Electron Transfer-Induced Tautomerization in Methylindanones: Electronic Control of the Tunnelling Rate for Enolization. by Pawel Bednarek, Zhendong Zhu and Thomas Bally* Institute of Physical Chemistry, University of Fribourg, Perolles, CH-1700 Fribourg, Switzerland and Tomasz Filipiak, Andrzej Marcinek, and Jerzy Gebicki* Institute of Applied Radiation Chemistry, Technical University 90-924 Lodz, Poland SUPPORTING INFORMATION ********************* a) Energies and geometries of all stationary points located and characterized in the course of the above study b) Results of TD-B3LYP calculations on the pi- and sigma-radical cations of MI and DMI Note: All energies are in hartree, unless otherwise noted. If no ³low frequencies² are given, the stationary points are potential energy minima. ******************************************** * * * Calculations on 7-methylindanone * * * ******************************************** Neutral 7-methylindanone (MI) Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=1-A'\HF=-462.3262321 6 -2.124330 -0.883183 0.000000 6 -1.479620 -2.124518 0.000000 6 -1.405816 0.317869 0.000000 6 0.000000 0.215720 0.000000 6 0.650209 -1.029613 0.000000 6 -0.085971 -2.210853 0.000000 6 1.018810 1.299378 0.000000 6 2.406323 0.636755 0.000000 6 2.160399 -0.886140 0.000000 8 0.837421 2.505161 0.000000 6 -2.132123 1.643065 0.000000 1 -3.211637 -0.847685 0.000000 1 -2.075447 -3.033959 0.000000 1 0.408846 -3.179003 0.000000 1 2.962706 0.982975 0.877895 1 2.962706 0.982975 -0.877895 1 2.600259 -1.375026 0.877921 1 2.600259 -1.375026 -0.877921 1 -2.780395 1.726576 0.881375 1 -1.433573 2.479423 0.000000 1 -2.780395 1.726576 -0.881375 Low frequencies -99.4600 -9.8192 -5.2908 0.0001 0.0006 0.0008 7.2799 (first negative frequency correspond to rotation of the methyl group) Zero-point correction= 0.173471 Thermal correction to Energy= 0.182090 Thermal correction to Enthalpy= 0.183034 Thermal correction to Gibbs Free Energy= 0.139253 ---------------------------------------------------- 7-methylindanone radical cation (MI+.) pi-radical state (2A") Symmetry: Cs Method: B3LYP Basis set: 6-31G* Optimized geometry of A" State=2-A"\HF=-462.0163499\S2=0.76503 6 -2.074978 -1.044772 0.000000 6 -1.371867 -2.246952 0.000000 6 -1.402619 0.250252 0.000000 6 0.000000 0.240715 0.000000 6 0.709157 -0.957069 0.000000 6 0.021817 -2.226154 0.000000 6 0.972938 1.394099 0.000000 6 2.380763 0.788443 0.000000 6 2.190104 -0.743123 0.000000 8 0.687054 2.568417 0.000000 6 -2.220305 1.487498 0.000000 1 -3.162052 -1.053047 0.000000 1 -1.906946 -3.190756 0.000000 1 0.592741 -3.150926 0.000000 1 2.927250 1.148095 0.877964 1 2.927250 1.148095 -0.877964 1 2.643535 -1.237360 0.872571 1 2.643535 -1.237360 -0.872571 1 -2.891962 1.490262 0.873744 1 -1.607881 2.387774 0.000000 1 -2.891962 1.490262 -0.873744 Low frequencies --- -0.4845 -0.0007 0.0002 0.0091 8.6774 10.4112 Zero-point correction= 0.171238 Thermal correction to Energy= 0.180962 Thermal correction to Enthalpy= 0.181906 Thermal correction to Gibbs Free Energy= 0.135352 A' state at the geometry of the A" state: State=2-A'\HF=-462.0024426\S2=0.756 --------------------------------------------------- 7-methylindanone radical cation (MI+.) sigma-radical state (2A') Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=2-A' HF=-462.0155051\S2=0.756096 6 -2.153270 -0.792530 0.000000 6 -1.540010 -2.054800 0.000000 6 -1.403410 0.385130 0.000000 6 0.000000 0.194880 0.000000 6 0.640150 -1.072980 0.000000 6 -0.148360 -2.212540 0.000000 6 1.016070 1.210870 0.000000 6 2.433430 0.569820 0.000000 6 2.139050 -0.950290 0.000000 8 0.893930 2.435410 0.000000 6 -2.055590 1.737720 0.000000 1 -3.237260 -0.727330 0.000000 1 -2.170730 -2.939290 0.000000 1 0.296440 -3.202710 0.000000 1 2.965880 0.931140 0.885750 1 2.965880 0.931140 -0.885750 1 2.580710 -1.425650 0.883110 1 2.580710 -1.425650 -0.883110 1 -2.690930 1.865410 0.883860 1 -1.319570 2.552600 0.000000 1 -2.690930 1.865410 -0.883860 Low frequencies --- -49.9227 -9.5157 -7.3490 -0.0024 -0.0008 -0.0005 5.3064 (first negative frequency corresponds to rotation of the methyl group which must, however, be fixed so the molecule retains Cs symmetry, otherwise it con- verges to the lower lying pi-radical state) Zero-point correction= 0.179082 Thermal correction to Energy= 0.187744 Thermal correction to Enthalpy= 0.188689 Thermal correction to Gibbs Free Energy= 0.144849 2A" (pi-radical) state at the geometry of the A' state State=2-A"\HF=-462.0015181\S2=0.765 ------------------------------------------------------- 7-methylindanone transition state for enolization (TS1) Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-461.9961086\S2=0.756631 6 2.098732 -0.960754 0.000000 6 1.380574 -2.177682 0.000000 6 -0.019170 -2.251566 0.000000 6 -0.736087 -1.057690 0.000000 6 0.000000 0.134890 0.000000 6 1.403205 0.245049 0.000000 6 1.964488 1.626479 0.000000 6 -0.865177 1.256259 0.000000 6 -2.304077 0.812851 0.000000 6 -2.217910 -0.747452 0.000000 8 -0.444195 2.455229 0.000000 1 3.183655 -0.977665 0.000000 1 1.950679 -3.102549 0.000000 1 -0.514586 -3.217256 0.000000 1 2.456041 1.970393 0.915001 1 2.456041 1.970393 -0.915001 1 0.860898 2.333305 0.000000 1 -2.817925 1.221680 -0.878362 1 -2.817925 1.221680 0.878362 1 -2.715393 -1.172058 -0.878752 1 -2.715393 -1.172058 0.878752 Low frequencies -1428.8977 -140.2339 -15.8537 -5.7805 -0.0002 0.0005 0.0011 14.5583 (second negative frequency corresponds to a slight twisting of the CH2 group. This imaginary mode dis- appears on unconstrained optimization, see below) Zero-point correction= 0.166983 Thermal correction to Energy= 0.174894 Thermal correction to Enthalpy= 0.175838 Thermal correction to Gibbs Free Energy 0.133651 ------------------------------------------------------ 7-methylindanone transition state for enolization (TS1) (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: 6-31G* HF=-461.997329\S2=0.761931 6 2.253914 0.481326 -0.120003 6 2.407559 -0.918306 -0.104221 6 1.327732 -1.806548 0.012111 6 0.033292 -1.274852 0.103973 6 -0.087207 0.112270 0.133663 6 0.977122 1.038543 0.062902 6 0.624758 2.451199 0.169844 6 -1.450694 0.499060 -0.034333 6 -2.335005 -0.721106 -0.041643 6 -1.337616 -1.917227 0.075697 8 -1.802039 1.700035 -0.212971 1 3.126340 1.121454 -0.204149 1 3.409243 -1.326161 -0.203990 1 1.499450 -2.877908 -0.024150 1 0.288090 2.804109 1.152650 1 1.234490 3.179743 -0.362219 1 -0.688175 2.353098 -0.224930 1 -2.923101 -0.741425 -0.966598 1 -3.055847 -0.667918 0.783271 1 -1.440681 -2.601040 -0.773663 1 -1.516630 -2.510381 0.979603 Low frequencies --- -1601.8759 -6.7285 -0.0009 -0.0004 -0.0003 4.5689 6.4172 Zero-point correction= 0.167830 Thermal correction to Energy= 0.176257 Thermal correction to Enthalpy= 0.177201 Thermal correction to Gibbs Free Energy= 0.133977 -------------------------------------------------------- Transition state for rotation of CH2 group in ME+. (TS2) Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-462.0098575\S2=0.753384 6 2.222967 -0.682037 0.000000 6 1.673023 -1.981042 0.000000 6 0.295341 -2.216093 0.000000 6 -0.555365 -1.117709 0.000000 6 0.000000 0.188090 0.000000 6 1.401722 0.440731 0.000000 6 1.934257 1.819641 0.000000 6 -1.065963 1.117458 0.000000 6 -2.398220 0.446878 0.000000 6 -2.063935 -1.065449 0.000000 8 -0.979928 2.410088 0.000000 1 3.301387 -0.561091 0.000000 1 2.353379 -2.828065 0.000000 1 -0.090609 -3.230516 0.000000 1 2.274333 2.273672 0.929303 1 2.274333 2.273672 -0.929303 1 -0.030805 2.696450 0.000000 1 -2.975049 0.769311 -0.876413 1 -2.975049 0.769311 0.876413 1 -2.477730 -1.573125 -0.878392 1 -2.477730 -1.573125 0.878392 Low frequencies --- -348.8810 -9.7692 -3.9699 -0.0007 0.0006 0.0017 2.1619 Zero-point correction= 0.171573 Thermal correction to Energy= 0.180284 Thermal correction to Enthalpy= 0.181228 Thermal correction to Gibbs Free Energy= 0.137334 --------------------------------------------------- Enol form of 7-methylindanone (ME+.) (syn conformation) Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A"\HF=-462.0292838\S2=0.778 6 -2.224331 -0.765050 0.000000 6 -1.645098 -2.026493 0.000000 6 -1.445286 0.435791 0.000000 6 0.000000 0.243336 0.000000 6 0.563099 -1.064000 0.000000 6 -0.248797 -2.193518 0.000000 6 1.072981 1.155434 0.000000 6 2.406038 0.481133 0.000000 6 2.068755 -1.022575 0.000000 8 1.065935 2.462629 0.000000 6 -2.109951 1.652451 0.000000 1 -3.305954 -0.672235 0.000000 1 -2.286275 -2.902774 0.000000 1 0.186101 -3.188087 0.000000 1 2.982762 0.802029 0.876764 1 2.982762 0.802029 -0.876764 1 2.475031 -1.537079 0.878264 1 2.475031 -1.537079 -0.878264 1 -3.194471 1.678629 0.000000 1 0.171095 2.845207 0.000000 1 -1.638020 2.629275 0.000000 Low frequencies -96.7345 -13.9885 -8.6249 -.9308 -.0009 -.0004 .0010 (First negative frequency corresponds to rotation of OH group) Zero-point correction= .172955 Thermal correction to Energy= .181344 Thermal correction to Enthalpy= .182288 Thermal correction to Gibbs Free Energy= .139188 2A' state at geometry of A" state: State=2-A'\HF=-461.8561252\S2=0.759 ******************************************* * * * Calculations on 4,7-dimethylindanone * * * ******************************************** Neutral 4,7-dimethylindanone (DMI) Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=1-A'\HF=-501.6444622 6 -2.233717 -0.264310 0.000000 6 -1.739706 -1.572170 0.000000 6 -1.381790 0.844345 0.000000 6 0.000000 0.568565 0.000000 6 0.494646 -0.745811 0.000000 6 -0.366896 -1.848167 0.000000 6 -1.946047 2.246083 0.000000 6 0.158101 -3.263011 0.000000 6 1.141966 1.521362 0.000000 6 2.010238 -0.784263 0.000000 6 2.439080 0.696906 0.000000 8 1.107423 2.740287 0.000000 1 -3.310249 -0.106282 0.000000 1 -2.444123 -2.401663 0.000000 1 -2.579186 2.406796 0.881712 1 -1.153505 2.994000 0.000000 1 -2.579186 2.406796 -0.881712 1 0.781449 -3.463508 0.881158 1 -0.660419 -3.989463 0.000000 1 0.781449 -3.463508 -0.881158 1 2.391023 -1.323913 -0.876858 1 2.391023 -1.323913 0.876858 1 3.033546 0.972597 -0.877964 1 3.033546 0.972597 0.877964 Low frequencies --- -85.1389 -8.1473 -7.8238 -0.0016 -0.0007 -0.0007 2.2784 (first negative frequency corresponds to twisting of one of the methyl groups) Zero-point correction= 0.201211 Thermal correction to Energy= 0.211557 Thermal correction to Enthalpy= 0.212501 Thermal correction to Gibbs Free Energy= 0.165081 --------------------------------------------------- 4,7-dimethylindanone radical cation (DMI+.) pi-radical state (2A") optimized in Cs Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A"\HF=-501.3459836\S2=0.761875 6 -2.242851 -0.392825 0.000000 6 -1.715055 -1.663847 0.000000 6 -1.399816 0.785741 0.000000 6 0.000000 0.574792 0.000000 6 0.539865 -0.699114 0.000000 6 -0.311443 -1.873315 0.000000 6 -2.026150 2.130210 0.000000 6 0.273684 -3.239175 0.000000 6 1.113385 1.592195 0.000000 6 2.044603 -0.683463 0.000000 6 2.429489 0.811359 0.000000 8 0.983811 2.794534 0.000000 1 -3.320455 -0.252377 0.000000 1 -2.375094 -2.525785 0.000000 1 -2.690400 2.229608 0.873479 1 -1.290929 2.932959 0.000000 1 -2.690400 2.229608 -0.873479 1 0.924164 -3.381500 0.875902 1 -0.490613 -4.018048 0.000000 1 0.924164 -3.381500 -0.875902 1 2.435100 -1.220923 -0.874954 1 2.435100 -1.220923 0.874954 1 3.017304 1.098629 -0.877911 1 3.017304 1.098629 0.877911 Low frequencies --- -337.9221 -14.5012 -14.3130 -7.3239 -0.0013 0.0003 0.0009 (first negative frequency correspond to rotation of one of the methyl groups) Zero-point correction= 0.197848 Thermal correction to Energy= 0.208873 Thermal correction to Enthalpy= 0.209817 Thermal correction to Gibbs Free Energy= 0.159937 sigma-radical state (2A') at geometry of 2A" state: \State=2-A'\HF=-501.323601\S2=0.756 --------------------------------------------------------- 4,7-dimethylindanone radical cation (DMI+.) pi-radical state fully optimized Symmetry: C1 Method: B3LYP Basis set: 6-31G* HF=-501.3473535\S2=0.758895 6 -0.652932 2.177722 -0.089438 6 -1.849241 1.491872 -0.029129 6 0.606135 1.491621 -0.028221 6 0.553114 0.074727 -0.008734 6 -0.637729 -0.626519 0.050529 6 -1.893988 0.074192 0.036157 6 1.881336 2.239924 0.081175 6 -3.186402 -0.665904 0.008913 6 1.697075 -0.889992 -0.031500 6 -0.423785 -2.117658 0.069585 6 1.103907 -2.301709 -0.062106 8 2.872765 -0.597260 -0.022566 1 -0.650558 3.263283 -0.122698 1 -2.784822 2.043019 -0.039646 1 2.200134 2.283329 1.135976 1 2.693916 1.701080 -0.425024 1 1.789803 3.265429 -0.283623 1 -3.215942 -1.437778 0.789372 1 -4.042904 0.000466 0.129251 1 -3.305624 -1.198184 -0.947597 1 -0.964087 -2.602797 -0.753915 1 -0.824515 -2.554938 0.993017 1 1.390879 -2.766883 -1.012037 1 1.546653 -2.907597 0.734070 Low frequencies -0.0013 -0.0006 -0.0003 1.7663 9.3744 12.1941 Zero-point correction= 0.198894 Thermal correction to Energy= 0.210233 Thermal correction to Enthalpy= 0.211177 Thermal correction to Gibbs Free Energy= 0.161133 -------------------------------------------------- 4,7-dimethylindanone radical cation (DMI+.) sigma radical state (2A') optimized Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-501.336067\S2=0.756104 6 0.362051 -1.853890 0.000000 6 -0.518199 -0.775831 0.000000 6 1.734082 -1.536902 0.000000 6 -0.097593 -3.292094 0.000000 6 0.000000 0.549258 0.000000 6 2.228555 -0.227075 0.000000 6 -2.023955 -0.785807 0.000000 6 1.374757 0.877984 0.000000 6 -1.104420 1.467300 0.000000 6 -2.455221 0.700163 0.000000 6 1.897851 2.285161 0.000000 8 -1.094284 2.698542 0.000000 1 2.451379 -2.354417 0.000000 1 -1.186490 -3.378721 0.000000 1 0.280482 -3.820530 0.882374 1 0.280482 -3.820530 -0.882374 1 3.302576 -0.065432 0.000000 1 -2.424917 -1.296988 0.882653 1 -2.424917 -1.296988 -0.882653 1 -3.019256 1.010911 0.885447 1 -3.019256 1.010911 -0.885447 1 1.089625 3.028961 0.000000 1 2.518562 2.472442 0.883752 1 2.518562 2.472442 -0.883752 Low frequencies --- -79.3147 -73.4247 -10.5610 -0.0027 -0.0004 0.0006 1.6149 3.1111 (The first two negative frequencies correspond to rotations of the two methyl groups which must, how- ever, be fixed so the molecule retains Cs symmetry, otherwise it converges to the lower lying pi-radical state) Zero-point correction= 0.198465 Thermal correction to Energy= 0.208471 Thermal correction to Enthalpy= 0.209416 Thermal correction to Gibbs Free Energy= 0.162322 pi radical (2A") state at geometry of 2A' state State=2-A"\HF=-501.3292637 ---------------------------------------------------------- 4,7-dimethylindanone radical cation transition state (TS1) (optimized in Cs symmetry) Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-501.3164451 6 2.237390 -0.256000 0.000000 6 1.717054 -1.566399 0.000000 6 0.344458 -1.886995 0.000000 6 -0.537290 -0.801823 0.000000 6 0.000000 0.494116 0.000000 6 1.365187 0.829622 0.000000 6 1.705616 2.279836 0.000000 6 -1.030569 1.463222 0.000000 6 -2.381023 0.801945 0.000000 6 -2.051746 -0.725013 0.000000 8 -0.804048 2.716469 0.000000 1 3.312380 -0.107611 0.000000 1 2.431564 -2.386503 0.000000 6 -0.114243 -3.323744 0.000000 1 2.128454 2.702766 0.915746 1 2.128454 2.702766 -0.915746 1 0.449150 2.807578 0.000000 1 -2.953059 1.124603 -0.878361 1 -2.953059 1.124603 0.878361 1 -2.479596 -1.219986 -0.878724 1 -2.479596 -1.219986 0.878724 1 -1.203908 -3.403948 0.000000 1 0.261299 -3.854318 -0.882224 1 0.261299 -3.854318 0.882224 Low frequencies -1578.7842 -215.2559 -75.9602 -10.2263 -6.7368 -2.8640 -0.0004 0.0004 0.0012 (The second negative frequency corresponds to twisting of the CH2 group, the third negative frequency to a twisting of the remote methyl group. These two imaginary modes dis- appear on unconstrained optimization, see below) Zero-point correction= 0.194269 Thermal correction to Energy= 0.203292 Thermal correction to Enthalpy= 0.204236 Thermal correction to Gibbs Free Energy= 0.159550 ----------------------------------------------------------- 4,7-dimethylindanone transition state for enolization (TS1) (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: 6-31G* HF=-501.3206478\S2=0.763825 6 -0.492651 2.196768 -0.135778 6 -1.737652 1.551669 -0.113169 6 -1.904695 0.156476 0.022858 6 -0.720727 -0.612647 0.120999 6 0.498641 0.050372 0.155517 6 0.684896 1.450749 0.076026 6 2.044589 1.939710 0.183909 6 1.575033 -0.873069 -0.036448 6 1.044337 -2.283182 -0.042780 6 -0.501640 -2.110524 0.081405 8 2.762735 -0.500262 -0.241982 1 -0.445701 3.276605 -0.237150 1 -2.629566 2.162611 -0.222657 6 -3.261803 -0.484360 -0.009246 1 2.293630 2.888644 -0.287135 1 2.553888 1.790083 1.144231 1 2.683793 0.787155 -0.254445 1 1.488264 -2.853726 0.782056 1 1.347451 -2.787668 -0.967305 1 -0.898598 -2.596987 0.980126 1 -1.017590 -2.566392 -0.771218 1 -3.348695 -1.182744 -0.851648 1 -3.441544 -1.065468 0.904154 1 -4.057176 0.258218 -0.102900 Low frequencies -1625.7993 -6.3383 -0.0010 0.0007 0.0004 4.1501 9.3117 Zero-point correction= 0.195569 Thermal correction to Energy= 0.205769 Thermal correction to Enthalpy= 0.206713 Thermal correction to Gibbs Free Energy= 0.159392 -------------------------------------------------------- Enol form of 4,7-dimethylindanone radical cation (DME+.) (syn conformation) Symmetry: CS Method: B3LYP Basis set: 6-31G* State=2-A"\HF=-501.3510779\S2=0.78 6 0.390589 -1.841604 0.000000 6 -0.479934 -0.747290 0.000000 6 0.000000 0.594657 0.000000 6 1.428250 0.885022 0.000000 6 2.278548 -0.269561 0.000000 6 1.779388 -1.556829 0.000000 6 -1.122978 1.441554 0.000000 6 -2.413734 0.691773 0.000000 6 -1.988780 -0.789246 0.000000 1 -3.009192 0.977259 0.876557 1 -3.009192 0.977259 -0.876557 1 -2.369750 -1.322976 0.878076 1 -2.369750 -1.322976 -0.878076 1 3.352919 -0.112605 0.000000 1 2.478922 -2.388935 0.000000 6 -0.086492 -3.267888 0.000000 6 2.015815 2.135758 0.000000 8 -1.193564 2.748780 0.000000 1 -1.175075 -3.346865 0.000000 1 0.292160 -3.800733 0.880766 1 0.292160 -3.800733 -0.880766 1 3.096880 2.226980 0.000000 1 1.487495 3.082942 0.000000 1 -0.323094 3.183070 0.000000 Low frequencies --- -107.0923 -75.7037 -16.4540 -12.8676 -6.7088 -.0011 -.0004 -.0004 (The first negative frequency corresponds to rota- tion of the OH roup, the second one to rotation of the remote methyl group) Zero-point correction= .200455 Thermal correction to Energy= .209870 Thermal correction to Enthalpy= .210815 Thermal correction to Gibbs Free Energy= .165458 ******************************************************** * * * Model calculations on methylacrolein radical cation * * * ******************************************************** Methylacrolein radical cation (MA+.) Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-230.8910951 8 1.479403 -0.764106 0.000000 6 1.262455 0.456713 0.000000 6 0.000000 1.132014 0.000000 6 -1.176904 0.438466 0.000000 6 -1.364097 -1.021066 0.000000 1 0.043876 2.214950 0.000000 1 -2.085733 1.044856 0.000000 1 -0.417329 -1.588583 0.000000 1 -1.950354 -1.326930 0.879898 1 -1.950354 -1.326930 -0.879898 1 2.195946 1.058730 0.000000 Zero-point correction= 0.087088 Thermal correction to Energy= 0.092897 Thermal correction to Enthalpy= 0.093841 Thermal correction to Gibbs Free Energy= 0.057694 -------------------------------------------------- Methylacrolein radical cation (MA+.) Symmetry: Cs Method: B3LYP Basis set: 6-311G** State=2-A'\HF=-230.9517806 8 1.484381 -0.758662 0.000000 6 1.262056 0.449495 0.000000 6 0.000000 1.126083 0.000000 6 -1.174098 0.437290 0.000000 6 -1.369272 -1.017082 0.000000 1 0.046172 2.206616 0.000000 1 -2.077789 1.048584 0.000000 1 -0.429733 -1.590011 0.000000 1 -1.958819 -1.315759 0.877184 1 -1.958819 -1.315759 -0.877184 1 2.191825 1.060912 0.000000 Zero-point correction= 0.086172 Thermal correction to Energy= 0.092001 Thermal correction to Enthalpy= 0.092945 Thermal correction to Gibbs Free Energy= 0.056780 -------------------------------------------------- Methylacrolein radical cation (MA+.) Symmetry: Cs Method: B3LYP Basis set: cc-pVDZ State=2-A'\HF=-230.903539 8 1.479060 -0.765325 0.000000 6 1.262165 0.450068 0.000000 6 0.000000 1.133207 0.000000 6 -1.177920 0.438927 0.000000 6 -1.362991 -1.018285 0.000000 1 0.046221 2.222193 0.000000 1 -2.090892 1.052544 0.000000 1 -0.408961 -1.585210 0.000000 1 -1.954866 -1.324842 0.883737 1 -1.954866 -1.324842 -0.883737 1 2.203359 1.059256 0.000000 Zero-point correction= 0.086116 Thermal correction to Energy= 0.091894 Thermal correction to Enthalpy= 0.092839 Thermal correction to Gibbs Free Energy= 0.056859 -------------------------------------------------- Methylacrolein radical cation (MA+.) Symmetry: Cs Method: B3LYP Basis set: cc-pVTZ State=2-A'\HF=-230.9751709 8 1.483708 -0.758896 0.000000 6 1.258710 0.448388 0.000000 6 0.000000 1.122721 0.000000 6 -1.172225 0.437139 0.000000 6 -1.367328 -1.013146 0.000000 1 0.046245 2.201014 0.000000 1 -2.073825 1.047308 0.000000 1 -0.429828 -1.584257 0.000000 1 -1.956676 -1.311315 0.874762 1 -1.956676 -1.311315 -0.874762 1 2.186162 1.059118 0.000000 Zero-point correction= 0.086277 Thermal correction to Energy= 0.092094 Thermal correction to Enthalpy= 0.093038 Thermal correction to Gibbs Free Energy= 0.056909 -------------------------------------------------- Methylacrolein radical cation (MA+.) Symmetry: Cs Method: QCISD Basis set: 6-31G* State=2-A'\QCISD=-230.184266 8 1.520568 -0.755133 0.000000 6 1.275975 0.467689 0.000000 6 0.000000 1.120862 0.000000 6 -1.180149 0.433802 0.000000 6 -1.402631 -1.031859 0.000000 1 0.040289 2.205884 0.000000 1 -2.080840 1.052552 0.000000 1 -0.483570 -1.628936 0.000000 1 -2.002493 -1.303947 0.880319 1 -2.002493 -1.303947 -0.880319 1 2.205389 1.076491 0.000000 (no thermochemical data available) ================================================== Transition state TS1 for enolization of MA+. (optimization in Cs) Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-230.8781553 8 1.256064 -0.844261 0.000000 6 0.000000 1.180819 0.000000 6 1.218489 0.419188 0.000000 6 -1.171462 0.493421 0.000000 6 -1.229406 -0.976632 0.000000 1 0.057253 2.262757 0.000000 1 -2.120445 1.038484 0.000000 1 0.092294 -1.242243 0.000000 1 -1.591753 -1.455124 0.917068 1 -1.591753 -1.455124 -0.917068 1 2.200169 0.904564 0.000000 Low frequencies -1370.9067 -110.4131 -10.5081 -9.4147 -0.0007 0.0006 0.0013 10.8286 (second imaginary frequency corresponds to twisting of the CH2 group) Zero-point correction= 0.083186 Thermal correction to Energy= 0.087506 Thermal correction to Enthalpy= 0.088450 Thermal correction to Gibbs Free Energy= 0.055444 -------------------------------------------------- Transition state TS1 for enolization of MA+. (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: 6-31G* HF=-230.8783849 8 1.117452 -1.014633 -0.066474 6 0.169991 1.165449 0.040959 6 1.266315 0.235754 0.022517 6 -1.091989 0.651005 -0.039653 6 -1.356819 -0.780480 0.049068 1 0.383732 2.227866 0.038046 1 -1.930210 1.322215 -0.245701 1 -0.127757 -1.226797 -0.191382 1 -1.407200 -1.205848 1.060937 1 -2.090113 -1.205526 -0.639013 1 2.306939 0.574781 0.071562 Low frequencies -1435.8602 -21.0846 -8.3375 -0.0012 0.0007 0.0012 9.6498 Zero-point correction= 0.083685 Thermal correction to Energy= 0.088631 Thermal correction to Enthalpy= 0.089575 Thermal correction to Gibbs Free Energy= 0.055307 -------------------------------------------------- Transition state TS1 for enolization of MA+. (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: 6-311G** HF=-230.9418006 8 -1.117709 -1.013237 -0.038019 6 -0.170836 1.164485 0.022601 6 -1.263610 0.230959 0.012108 6 1.084424 0.655222 -0.022020 6 1.352036 -0.782651 0.026329 1 -0.387280 2.223811 0.021317 1 1.934902 1.331144 -0.134632 1 0.137106 -1.233440 -0.112333 1 1.979938 -1.199296 -0.763094 1 1.568713 -1.197892 1.017161 1 -2.303793 0.573474 0.041626 Low frequencies -1268.0201 -0.0009 -0.0006 0.0003 6.0594 17.8863 24.57355 Zero-point correction= 0.082772 Thermal correction to Energy= 0.087841 Thermal correction to Enthalpy= 0.088785 Thermal correction to Gibbs Free Energy= 0.054019 -------------------------------------------------- Transition state TS1 for enolization of MA+ (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: cc-pVDZ HF=-230.8946761 8 1.121957 -1.014920 -0.050231 6 0.169970 1.167399 0.029704 6 1.266008 0.232963 0.015463 6 -1.091175 0.652850 -0.027802 6 -1.354311 -0.784077 0.034365 1 0.385669 2.235669 0.029590 1 -1.942950 1.333688 -0.179705 1 -0.140564 -1.229587 -0.146804 1 -1.491911 -1.208399 1.045822 1 -2.043186 -1.206293 -0.711627 1 2.314328 0.579476 0.054193 Low frequencies -1216.4855 -8.0885 -0.0007 -0.0004 0.0007 9.6465 19.2008 Zero-point correction= 0.082603 Thermal correction to Energy= 0.087650 Thermal correction to Enthalpy= 0.088594 Thermal correction to Gibbs Free Energy= 0.054016 -------------------------------------------------- Transition state TS1 for enolization of MA+ (unconstrained optimization) Symmetry: C1 Method: B3LYP Basis set: cc-pVTZ HF=-230.9657872 8 -1.118354 -1.011117 -0.041633 6 -0.169192 1.161252 0.024322 6 -1.261180 0.231948 0.013397 6 1.082872 0.652355 -0.023407 6 1.350299 -0.780393 0.028684 1 -0.383730 2.218723 0.023213 1 1.930077 1.326654 -0.147859 1 0.143590 -1.232622 -0.126126 1 1.997558 -1.195267 -0.742211 1 1.540687 -1.197374 1.021890 1 -2.298141 0.577842 0.046185 Low frequencies -1264.8758 -1.2435 -0.0009 -0.0008 0.0012 16.4554 24.1977 Zero-point correction= 0.082831 Thermal correction to Energy= 0.087886 Thermal correction to Enthalpy= 0.088830 Thermal correction to Gibbs Free Energy= 0.054157 -------------------------------------------------- Transition state TS1 for enolization of MA+ (unconstrained optimization) Symmetry: Cs Method: QCISD Basis set: 6-31G* State=2-A'\QCISD=-230.1677186 8 1.261344 -0.849974 0.000000 6 0.000000 1.184662 0.000000 6 1.223049 0.412004 0.000000 6 -1.168063 0.502562 0.000000 6 -1.225764 -0.975825 0.000000 1 0.070038 2.267736 0.000000 1 -2.118154 1.045207 0.000000 1 0.002239 -1.271722 0.000000 1 -1.614833 -1.437351 0.915371 1 -1.614833 -1.437351 -0.915371 1 2.209462 0.892853 0.000000 (no thermochemical data available) ========================================================= Enol form of methylacrolein radical cation (MAE+.) Symmetry: C1 Method: B3LYP Basis set: 6-31G* HF=-230.9146062 6 1.269706 0.376965 0.134343 6 0.039245 1.050955 0.021203 6 -1.250266 0.493130 -0.142487 6 -1.636419 -0.799699 0.146558 8 1.512680 -0.871593 -0.133167 1 0.119194 2.135170 0.048087 1 -2.026156 1.187888 -0.458210 1 0.754459 -1.343087 -0.535061 1 -0.985287 -1.529087 0.623800 1 -2.661509 -1.115074 -0.022552 1 2.164267 0.908826 0.451568 Zero-point correction= 0.091126 Thermal correction to Energy= 0.096566 Thermal correction to Enthalpy= 0.097511 Thermal correction to Gibbs Free Energy= 0.062189 -------------------------------------------------- Enol form of methylacrolein radical cation (MAE+.) Symmetry: C1 Method: B3LYP Basis set: 6-311G** HF=-230.980191 6 1.268053 0.377246 0.130003 6 0.037308 1.045955 0.020972 6 -1.250562 0.491109 -0.139494 6 -1.636670 -0.798674 0.142565 8 1.515494 -0.867359 -0.128994 1 0.116488 2.128319 0.047392 1 -2.025915 1.187797 -0.444957 1 0.764512 -1.346233 -0.519766 1 -0.984017 -1.533127 0.604896 1 -2.661715 -1.109247 -0.021269 1 2.157918 0.917550 0.441380 Zero-point correction= 0.090597 Thermal correction to Energy= 0.096065 Thermal correction to Enthalpy= 0.097009 Thermal correction to Gibbs Free Energy= 0.061631 -------------------------------------------------- Enol form of methylacrolein radical cation (MAE+.) Symmetry: C1 Method: B3LYP Basis set: cc-pVDZ HF=-230.9305752 6 1.272426 0.377497 0.123091 6 0.039250 1.052419 0.018552 6 -1.254085 0.496924 -0.128919 6 -1.635189 -0.803999 0.135703 8 1.512732 -0.873593 -0.123863 1 0.121367 2.143122 0.041819 1 -2.040043 1.201852 -0.418928 1 0.743350 -1.348398 -0.497715 1 -0.966847 -1.549171 0.579470 1 -2.669462 -1.117724 -0.025994 1 2.175368 0.922018 0.421692 Zero-point correction= 0.090430 Thermal correction to Energy= 0.095910 Thermal correction to Enthalpy= 0.096854 Thermal correction to Gibbs Free Energy= 0.061450 -------------------------------------------------- Enol form of methylacrolein radical cation (MAE+.) Symmetry: C1 Method: B3LYP Basis set: cc-pVTZ HF=-231.0050829 6 1.266306 0.377920 0.127240 6 0.037207 1.043117 0.021140 6 -1.248183 0.490456 -0.136028 6 -1.634450 -0.796528 0.139706 8 1.513060 -0.866542 -0.126791 1 0.116181 2.123354 0.045496 1 -2.021613 1.187186 -0.438729 1 0.760767 -1.353031 -0.504567 1 -0.982723 -1.531297 0.597047 1 -2.657280 -1.105563 -0.026002 1 2.154912 0.921899 0.428734 Zero-point correction= 0.090677 Thermal correction to Energy= 0.096135 Thermal correction to Enthalpy= 0.097079 Thermal correction to Gibbs Free Energy= 0.061721 ================================================== Transition state TS2 for rotation of CH2 group in MAE+. Symmetry: Cs Method: B3LYP Basis set: 6-31G* State=2-A'\HF=-230.8863475 6 1.242355 0.433998 0.000000 6 0.000000 1.126223 0.000000 6 -1.209936 0.489717 0.000000 6 -1.439201 -0.951749 0.000000 8 1.407606 -0.837876 0.000000 1 0.051812 2.209779 0.000000 1 -2.103890 1.124754 0.000000 1 0.537424 -1.328302 0.000000 1 -1.745045 -1.436970 0.929006 1 -1.745045 -1.436970 -0.929006 1 2.184587 0.981573 0.000000 Low frequencies -521.0818 -13.3039 -5.4179 -0.0006 0.0003 0.0008 12.5881 Zero-point correction= 0.087979 Thermal correction to Energy= 0.093080 Thermal correction to Enthalpy= 0.094025 Thermal correction to Gibbs Free Energy= 0.059464 *************************************************** * * * Time-dependent Density Functional Calculations * * * *************************************************** 7-methylindanone radical cation (MI+.) pi-radical (2A") ground state calculated at optimized 2A" B3LYP geometry 39A HOMO (A') ??? 39B LUMO (A") ??? Excitation energies and oscillator strengths: Excited State 1: ?Spin -A" -0.1483 eV -8360.67 nm f=-0.0000 38B -> 39B 0.96025 This state for optimization and/or second-order correction. Total Energy, E(Cis) = -462.021799657 Excited State 2: ?Spin -A' 0.7392 eV 1677.24 nm f=0.0000 36B -> 39B 0.16907 37B -> 39B 1.06596 Excited State 3: ?Spin -A' 2.4835 eV 499.22 nm f=0.0283 37A -> 41A 0.11071 38A -> 40A -0.18857 34B -> 39B 0.15302 36B -> 39B 0.95845 37B -> 39B -0.12926 Excited State 4: ?Spin -A" 2.9009 eV 427.40 nm f=0.0000 3A -> 40A 0.59472 39A -> 41A 0.60921 39A -> 42A 0.22507 33B -> 39B -0.11199 35B -> 39B -0.11956 38B -> 40B -0.49259 38B -> 42B -0.15828 Excited State 5: ?Spin -A" 2.9988 eV 413.44 nm f=0.0003 39A -> 40A 0.12147 29B -> 39B 0.14845 32B -> 39B 0.16660 33B -> 39B 0.46192 35B -> 39B 0.84086 Excited State 6: ?Spin -A" 3.2282 eV 384.07 nm f=0.0000 32B -> 39B 0.64591 33B -> 39B 0.60653 35B -> 39B -0.44034 Excited State 7: ?Spin -A' 3.2908 eV 376.76 nm f=0.0195 37A -> 40A 0.20471 37A -> 41A 0.13698 38A -> 40A -0.29892 38A -> 41A 0.17465 28B -> 39B -0.12556 31B -> 39B 0.13171 34B -> 39B 0.89540 36B -> 39B -0.21032 Excited State 8: ?Spin -A" 3.3856 eV 366.21 nm f=0.0000 39A -> 40A 0.55079 32B -> 39B -0.23119 33B -> 39B 0.13596 38B -> 40B 0.74595 38B -> 42B 0.16013 Excited State 9: ?Spin -A" 3.4587 eV 358.46 nm f=0.0001 39A -> 40A 0.15001 32B -> 39B 0.70131 33B -> 39B -0.61134 35B -> 39B 0.19647 38B -> 40B 0.21835 Excited State 10: ?Spin -A" 3.6115 eV 343.30 nm f=0.0000 39A -> 40A -0.54624 39A -> 41A 0.76278 38B -> 40B 0.30596 Excited State 11: ?Spin -A" 3.9558 eV 313.42 nm f=0.0000 29B -> 39B -0.48242 30B -> 39B 0.84591 35B -> 39B 0.20097 -------------------------------------------------------------- 7-methylindanone radical cation (MI+.) sigma-radical (2A') ground state calculated at B3LYP optimized geometry of 2A' state 39A HOMO (A") 39B LUMO (A') Excitation energies and oscillator strengths: Excited State 1: ?Spin -A" -0.0041 eV -301092.83 nm f=-0.0000 ??? 38B -> 39B 1.07366 This state for optimization and/or second-order correction. Total Energy, E(Cis) = -462.015656425 Excited State 2: ?Spin -A" 0.2261 eV 5484.29 nm f=0.0000 27B -> 39B -0.15528 35B -> 39B -0.23976 37B -> 39B 1.26095 Excited State 3: ?Spin -A" 2.4713 eV 501.68 nm f=0.0000 27B -> 39B 0.25515 32B -> 39B -0.25092 35B -> 39B 0.93051 37B -> 39B 0.19095 Excited State 4: ?Spin -A' 2.6138 eV 474.35 nm f=0.0002 39A -> 40A 0.12340 36B -> 39B 0.99008 Excited State 5: ?Spin -A' 2.7571 eV 449.69 nm f=0.0000 39A -> 40A 0.84111 38B -> 40B -0.76403 38B -> 42B -0.10360 Excited State 6: ?Spin -A' 2.9743 eV 416.85 nm f=0.0010 38A -> 40A -0.18616 34B -> 39B 0.97296 37B -> 40B -0.12200 Excited State 7: ?Spin -A' 3.1175 eV 397.70 nm f=0.0000 38A -> 40A -0.84300 38A -> 42A -0.12452 39A -> 41A -0.23114 37B -> 40B 0.85790 37B -> 42B 0.11821 38B -> 41B 0.22771 Excited State 8: ?Spin -A' 3.3476 eV 370.36 nm f=0.0002 39A -> 40A 0.25219 31B -> 39B 0.21071 33B -> 39B 0.88074 36B -> 39B -0.10044 38B -> 40B 0.30688 Excited State 9: ?Spin -A" 3.4050 eV 364.12 nm f=0.0000 27B -> 39B -0.35070 32B -> 39B 0.88506 35B -> 39B 0.33116 Excited State 10: ?Spin -A' 3.6363 eV 340.96 nm f=0.0080 38A -> 41A -0.11381 39A -> 40A 0.52602 31B -> 39B -0.13638 33B -> 39B -0.34890 37B -> 41B -0.11953 38B -> 40B 0.59380 ------------------------------------------------------------------- Enol form of 7-methylindanone radical cation (ME+.) Calculated for B3LYP optimized igeometry of 2A" state 39A HOMO (A") Excition energies and oscillator strengths: Excited State 1: ?Spin -A' 2.2601 eV 548.58 nm f=0.0241 39A -> 40A 0.93387 37B -> 39B 0.40123 38B -> 40B 0.10465 38B -> 41B 0.12619 This state for optimization and/or second-order correction. Total Energy, E(RPA) = -461.946239371 ??? Excited State 2: ?Spin -A' 2.8466 eV 435.54 nm f=0.0361 38A -> 40A 0.26255 39A -> 41A 0.17694 39A -> 42A 0.11960 38B -> 39B 0.95379 Excited State 3: ?Spin -A' 3.2517 eV 381.29 nm f=0.0969 37A -> 42A 0.12693 38A -> 40A -0.25170 39A -> 40A -0.26810 39A -> 41A 0.29010 39A -> 42A 0.15402 37B -> 39B 0.81897 38B -> 40B 0.24245 38B -> 41B -0.17770 Excited State 4: ?Spin -A' 3.7593 eV 329.80 nm f=0.0283 37A -> 40A -0.15190 38A -> 40A -0.48441 38A -> 41A 0.11633 39A -> 41A 0.51771 39A -> 42A -0.13637 32B -> 39B 0.11762 34B -> 39B 0.13156 37B -> 39B -0.34777 38B -> 40B 0.62395 Excited State 5: ?Spin -A' 4.2966 eV 288.56 nm f=0.0246 37A -> 40A -0.40228 38A -> 40A 0.42880 39A -> 41A 0.33106 39A -> 42A 0.18052 37B -> 40B 0.73688 38B -> 39B -0.14789 Excited State 6: ?Spin -A' 4.6653 eV 265.76 nm f=0.0144 37A -> 40A 0.60901 38A -> 40A 0.32605 39A -> 41A 0.63038 39A -> 42A -0.17895 37B -> 40B -0.18364 38B -> 40B -0.17097 Excited State 7: ?Spin -A" 4.7035 eV 263.60 nm f=0.0000 36B -> 39B 0.98939 Excited State 8: ?Spin -A" 4.8806 eV 254.03 nm f=0.0000 35B -> 39B 0.99254 Excited State 9: ?Spin -A' 5.0161 eV 247.17 nm f=0.0538 37A -> 40A -0.17805 38A -> 40A 0.50936 39A -> 41A -0.15012 39A -> 42A -0.52916 34B -> 39B -0.16426 37B -> 40B -0.16952 38B -> 40B 0.53005 Excited State 10: ?Spin -A' 5.1250 eV 241.92 nm f=0.0003 37A -> 40A -0.41276 39A -> 41A 0.10723 39A -> 42A -0.43039 32B -> 39B 0.19429 34B -> 39B 0.59338 37B -> 40B -0.25439 37B -> 42B 0.11841 38B -> 40B -0.37630 ====================================================================== 4,7-dimethylindanone radical cation (DMI+.) pi-radical (2A") ground state calculated for optimized A" geometry 43A HOMO (A') ??? 43B LUMO (A") ??? Excitation energies and oscillator strengths: Excited State 1: ?Spin -A" 0.0885 eV 14004.54 nm f=0.0000 ??? 42B -> 43B 1.04271 This state for optimization and/or second-order correction. Total Energy, E(RPA) = -501.342048683 Excited State 2: ?Spin -A' 0.9043 eV 1370.98 nm f=0.0004 40B -> 43B 0.13756 41B -> 43B 1.02011 Excited State 3: ?Spin -A' 2.6292 eV 471.56 nm f=0.0350 41A -> 45A 0.20374 42A -> 44A 0.22234 39B -> 43B 0.15934 40B -> 43B 0.95307 41B -> 43B -0.11085 Excited State 4: ?Spin -A" 2.8688 eV 432.18 nm f=0.0000 43A -> 44A 0.81812 43A -> 45A 0.36228 43A -> 46A 0.22612 42B -> 44B -0.43140 42B -> 46B 0.14705 Excited State 5: ?Spin -A" 3.0745 eV 403.27 nm f=0.0003 35B -> 43B 0.11282 37B -> 43B 0.23053 38B -> 43B 0.95949 Excited State 6: ?Spin -A' 3.3641 eV 368.54 nm f=0.0227 41A -> 45A 0.21378 42A -> 44A 0.30399 39B -> 43B 0.91596 40B -> 43B -0.22189 Excited State 7: ?Spin -A" 3.3806 eV 366.75 nm f=0.0000 35B -> 43B 0.13106 36B -> 43B 0.62158 37B -> 43B 0.73136 38B -> 43B -0.19584 42B -> 44B -0.11637 Excited State 8: ?Spin -A" 3.4124 eV 363.33 nm f=0.0000 43A -> 44A 0.42482 37B -> 43B 0.15565 42B -> 44B 0.84470 42B -> 46B -0.19207 Excited State 9: ?Spin -A" 3.6972 eV 335.34 nm f=0.0001 35B -> 43B 0.52349 36B -> 43B 0.60635 37B -> 43B -0.57040 42B -> 44B 0.10694 Excited State 10: ?Spin -A" 3.8602 eV 321.19 nm f=0.0000 33B -> 43B 0.18155 35B -> 43B 0.81536 36B -> 43B -0.46757 37B -> 43B 0.22636 38B -> 43B -0.14954 Excited State 11: ?Spin -A' 3.9126 eV 316.88 nm f=0.0121 40A -> 46A 0.14393 41A -> 44A -0.55111 41A -> 45A -0.51493 42A -> 44A 0.39807 40B -> 46B 0.14615 41B -> 44B 0.62898 41B -> 45B 0.15784 --------------------------------------------------------------------- Enol form of 4,7-dimethylindanone of radical cation (DME+.) Calculated for optimized A" geometry 43A HOMO (A") Excitation energies and oscillator strengths: Excited State 1: ?Spin -A' 2.1576 eV 574.63 nm f=0.0206 43A -> 44A 0.91988 41B -> 43B -0.38668 42B -> 43B -0.22931 42B -> 44B 0.12410 42B -> 45B 0.12525 This state for optimization and/or second-order correction. Total Energy, E(RPA) = -501.271843680 Copying the excited state density for this state as the 1-particle RhoCI density. Excited State 2: ?Spin -A' 2.8597 eV 433.55 nm f=0.0431 42A -> 44A 0.25069 43A -> 45A -0.16006 43A -> 46A -0.14828 41B -> 43B -0.39306 42B -> 43B 0.86840 Excited State 3: ?Spin -A' 3.1152 eV 398.00 nm f=0.1142 41A -> 44A -0.11411 42A -> 44A -0.17015 42A -> 46A -0.12047 43A -> 44A 0.31454 43A -> 45A -0.15920 43A -> 46A -0.14701 41B -> 43B 0.78160 42B -> 43B 0.31941 42B -> 44B -0.12838 42B -> 45B 0.15486 Excited State 4: ?Spin -A' 3.7145 eV 333.78 nm f=0.0094 41A -> 44A 0.33533 42A -> 44A 0.38392 43A -> 45A 0.60827 36B -> 43B -0.11472 38B -> 43B -0.15213 41B -> 43B 0.19722 41B -> 44B -0.25880 42B -> 44B 0.58001 Excited State 5: ?Spin -A' 4.0778 eV 304.05 nm f=0.0220 41A -> 44A 0.35540 42A -> 44A -0.56194 43A -> 45A 0.13470 43A -> 46A 0.18743 41B -> 44B 0.66756 42B -> 43B 0.12521 42B -> 44B 0.34359 Excited State 6: ?Spin -A' 4.5659 eV 271.54 nm f=0.0156 41A -> 44A -0.65616 42A -> 44A -0.17671 43A -> 45A 0.67111 41B -> 44B 0.13467 42B -> 44B -0.17712 Excited State 7: ?Spin -A" 4.6444 eV 266.95 nm f=0.0000 39B -> 43B -0.30169 40B -> 43B 0.94455 Excited State 8: ?Spin -A" 4.7224 eV 262.54 nm f=0.0000 37B -> 43B 0.10288 39B -> 43B 0.94553 40B -> 43B 0.29707 Excited State 9: ?Spin -A' 4.9076 eV 252.63 nm f=0.0264 41A -> 44A -0.17782 42A -> 44A 0.50795 43A -> 46A 0.73708 41B -> 43B 0.10765 41B -> 44B 0.36537 Excited State 10: ?Spin -A' 5.0796 eV 244.08 nm f=0.0140 41A -> 44A -0.35665 42A -> 44A -0.13889 43A -> 45A -0.18569 36B -> 43B 0.18551 38B -> 43B 0.54175 41B -> 44B -0.20224 42B -> 44B 0.61677 ---------------------------------------------------------------------