-B1, Transition state Program: Gaussian92/DFT, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 .751900 .886400 .617311 2 6 .751900 -.886400 .617311 3 6 -.751900 -.886400 .617311 4 6 -.751900 .886400 .617311 5 6 1.531286 .668100 -.648133 6 6 1.531286 -.668100 -.648133 7 6 -1.531286 -.668100 -.648133 8 6 -1.531286 .668100 -.648133 9 1 1.236332 1.273572 1.516379 10 1 1.236332 -1.273572 1.516379 11 1 -1.236332 -1.273572 1.516379 12 1 -1.236332 1.273572 1.516379 13 1 1.926801 1.413642 -1.331444 14 1 1.926801 -1.413642 -1.331444 15 1 -1.926801 -1.413642 -1.331444 16 1 -1.926801 1.413642 -1.331444 ---------------------------------------------------------- nuclear repulsion energy 343.9003008181 Hartrees. ZERO-POINT VIBRATIONAL ENERGY 80.79747 (KCAL/MOL) Low frequencies --- -214.1497(B1) A5. 2A' syn-TOD (Cs minimum to which 2B1 decays) ************************************************ E(B3LYP/6-31G*) = -309.195439470 a.u. = 0.7518 E(ROHF/cc-pVDZ) = -307.17594714 a.u. E(RCCSD/cc-pVDZ)= -308.265590803363 a.u. E(RCCSD(T)/cc-pVDZ)= -308.313566479774 a.u. Pointgroup: Cs State: 2-A', minimum Program: Gaussian94, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -.613363 -.728974 .970566 2 6 -.613363 -.728974 -.970566 3 6 -.613363 .792749 -.799529 4 6 -.613363 .792749 .799529 5 6 .581817 -1.555593 .671707 6 6 .581817 -1.555593 -.671707 7 6 .705865 1.522996 -.671293 8 6 .705865 1.522996 .671293 9 1 -1.473877 -1.189843 1.460126 10 1 -1.473877 -1.189843 -1.460126 11 1 -1.473718 1.268206 -1.274518 12 1 -1.473718 1.268206 1.274518 13 1 1.178719 -2.123763 1.380578 14 1 1.178719 -2.123763 -1.380578 15 1 1.403143 1.858326 -1.432278 16 1 1.403143 1.858326 1.432278 ---------------------------------------------------------- nuclear repulsion energy 342.7877856949 Hartrees. Zero-point correction= .129015 Thermal correction to Energy= .135903 Thermal correction to Enthalpy= .136848 Thermal correction to Gibbs Free Energy= .098021 A6. TS between syn-A'-TOD and COT ********************************* E(B3LYP/6-31G*) = -309.194775492 a.u. = 0.7552 E(ROHF/cc-pVDZ) = -307.17580886 a.u. E(RCCSD/cc-pVDZ)= -308.264570705185 a.u. E(RCCSD(T)/cc-pVDZ) = -308.312720184673 a.u. Pointgroup: C1 State: 2-A, TS Program: Gaussian94, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -1.448299 -0.801570 -0.596405 2 6 1.473808 0.732517 -0.685976 3 6 -0.847463 1.032624 0.523315 4 6 0.846125 -0.763826 0.658481 5 6 -1.626697 0.531181 -0.616134 6 6 1.612720 -0.600041 -0.637877 7 6 -0.638304 -0.995090 0.634379 8 6 0.681397 0.829166 0.605928 9 1 -1.866336 -1.586134 -1.221137 10 1 1.756474 1.506834 -1.392054 11 1 -1.313589 1.690628 1.258224 12 1 1.338800 -1.166700 1.545636 13 1 -2.295243 1.122734 -1.237486 14 1 2.082446 -1.337848 -1.279224 15 1 -1.123947 -1.363674 1.540309 16 1 1.101677 1.344393 1.471457 ---------------------------------------------------------- nuclear repulsion energy 342.0583369644 Hartrees. Low frequencies --- -269.7963 Zero-point correction= 0.128965 Thermal correction to Energy= 0.135243 Thermal correction to Enthalpy= 0.136188 Thermal correction to Gibbs Free Energy= 0.098423 A7. TS : 2A' syn-TOD -> 2A1 syn-TOD *********************************** E(B3LYP/6-31G*) = -309.194753954 a.u. = 0.7521 E(RCCSD(T)/cc-pVDZ) = -308.310473554307 a.u. (different nucrep=342.99091751) Pointgroup: Cs State: 2-A', TS Program: Gaussian94 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -.617391 -.742738 .908782 2 6 -.617391 -.742738 -.908782 3 6 -.617391 .828588 -.777187 4 6 -.617391 .828588 .777187 5 6 .581517 -1.573883 .678565 6 6 .581517 -1.573883 -.678565 7 6 .709661 1.529566 -.677718 8 6 .709661 1.529566 .677718 9 1 -1.450899 -1.180676 1.461491 10 1 -1.450899 -1.180676 -1.461491 11 1 -1.454288 1.267729 -1.323254 12 1 -1.454288 1.267729 1.323254 13 1 1.141599 -2.173685 1.391593 14 1 1.141599 -2.173685 -1.391593 15 1 1.425207 1.837428 -1.433892 16 1 1.425207 1.837428 1.433892 ---------------------------------------------------------- nuclear repulsion energy 342.9764588056 Hartrees. Zero-point correction= .128468 (Hartree/Particle) Thermal correction to Energy= .134817 Thermal correction to Enthalpy= .135761 Thermal correction to Gibbs Free Energy= .097841 Low frequencies --- -431.3829 A8. BCB radical cation ********************* E(B3LYP/6-31G*) = -309.212196692 a.u. = 0.7673 E(RCCSD/cc-pVDZ)= -308.273413985595 a.u. E(RCCSD(T)/cc-pVDZ) = -308.323502546726 a.u. Pointgroup: C2v State: 2-B1, minimum Program: Gaussian98, Molpro 98.1 ------------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ------------------------------------------------------------- 1 6 0.000000 0.774286 0.966924 2 6 0.000000 -0.774286 0.966924 3 6 0.000000 1.792248 -0.900396 4 6 0.000000 -1.792248 -0.900396 5 6 -1.004026 1.348816 -0.038713 6 6 1.004026 1.348816 -0.038713 7 6 1.004026 -1.348816 -0.038713 8 6 -1.004026 -1.348816 -0.038713 9 1 0.000000 1.212330 1.968399 10 1 0.000000 -1.212330 1.968399 11 1 0.000000 2.311784 -1.851588 12 1 0.000000 -2.311784 -1.851588 13 1 -2.085107 1.453538 -0.025711 14 1 2.085107 1.453538 -0.025711 15 1 2.085107 -1.453538 -0.025711 16 1 -2.085107 -1.453538 -0.025711 ------------------------------------------------------------- nuclear repulsion energy 334.8047346350 Hartrees. Zero-point correction= 0.130390 Thermal correction to Energy= 0.137448 Thermal correction to Enthalpy= 0.138392 Thermal correction to Gibbs Free Energy= 0.099312 A9. TS: BCB -> TCO ****************** E(B3LYP/6-31G*) = -309.196913798 a.u. = 0.7731 E(ROHF/cc-pVDZ) = -307.18104729 a.u. E(RCCSD/cc-pVDZ)= -308.266754053613 a.u. E(RCCSD(T)/cc-pVDZ) = -308.314853252750 a.u. Pointgroup: C1 State: 2-A, TS Program: Gaussian94, Molpro 96.1 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 1.953530 .670485 .345356 2 6 1.583718 -.651846 .603003 3 6 1.147704 .761412 -.794569 4 6 .686843 -.687757 -.648217 5 6 -1.493491 .988970 .453579 6 6 -.812211 -.926660 -.316172 7 6 -1.768200 .187693 -.646445 8 6 -1.196292 -.268757 .993360 9 1 2.641246 1.356663 .827781 10 1 1.897733 -1.410761 1.310785 11 1 1.010856 1.505475 -1.571163 12 1 .998526 -1.362918 -1.451538 13 1 -1.832644 1.944994 .828803 14 1 -1.145409 -1.952232 -.485907 15 1 -2.629540 .198271 -1.315586 16 1 -1.550379 -.720737 1.917449 ---------------------------------------------------------- nuclear repulsion energy 334.8608714377 Hartrees. Zero-point correction= .128834 Thermal correction to Energy= .135403 Thermal correction to Enthalpy= .136347 Thermal correction to Gibbs Free Energy= .097677 Low frequencies --- -282.6768 A10. TCO radical cation *********************** E(B3LYP/6-31G*) = -309.222156793 a.u. = 0.7538 E(ROHF/cc-pVDZ) = -307.19099203 a.u. E(RCCSD/cc-pVDZ)= -308.288702259799 a.u. E(RCCSD(T)/cc-pVDZ) = -308.337566016095 a.u. Pointgroup: Cs State: 2-A', minimum Program: Gaussian98 -------------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z -------------------------------------------------------------- 1 6 -1.004720 -1.488908 0.685680 2 6 -1.004720 -1.488908 -0.685680 3 6 0.306455 -0.780434 -0.785072 4 6 0.306455 -0.780434 0.785072 5 6 0.306455 0.794908 1.084284 6 6 0.306455 0.794908 -1.084284 7 6 1.148583 1.386256 0.000000 8 6 -0.426369 1.480180 0.000000 9 1 -1.679824 -1.903084 1.428503 10 1 -1.679824 -1.903084 -1.428503 11 1 1.114906 -1.257891 -1.343932 12 1 1.114906 -1.257891 1.343932 13 1 0.319375 1.158870 2.106801 14 1 0.319375 1.158870 -2.106801 15 1 1.922392 2.143331 0.000000 16 1 -1.062867 2.355475 0.000000 -------------------------------------------------------------- nuclear repulsion energy 349.2015258202 Hartrees. Zero-point correction= 0.131539 Thermal correction to Energy= 0.137404 Thermal correction to Enthalpy= 0.138348 Thermal correction to Gibbs Free Energy= 0.101535 A11. TS : TCO -> BOT (-> COT) ***************************** E(B3LYP/6-31G*) = -309.194763481 a.u. = 0.7576 E(RCCSD(T)/cc-pVDZ) = -308.313549770844 Pointgroup: C1 State: 2-A, TS Program: Gaussian94, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 1.728052 0.569139 0.495578 2 6 1.703082 -0.741208 0.228688 3 6 0.583090 0.880822 -0.492867 4 6 0.542471 -0.662805 -0.764128 5 6 -0.769783 1.281141 -0.050466 6 6 -0.862190 -1.072115 -0.275230 7 6 -1.735219 0.236641 -0.151270 8 6 -1.206253 -0.557834 1.015855 9 1 2.328804 1.224756 1.115519 10 1 2.300468 -1.583403 0.562041 11 1 0.873988 1.520315 -1.342411 12 1 0.731979 -0.993015 -1.788718 13 1 -1.025838 2.282619 0.294304 14 1 -1.353641 -1.974240 -0.637271 15 1 -2.805946 0.361871 -0.300634 16 1 -0.949320 -0.441592 2.060209 ---------------------------------------------------------- nuclear repulsion energy 345.7929946180 Hartrees. Zero-point correction= 0.128755 Thermal correction to Energy= 0.134705 Thermal correction to Enthalpy= 0.135649 Thermal correction to Gibbs Free Energy= 0.098554 Low frequencies --- -219.7692 A12. BOT radical cation *********************** E(B3LYP/6-31G*) = -309.291716491 a.u. = 0.7589 E(ROHF/cc-pVDZ) = -307.27581232 a.u. E(RCCSD/cc-pVDZ) = -308.354679770517 a.u. E(RCCSD(T)/cc-pVDZ) = -308.402002960505 a.u. Pointgroup: Cs State: 2-A", minimum Program: Gaussian94, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -0.359734 0.796867 0.781118 2 6 -0.359734 0.796867 -0.781118 3 6 -0.359734 -0.526088 1.430745 4 6 -0.359734 -0.526088 -1.430745 5 6 -0.330130 -1.711441 0.707920 6 6 -0.330130 -1.711441 -0.707920 7 6 1.052049 1.435417 0.666076 8 6 1.052049 1.435417 -0.666076 9 1 -1.087796 1.475950 1.245223 10 1 -1.087796 1.475950 -1.245223 11 1 1.728091 1.782543 1.440142 12 1 1.728091 1.782543 -1.440142 13 1 -0.350289 -0.566730 2.518300 14 1 -0.350289 -0.566730 -2.518300 15 1 -0.304706 -2.660292 1.235879 16 1 -0.304706 -2.660292 -1.235879 ---------------------------------------------------------- nuclear repulsion energy 335.6557146979 Hartrees. Zero-point correction= 0.132663 Thermal correction to Energy= 0.139057 Thermal correction to Enthalpy= 0.140002 Thermal correction to Gibbs Free Energy= 0.101796 A13. TS : BOT -> COT ********************* E(B3LYP/6-31G*) = -309.257682811 a.u. = 0.7732 E(ROHF/cc-pVDZ) = -307.22427424 a.u. E(RCCSD/cc-pVDZ)= -308.315113078545 a.u. E(RCCSD(T)/cc-pVDZ) = -308.367420424867 a.u. Pointgroup: C1 State: 2-A, TS Program: Gaussian98, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -0.600637 -0.938588 0.695373 2 6 -0.765601 1.154866 0.410879 3 6 0.704462 -1.439336 0.291127 4 6 0.595219 1.474935 0.274228 5 6 -1.586036 -0.809184 -0.424441 6 6 -1.654459 0.505182 -0.601111 7 6 1.653182 -0.681658 -0.368508 8 6 1.606591 0.724551 -0.362814 9 1 -0.954541 -1.118907 1.713800 10 1 -1.290739 1.767940 1.147801 11 1 0.901509 -2.497167 0.481916 12 1 0.939578 2.364812 0.804205 13 1 -2.071927 -1.632061 -0.939843 14 1 -2.288666 1.082214 -1.271085 15 1 2.546790 -1.168247 -0.746613 16 1 2.501666 1.256808 -0.678574 ---------------------------------------------------------- nuclear repulsion energy 331.2732046372 Hartrees. Low frequencies --- -496.5800 Zero-point correction= 0.130079 Thermal correction to Energy= 0.136510 Thermal correction to Enthalpy= 0.137455 Thermal correction to Gibbs Free Energy= 0.099175 A14. COT radical cation *********************** E(B3LYP/6-31G*) = -309.319321411 a.u. = 0.7527 E(ROHF/cc-pVDZ) = -307.29249610 a.u. E(RCCSD/cc-pVDZ)= -308.370443740796 a.u. E(RCCSD(T)/cc-pVDZ) = -308.420812346341 a.u. Pointgroup: D2d State: 2-A1, minimum Program: Gaussian98, Molpro 96.4 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.685831 1.648338 0.235802 2 6 -0.685831 -1.648338 0.235802 3 6 -1.648338 0.685831 -0.235802 4 6 1.648338 -0.685831 -0.235802 5 6 -0.685831 1.648338 0.235802 6 6 0.685831 -1.648338 0.235802 7 6 1.648338 0.685831 -0.235802 8 6 -1.648338 -0.685831 -0.235802 9 1 1.138369 2.590884 0.539117 10 1 -1.138369 -2.590884 0.539117 11 1 -2.590884 1.138369 -0.539117 12 1 2.590884 -1.138369 -0.539117 13 1 -1.138369 2.590884 0.539117 14 1 1.138369 -2.590884 0.539117 15 1 2.590884 1.138369 -0.539117 16 1 -2.590884 -1.138369 -0.539117 ---------------------------------------------------------- nuclear repulsion energy 318.7295407100 Hartrees. Zero-point correction= 0.134502 Thermal correction to Energy= 0.141296 Thermal correction to Enthalpy= 0.142241 Thermal correction to Gibbs Free Energy= 0.104293 =========================================================== B) Results of CASSCF/CASPT2 calculations =========================================================== B1. 2A1-Tricyclooctadiene radical cation (2A1-TOD) at the neutral geometry *************************************************** (for comparison with photoelectron spectrum) Geometry: B3LYP/6-31G*, neutral in C2v symmetry Basis: ANO-S [3s2p1d] on C, ANO-S [2s] on H Active Space: 15 electrons in 10 active orbitals | A1 B1 B2 A2 -------------------+---------------- Frozen orbitals | 2 2 2 2 (in CAS and PT2 calc.) Inactive orbitals | 5 4 2 2 Active occupied | 2 3 2 1 Active virtual | 0 0 1 1 Orbitals 8-9 of symmetry A1 are active Orbitals 7-9 of symmetry B1 are active Orbitals 5-7 of symmetry B2 are active Orbitals 5-6 of symmetry A2 are active State averaging: The lowest two states are averaged in A1, B2, and A2-symmetry, the lowest three states in B1-symmetry. Summary of the Calculation: ========================== CAS(15/10) + CASPT2 (no level shift for CASPT2) ------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) osc ------------------------------------------------------------------- 2A1,root 1 -307.181243 -308.149169 72.4% 2B1,root 1 -307.163983 -308.132884 72.3% 0.44 eV 0.0420 2B1,root 2 -307.151398 -308.123185 72.0% 0.71 eV 0.0047 2A2,root 1 -307.114529 -308.090911 71.9% 1.59 eV 0.0000 2B2,root 1 -307.127433 -308.089030 72.3% 1.64 eV 0.0060 2A1,root 2 -307.057302 -308.044323 71.0% 2.85 eV 0.0170 2B1,root 3 -307.038931 -308.029368 71.0% 3.26 eV 0.0121 2B2,root 2 -307.095109 -307.984602 71.1% 3.37 eV 0.0125 ------------------------------------------------------------------- B2. 2A1-Tricyclooctadiene radical cation (2A1-TOD) *************************************************** Geometry: B3LYP/6-31G*, 2A1-State in C2v Basis: ANO-S [3s2p1d] on C ANO-S [2s] on H Active Space: 13 electrons in 13 active orbitals | A1 B1 B2 A2 -------------------+---------------- Frozen orbitals | 2 2 2 2 (in CAS and PT2 calc.) Inactive orbitals | 5 4 2 2 Frozen+Inactive | 7 6 4 4 Active Orbitals | 2 3 5 3 Orbitals 8-9 of symmetry A1 are active Orbitals 7-9 of symmetry B1 are active Orbitals 5-9 of symmetry B2 are active Orbitals 5-7 of symmetry A2 are active State averaging: The lowest two states are averaged in A1, B2, and A2-symmetry, the lowest three states in B1-symmetry. Summary of the Calculation: ========================== CAS(13/13) + CASPT2 (no level shift for CASPT2) ------------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------- 2A1,root 1 -307.246395 -308.159835 74.0% 2B1,root 1 -307.200622 -308.115587 73.2% 1.20 eV 1030 nm 0.0811 2B1,root 2 -307.189085 -308.104299 73.0% 1.51 eV 820 nm 0.0002 2B2,root 1 -307.171979 -308.086961 73.7% 1.98 eV 625 nm 0.0041 2A2,root 1 -307.130373 -308.069523 72.3% 2.46 eV 505 nm 0.0000 2A1,root 2 -307.092257 -308.014155 41.4% 3.96 eV 313 nm 0.0485 2B2,root 2 -307.089843 -308.009354 72.3% 4.09 eV 303 nm 0.0152 2A2,root 2 -307.095109 -307.984602 2.1% 4.77 eV 260 nm 0.0000 2B1,root 3 -306.993791 -307.937789 43.4% 6.04 eV 205 nm 0.1206 ------------------------------------------------------------------------------- CAS(13/13) + CASPT2 (0.1 a.u. level shift for CASPT2) ------------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------- 2A1,root 1 -307.246395 -308.158391 75.7% 2B1,root 1 -307.200622 -308.113875 75.2% 1.21 eV 1024 nm 0.0816 2B1,root 2 -307.189085 -308.102574 75.3% 1.52 eV 816 nm 0.0002 2B2,root 1 -307.171979 -308.085459 75.4% 1.98 eV 625 nm 0.0041 2A2,root 1 -307.130373 -308.067780 74.2% 2.47 eV 503 nm 0.0000 2A1,root 2 -307.092257 -308.023351 73.7% 3.67 eV 337 nm 0.0449 2B2,root 2 -307.089843 -308.009409 74.3% 4.05 eV 306 nm 0.0150 2A2,root 2 -307.095109 -308.009389 74.9% 4.05 eV 306 nm 0.0000 2B1,root 3 -306.993791 -307.935538 72.7% 6.06 eV 204 nm 0.1210 ------------------------------------------------------------------------------- B3. 2B1-Tricyclooctadiene radical cation (2B1-TOD) ************************************************** Geometry: B3LYP/6-31G*, 2B1-State in C2v Basis: ANO-S [3s2p1d] on C, ANO-S [2s] on H Active Space: 13 electrons in 13 active orbitals | A1 B1 B2 A2 -------------------+---------------- Frozen orbitals | 2 2 2 2 (in CAS and PT2 calc.) Inactive orbitals | 5 4 2 2 Frozen+Inactive | 7 6 4 4 Active Orbitals | 2 3 5 3 Orbitals 8-9 of symmetry A1 are active Orbitals 7-9 of symmetry B1 are active Orbitals 5-9 of symmetry B2 are active Orbitals 5-7 of symmetry A2 are active State averaging: The lowest two states are averaged in A1, B2, and A2-symmetry, the lowest three states in B1-symmetry. Summary of the Calculation: ========================== CAS(13/13) + CASPT2 ------------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------- 2B1,root 1 -307.260791 -308.162323 74.5% 2A1,root 1 -307.185111 -308.098606 73.5% 1.73 eV 715 nm 0.0123 2B1,root 2 -307.164944 -308.087111 72.7% 2.05 eV 606 nm 0.0000 2B2,root 1 -307.106191 -308.016613 73.7% 3.97 eV 313 nm 0.0000 2A1,root 2 -307.085873 -308.011685 71.4% 4.10 eV 302 nm 0.1202 2A2,root 1 -307.094975 -308.005899 64.8% *) 4.26 eV 291 nm 0.0001 2B2,root 2 -307.098616 -308.005269 72.7% 4.27 eV 290 nm 0.0000 2A2,root 2 -307.012043 -307.950603 8.3% *) 5.76 eV 215 nm 0.0000 2B1,root 3 -306.939734 -307.840590 73.1% 8.75 eV 142 nm 0.0000 ------------------------------------------------------------------------------- *) Low weight due to intruder state in CASPT2 calc. of A2-states (orbital 10-b2) Due to low the zero or low oscillator strengths and high energies of these transitions, an improvment of the description of these states by increasing the active was not attempted. B4. Tricyclooctadiene radical cation (2A' in Cs) ************************************************ Geometry: B3LYP/6-31G* in Cs, 2A' State in Cs Basis: ANO-S [3s2p1d] on C, ANO-S [2s] on H Active Space: 13 electrons in 10 active orbitals Active space | A' A" ------------------+--------- Frozen orbitals | 4 4 Inactive orbitals | 9 4 Frozen + Inactive | 13 8 Active orbitals | 4 6 Orbitals 14-17 of symmetry A' are active Orbitals 9-14 of symmetry A" are active State averaging: the lowest six states of each symmetry are averaged Summary of the Calculation: ========================== CAS(13,10) + CASPT2 (no level shift for CASPT2) ------------------------------------------------------------------------------ State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------ A',root 1 -307.217345 -308.158597 72.8% A',root 2 -307.142007 -308.101240 71.3% 1.56 eV 794 nm 0.0245 A',root 3 -307.128081 -308.088762 71.6% 1.90 eV 652 nm 0.0140 A",root 2 -307.071058 -308.054297 44.4% 2.84 eV 437 nm 0.0001 A",root 1 -307.094732 -308.049493 70.8% 2.97 eV 418 nm 0.0167 A",root 5 -307.051143 -308.033901 69.8% 3.39 eV 365 nm 0.0003 A",root 3 -307.062798 -308.016250 62.1% 3.87 eV 320 nm 0.0098 A",root 4 -307.061390 -308.007164 70.8% 4.12 eV 301 nm 0.0000 A',root 4 -307.037312 -308.006327 68.2% 4.14 eV 299 nm 0.0713 A',root 5 -306.961985 -307.957502 25.8% 5.47 eV 227 nm 0.0066 A",root 6 -307.021407 -307.956915 7.0% 5.49 eV 226 nm 0.0000 A',root 6 -306.937879 -307.930113 66.7% 6.22 eV 199 nm 0.0067 ------------------------------------------------------------------------------ CAS(13,10) + CASPT2 (0.1 a.u. level shift for CASPT2) ------------------------------------------------------------------------------ State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------ A',root 1 -307.217345 -308.156906 74.8% A',root 2 -307.142007 -308.099122 73.7% 1.57 eV 789 nm 0.0247 A',root 3 -307.128081 -308.086805 73.9% 1.91 eV 650 nm 0.0140 A",root 1 -307.094732 -308.047128 74.0% 2.99 eV 415 nm 0.0168 A",root 2 -307.071058 -308.045602 72.6% 3.03 eV 409 nm 0.0001 A",root 5 -307.051143 -308.031519 72.6% 3.41 eV 363 nm 0.0003 A",root 3 -307.062798 -308.018005 72.5% 3.78 eV 328 nm 0.0096 A",root 4 -307.061390 -308.004857 74.1% 4.14 eV 300 nm 0.0000 A',root 4 -307.037312 -308.002847 72.9% 4.19 eV 296 nm 0.0721 A',root 5 -306.961985 -308.149867 29.6% *) 0.19 eV 6473 nm 0.0002 A",root 6 -307.021407 -307.995499 71.0% 4.39 eV 282 nm 0.0000 A',root 6 -306.937879 -307.929914 71.1% 6.18 eV 201 nm 0.0066 ------------------------------------------------------------------------------ *) root 5 of Ać symmetry cannot be described satisfactorily with this active space. However, it seems to lie outside the experimentally accessible re- gion and its oscillator strength is very small, hence it was disregarded. B5. Bis(cyclobutenylium) radical cation *************************************** Geometry : B2LYP/6-21G* in C2 (2B1 ground state) Basis set: ANO-S [2s2p1d] on C, ANO-S [2s] on H Active Space: 12 electrons in 10 active orbitals | A1 B1 B2 A2 ------------------+------------------- Frozen orbitals | 3 1 1 3 Inactive orbitals | 5 2 6 0 Active occupied | 2 2 2 1 Active virtual | 1 0 1 1 Orbitals 9-11 of symmetry A1 are active Orbitals 4- 5 of symmetry B1 are active Orbitals 8-10 of symmetry B2 are active Orbitals 4- 5 of symmetry A2 are active State averaging: the lowest 2 States of each symmetry are averaged Summary of the Calculation: ========================== CAS(12,10) + CASPT2 (no level shift for CASPT2) ------------------------------------------------------------------------------ State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ------------------------------------------------------------------------------ B1, root 1 -307.235814 -308.033487 76.2% A2, root 1 -307.150805 -307.956762 75.2% 2.09 eV 593 nm 0.2221 B2, root 1 -307.126098 -307.927429 75.4% 2.89 eV 429 nm (0) A2, root 2 -307.094072 -307.904821 74.8% 3.50 eV 354 nm 0.0419 B2, root 2 -307.052197 -307.882333 72.8% 4.11 eV 302 nm (0) B1 ,root 2 -307.045324 -307.860076 50.8% 4.72 eV 263 nm <0.0001 *) A1, root 1 -307.130643 -307.849960 77.7% 4.99 eV 253 nm 0.0042 A1, root 2 -307.068943 -307.796099 74.0% 6.46 eV 192 nm 0.0024 ------------------------------------------------------------------------------ *) This state is not satisfactorily described at the CASPT2 level. In view of the small oscillator strenght for the electronic transition, and in view of its high energy, it is disregarded. B6. Tricyclooctene radical cation (TCO) *************************************** Geometry: B3LYP/6-31G* , 2A' state in Cs Basis: ANO-S, [3s2p1d] on C, [2s] on H Active space: 15 electrons in 13 orbitals | A' A" ------------------+--------- Inactive Orbitals | 13 7 Active Orbitals | 8 5 Frozen Orbitals | 5 3 (only in CASPT2) Orbitals 14-21 of symmetry A' are active Orbitals 8-12 of symmetry A" are active State averaging: the lowest four states of each symmetry are averaged Summary of the Calculation: ========================== CAS(15/13) + CASPT2 ---------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ---------------------------------------------------------------------------- 1-A' -307.266046 -308.188946 73.9% 2-A' -307.203834 -308.132412 73.4% 1.54 eV 806 nm 0.0953 1-A" -307.178275 -308.101568 73.7% 2.38 eV 521 nm 0.0003 3-A' -307.164379 -308.088884 73.3% 2.72 eV 455 nm 0.0051 4-A' -307.121908 -308.063491 72.1% 3.41 eV 363 nm 0.0061 2-A" -307.118609 -308.058535 71.1% 3.55 eV 349 nm 0.0071 3-A" -307.114473 -308.038083 71.5% 4.11 eV 302 nm 0.0069 4-A" -307.085428 -308.033448 72.0% 4.23 eV 293 nm 0.0128 ----------------------------------------------------------------------------