Electronic Supplementary Material for PCCP This journal is © The Owner Societies 2006 Matrix isolation and computational study of the photochemistry of p-azidoaniline Elena A. Pritchina, Nina P. Gritsan, Thomas Bally ------------------------------------------------------------------- SUPPORTING INFORMATION, PART 1 (ASCII) ------------------------------------------------------------------- A.) B3LYP/6-31G(d) optimized geometries, energies, and thermal corrections of all the stationary points discussed in this work ================================================== A1. p-azidoaniline (1) -------------------------------------------------- E(RB3LYP) = -451.190895 nuclear repulsion energy 461.471797 Zero-point correction= 0.120397 Thermal correction to Energy= 0.128872 Thermal correction to Enthalpy= 0.129817 Thermal correction to Gibbs Free Energy= 0.086788 6 1.141710 -1.209228 -0.008307 6 2.103223 -0.184494 -0.007448 6 1.654266 1.147667 -0.004170 6 0.296623 1.442812 -0.001164 6 -0.652556 0.414989 -0.001369 6 -0.217996 -0.916144 -0.005538 1 1.464343 -2.247878 -0.016345 1 2.379387 1.958159 -0.008770 1 -0.044440 2.473273 0.003753 1 -0.939969 -1.728578 -0.004045 7 -2.018872 0.813691 0.005468 7 -2.889668 -0.061624 0.004954 7 -3.790014 -0.766993 0.005318 7 3.468436 -0.481701 -0.071681 1 4.077365 0.240215 0.293860 1 3.722507 -1.392409 0.291114 ================================================== A2. triplet p-aminophenylnitrene (4), 3A" -------------------------------------------------- E(UB3LYP) = -341.665667, S**2 =2.0448 nuclear repulsion energy 322.812367 Zero-point correction= 0.108376 Thermal correction to Energy= 0.115088 Thermal correction to Enthalpy= 0.116032 Thermal correction to Gibbs Free Energy= 0.076908 6 0.005158 -1.557064 0.000000 6 0.000000 1.293131 0.000000 6 0.005136 -0.806047 1.226183 6 0.005136 -0.806047 -1.226183 6 0.003149 0.571494 1.216667 6 0.003149 0.571494 -1.216667 1 0.007051 1.118351 -2.157299 1 0.007051 1.118351 2.157299 1 0.004093 -1.352945 2.163548 1 0.004093 -1.352945 -2.163548 7 0.002814 -2.880334 0.000000 7 0.049516 2.677723 0.000000 1 -0.259480 3.142850 0.843399 1 -0.259480 3.142850 -0.843399 ================================================== A3. keteneimine (5) -------------------------------------------------- E(RB3LYP) = -341.638264, S**2 =0.0000 nuclear repulsion energy 330.226414 Zero-point correction= 0.108900 Thermal correction to Energy= 0.115526 Thermal correction to Enthalpy= 0.116470 Thermal correction to Gibbs Free Energy= 0.078667 7 -1.860648 -0.497015 -0.567240 6 -1.043253 -1.414686 0.140793 6 0.267645 -1.173251 0.399452 6 1.064059 0.011929 0.040504 6 0.593632 1.299476 -0.032035 6 -0.795235 1.596259 0.332691 6 -1.591165 0.658245 -0.157136 1 1.262870 2.091162 -0.373333 1 -1.498271 -2.369067 0.397136 1 0.837534 -1.991586 0.834866 1 -1.112307 2.412962 0.971994 7 2.426092 -0.271545 -0.146535 1 2.613616 -1.129844 -0.652877 1 2.964350 0.498467 -0.526976 ================================================== A4. azirine (6) -------------------------------------------------- E(RB3LYP) = -341.628345, S**2 =0.0000 nuclear repulsion energy 332.548879 Zero-point correction= 0.108669 Thermal correction to Energy= 0.115264 Thermal correction to Enthalpy= 0.116208 Thermal correction to Gibbs Free Energy= 0.078437 7 -2.044937 -0.475828 0.751480 6 -1.526899 0.355821 -0.050349 6 -0.730126 1.544077 -0.175808 6 0.596054 1.247850 -0.090654 6 -1.125447 -1.013265 -0.414807 6 0.302938 -1.210911 -0.203074 6 1.109379 -0.117442 0.013099 1 -1.118488 2.547035 -0.313238 1 1.324033 2.057300 -0.089771 1 -1.654133 -1.581657 -1.176890 1 0.756741 -2.192339 -0.337466 7 2.475429 -0.238445 0.307864 1 3.062323 0.489124 -0.084163 1 2.860682 -1.156336 0.115686 ================================================== A5. cis-p-aminophenyl nitrosooxide (7) -------------------------------------------------- E(RB3LYP) = -492.009040 nuclear repulsion energy 488.247458 Zero-point correction= 0.118184 Thermal correction to Energy= 0.126654 Thermal correction to Enthalpy= 0.127598 Thermal correction to Gibbs Free Energy= 0.084781 6 -1.139886 -1.199808 -0.006979 6 -2.103682 -0.167667 -0.004167 6 -1.659027 1.176824 -0.002169 6 -0.313085 1.456163 -0.001545 6 0.669594 0.424270 -0.002341 6 0.215215 -0.927553 -0.006207 1 -1.474111 -2.234638 -0.012165 1 -2.387576 1.983631 -0.004219 1 0.038088 2.482943 0.001877 1 0.937578 -1.725849 -0.006020 7 1.936849 0.950648 0.001812 7 -3.442195 -0.457939 -0.042223 1 -4.105467 0.268519 0.186149 1 -3.742296 -1.397535 0.174511 8 2.990058 0.204737 0.004908 8 2.916996 -1.129663 0.005490 ============================================================= A6. cis-p-aminophenyl nitrosooxide (7) 1A' (CS-symmetry, NImag=1) ------------------------------------------------------------- E(RB3LYP) = -492.008837 nuclear repulsion energy 488.300194 Zero-point correction= 0.117475 Thermal correction to Energy= 0.125576 Thermal correction to Enthalpy= 0.126521 Thermal correction to Gibbs Free Energy= 0.084272 6 0.404267 -1.605011 0.000000 6 -0.984817 -1.866886 0.000000 6 -1.883067 -0.770467 0.000000 6 -1.397796 0.515021 0.000000 6 0.000000 0.793222 0.000000 6 0.898552 -0.315049 0.000000 1 1.099209 -2.441469 0.000000 1 -2.954495 -0.954017 0.000000 1 -2.077012 1.361376 0.000000 1 1.959204 -0.130347 0.000000 7 0.233608 2.144779 0.000000 7 -1.453268 -3.146394 0.000000 1 -2.441877 -3.341446 0.000000 1 -0.822665 -3.932437 0.000000 8 1.427771 2.635204 0.000000 8 2.516282 1.857880 0.000000 ================================================== A7. trans-p-aminophenyl nitrosooxide (8) -------------------------------------------------- E(RB3LYP) = -492.002768 nuclear repulsion energy 481.156493 Zero-point correction= 0.117750 Thermal correction to Energy= 0.126391 Thermal correction to Enthalpy= 0.127335 Thermal correction to Gibbs Free Energy= 0.084190 6 -1.332801 -1.215061 -0.006177 6 -2.225798 -0.116095 -0.004297 6 -1.692223 1.190002 -0.002937 6 -0.324037 1.385272 -0.002224 6 0.567641 0.290664 -0.002292 6 0.033171 -1.020976 -0.004904 1 -1.734710 -2.225407 -0.011911 1 -2.364771 2.043986 -0.005669 1 0.094761 2.386492 0.001123 1 0.701550 -1.874441 -0.003657 7 1.906084 0.638420 0.002943 7 -3.585830 -0.323405 -0.050152 1 -4.190355 0.443960 0.208129 1 -3.935655 -1.234161 0.212684 8 2.665687 -0.413014 0.001659 8 3.963273 -0.190533 0.006685 ================================================== A8. trans-p-aminophenylnitroso oxide (8) -------------------------------------------------- E(UB3LYP) = -492.005416, S**2 =0.4747 nuclear repulsion energy 480.378624 Zero-point correction= 0.116775 Thermal correction to Energy= 0.125523 Thermal correction to Enthalpy= 0.126467 Thermal correction to Gibbs Free Energy= 0.083135 6 -1.324890 -1.214225 -0.006675 6 -2.224334 -0.121240 -0.004272 6 -1.697212 1.189041 -0.003238 6 -0.332317 1.393759 -0.002285 6 0.572330 0.302857 -0.002483 6 0.039955 -1.014099 -0.005341 1 -1.721222 -2.226925 -0.012628 1 -2.375346 2.038802 -0.006214 1 0.079618 2.397822 0.001157 1 0.711490 -1.864613 -0.004146 7 -3.584926 -0.334845 -0.051288 1 -4.190108 0.429009 0.216395 1 -3.928056 -1.246286 0.218640 7 1.897991 0.656225 0.002740 8 2.669408 -0.437977 0.001553 8 3.959463 -0.186277 0.007497 =================================================================== A9. trans-p-aminophenylnitroso oxide (8) 1A' (CS-symmetry, NImag=1) ------------------------------------------------------------------ E(RB3LYP) = -492.002390 nuclear repulsion energy 481.188684 Zero-point correction= 0.117004 Thermal correction to Energy= 0.125312 Thermal correction to Enthalpy= 0.126257 Thermal correction to Gibbs Free Energy= 0.083636 6 -0.475035 -1.740430 0.000000 6 0.911779 -2.034977 0.000000 6 1.831880 -0.963214 0.000000 6 1.380983 0.342394 0.000000 6 0.000000 0.638111 0.000000 6 -0.923510 -0.436392 0.000000 1 -1.191125 -2.558742 0.000000 1 2.898485 -1.172576 0.000000 1 2.081202 1.171642 0.000000 1 -1.987780 -0.230265 0.000000 7 -0.301047 1.987007 0.000000 7 1.343859 -3.331008 0.000000 1 2.326351 -3.553561 0.000000 1 0.691989 -4.098975 0.000000 8 -1.583432 2.184488 0.000000 8 -1.975991 3.442703 0.000000 =============================================================== A10. p-aminophenyl dioxaziridine --------------------------------------------------------------- E(RB3LYP) = -491.982249 nuclear repulsion energy 493.278852 Zero-point correction= 0.117209 Thermal correction to Energy= 0.125685 Thermal correction to Enthalpy= 0.126629 Thermal correction to Gibbs Free Energy= 0.083665 6 -1.195237 -1.201992 -0.008945 6 -2.091429 -0.110286 -0.006349 6 -1.568362 1.195356 -0.003429 6 -0.193384 1.400299 -0.003654 6 0.678285 0.310751 -0.004806 6 0.174050 -0.995778 -0.008196 1 -1.590369 -2.215102 -0.016552 1 -2.245083 2.046157 -0.005936 1 0.218311 2.404992 0.000082 1 0.861420 -1.833869 -0.007931 7 2.074396 0.646684 0.000478 7 -3.460849 -0.327096 -0.060678 1 -4.047229 0.433532 0.256634 1 -3.784283 -1.229255 0.262677 8 2.838345 -0.337299 0.740931 8 2.845262 -0.341909 -0.722842 =============================================================== A11. p-aminophenyl dioxaziridine 1A' (CS-symmetry, NImag=1) --------------------------------------------------------------- E(RB3LYP) = -491.981307 nuclear repulsion energy 493.496864 6 0.595415 -1.587634 0.000000 6 -0.772148 -1.948321 0.000000 6 -1.741819 -0.926798 0.000000 6 -1.353765 0.407211 0.000000 6 0.000000 0.746933 0.000000 6 0.976886 -0.257339 0.000000 1 1.352264 -2.368545 0.000000 1 -2.797415 -1.186464 0.000000 1 -2.095741 1.199954 0.000000 1 2.025285 0.017876 0.000000 7 0.276691 2.154488 0.000000 7 -1.141436 -3.269602 0.000000 1 -2.111367 -3.539066 0.000000 1 -0.451546 -4.002646 0.000000 8 1.494020 2.442524 0.730000 8 1.494020 2.442524 -0.730000 ============================================ A12. triplet syn-p-aminophenylnitroso oxide -------------------------------------------- E(UB3LYP) = -491.989393, S**2 = 2.0286 nuclear repulsion energy 485.284101 Zero-point correction= 0.115916 Thermal correction to Energy= 0.124853 Thermal correction to Enthalpy= 0.125798 Thermal correction to Gibbs Free Energy= 0.080867 6 1.110706 -1.191068 -0.161333 6 2.096189 -0.192069 0.029286 6 1.682172 1.158768 0.143419 6 0.350889 1.490070 0.068273 6 -0.655630 0.489180 -0.124755 6 -0.226266 -0.871579 -0.236712 1 1.421443 -2.229782 -0.248308 1 2.429367 1.934144 0.294924 1 0.026532 2.522096 0.153603 1 -0.961655 -1.651964 -0.383382 7 -1.915391 0.953631 -0.194398 7 3.424428 -0.530486 0.145961 1 4.115120 0.197290 0.026391 1 3.715153 -1.441640 -0.180059 8 -2.857079 -0.127786 -0.401036 8 -3.075117 -0.821210 0.696888 ============================================ A13. triplet anti-p-aminophenylnitroso oxide -------------------------------------------- E(UB3LYP) = -491.989642, S**2 = 2.0281 nuclear repulsion energy 478.253463 Zero-point correction= 0.115872 Thermal correction to Energy= 0.124957 Thermal correction to Enthalpy= 0.125902 Thermal correction to Gibbs Free Energy= 0.080197 6 -1.295610 -1.214410 -0.007690 6 -2.217670 -0.140708 -0.003505 6 -1.715938 1.186606 -0.003700 6 -0.364112 1.424603 -0.002738 6 0.582707 0.346055 -0.003366 6 0.063499 -0.991105 -0.007157 1 -1.672758 -2.234722 -0.013546 1 -2.415293 2.019450 -0.006998 1 0.025196 2.437516 0.000529 1 0.750041 -1.827724 -0.007032 7 1.871285 0.716795 0.001610 7 -3.573700 -0.376396 -0.047550 1 -4.194394 0.375726 0.218046 1 -3.903625 -1.296863 0.208167 8 2.679557 -0.506727 0.001412 8 3.946753 -0.183576 0.010009 B.) CASSCF(8,8)/6-31G(d) optimized geometries, energies, and thermal corrections of triplet p-aminophenylnitrene (4) ================================================== B1. Cs-symmetry, 3A"-state -------------------------------------------------- Active space: 8 electrons in 8 Orbitals (5/4 a' + 3/4 a") PRIMARY BASIS FUNCTION= 1 2 3 4 5 1 2 3 Coeff. 0.9136446 Weight 0.834746 Final one electron symbolic density matrix: 1 2 3 4 5 1 0.195442D+01 2 0.000000D+00 0.189272D+01 3 0.854798D-06 0.000000D+00 0.188837D+01 4 0.000000D+00 0.263530D-05 0.000000D+00 0.100000D+01 5 -0.842951D-05 0.000000D+00 -0.178930D-07 0.000000D+00 0.100064D+01 6 0.000000D+00 -0.129184D-05 0.000000D+00 0.456776D-06 0.000000D+00 7 -0.423380D-05 0.000000D+00 -0.726502D-06 0.000000D+00 0.547710D-06 8 0.225548D-05 0.000000D+00 0.263591D-06 0.000000D+00 0.230120D-05 6 7 8 6 0.109740D+00 7 0.000000D+00 0.112626D+00 8 0.000000D+00 0.103535D-05 0.414827D-01 E(CASSCF) = -339.622141 Nuclear repulsion energy 323.462678 Zero-point correction= 0.113884 Thermal correction to Energy= 0.120447 Thermal correction to Enthalpy= 0.121391 Thermal correction to Gibbs Free Energy= 0.082401 7 -0.004558 -2.878514 0.000000 6 -0.005713 -1.542730 0.000000 6 -0.007323 -0.811245 1.222457 6 -0.007323 -0.811245 -1.222457 6 -0.005852 0.572190 1.211986 6 -0.005852 0.572190 -1.211986 6 0.000000 1.287337 0.000000 7 -0.055314 2.687360 0.000000 1 -0.009746 -1.350488 2.151516 1 -0.009746 -1.350488 -2.151516 1 -0.015013 1.111230 2.143297 1 -0.015013 1.111230 -2.143297 1 0.330499 3.108808 0.818056 1 0.330499 3.108808 -0.818056 ============================================ B2. C2V-symmetry, NImag=1 - planar NH2-group -------------------------------------------- Active space: 8 electrons in 8 Orbitals (5/5 b1 + 2/2 a2 + 1/1 b2) PRIMARY BASIS FUNCTION= 1 2 3 4 5 1 2 3 Coeff. 0.9153301 Weight 0.837829 Final one electron symbolic density matrix: 1 2 3 4 5 1 0.195508D+01 2 0.000000D+00 0.189479D+01 3 0.359690D-06 0.000000D+00 0.189084D+01 4 0.000000D+00 0.000000D+00 0.000000D+00 0.100000D+01 5 -0.828733D-06 0.000000D+00 -0.729586D-05 0.000000D+00 0.100045D+01 6 0.000000D+00 -0.878900D-06 0.000000D+00 0.000000D+00 0.000000D+00 7 -0.209619D-05 0.000000D+00 0.945415D-06 0.000000D+00 -0.513221D-05 8 -0.108974D-06 0.000000D+00 -0.136076D-05 0.000000D+00 0.649075D-06 6 7 8 6 0.108202D+00 7 0.000000D+00 0.110049D+00 8 0.000000D+00 0.178256D-06 0.405836D-01 E(CASSCF) = -339.619102 Nuclear repulsion energy 323.724681 7 0.000000 0.000000 2.879649 6 0.000000 0.000000 1.544553 6 0.000000 1.221421 0.811024 6 0.000000 -1.221421 0.811024 6 0.000000 1.212309 -0.571586 6 0.000000 -1.212309 -0.571586 6 0.000000 0.000000 -1.289561 7 0.000000 0.000000 -2.668111 1 0.000000 2.151060 1.349438 1 0.000000 -2.151060 1.349438 1 0.000000 2.144360 -1.109492 1 0.000000 -2.144360 -1.109492 1 0.000000 0.847543 -3.181937 1 0.000000 -0.847543 -3.181937 C.) Result of CASSCF/CASPT2-calculation on triplet p-aminophenylnitrene Note: The states are ordered according to their CASSCF energies, not according to their occurrence in the experimental spectra or the CASPT2 energies, as in the tables of the paper. =============================================== C1. Geometry: CASSCF(8,8)/6-31G(d), Cs-symmetry ----------------------------------------------- Active space: 12 electrons in 12 Orbitals (9/8 a' + 3/4 a") Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-7 of A' are averaged. State averaging: States 1-5 of A" are averaged. Summary of the calculation (Description of the excited states is presented in Table S1, MOs are in Figure S1, dependence of energy and reference weight of CASPT2 states on level shift - Table S2): CAS(12/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 13A" -339.684477 -340.604311 74.9% 13A' -339.572287 -340.498338 43.7% 2.88 eV 430 nm 0.0013 23A" -339.564169 -340.504202 44.6% 2.72 eV 455 nm 0.0141 43A' -339.484392 -340.470241 65.9% 3.65 eV 340 nm 0.0459 23A' -339.541594 -340.459211 65.4% 3.95 eV 314 nm 0.0000 33A' -339.524377 -340.452022 73.7% 4.14 eV 299 nm 0.0142 33A" -339.514546 -340.441194 61.9% 4.44 eV 279 nm 0.0035 73A" -339.444739 -340.436084 34.7% 4.58 eV 271 nm 0.3227 53A" -339.492213 -340.769466 0.0% - eV - nm - 43A" -339.503699 -340.433844 74.1% 4.64 eV 267 nm 0.0000 63A" -339.491373 -340.424788 56.8% 4.89 eV 254 nm 0.0017 53A' -339.475532 -340.396714 74.3% 5.65 eV 219 nm 0.0000 --------------------------------------------------------------------------- CAS(12/12) + CASPT2 (0.10 h level shift for A' states, 0.2 h - for A" states) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 13A" -339.684477 -340.599503 77.8% 13A' -339.572287 -340.496880 75.7% 2.89 eV 429 nm 0.0013 23A" -339.564169 -340.491066 77.1% 2.95 eV 420 nm 0.0152 43A' -339.484392 -340.467712 72.8% 3.68 eV 337 nm 0.0463 23A' -339.541594 -340.457530 76.3% 3.96 eV 313 nm 0.0000 33A' -339.524377 -340.450325 76.0% 4.15 eV 298 nm 0.0142 33A" -339.514546 -340.435909 77.0% 4.45 eV 279 nm 0.0035 73A" -339.444739 -340.430405 73.6% 4.60 eV 269 nm 0.3243 53A" -339.492213 -340.429910 76.9% 4.61 eV 269 nm 0.0061 43A" -339.503699 -340.428572 77.3% 4.65 eV 267 nm 0.0000 63A" -339.491373 -340.421655 76.1% 4.84 eV 256 nm 0.0017 53A' -339.475532 -340.395271 76.0% 5.65 eV 219 nm 0.0000 --------------------------------------------------------------------------- | A' A" ------------------+---------- Inactive Orbitals | 8 6 Ras2 Orbitals | 8 4 Frozen Orbitals | 6 2 Orbitals 15-22 of Symmetry A' are active (see Figure S1) Orbitals 9-12 of Symmetry A" are active (see Figure S1) A'-States: ---------- root 1: CASSCF energy: -339.572287 CASPT2 energy: -340.498338 Reference weight: 0.437 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 14 22222000 uu00 0.64197 0.41212 3694 22220000 2uu0 0.55515 0.30819 Natural orbitals and occupation numbers for root 1 sym 1: 1.932072 1.975121 1.997423 1.870968 1.065627 0.112612 0.020454 0.058851 sym 2: 1.426906 0.992946 0.538024 0.008995 root 2: CASSCF energy: -339.541594 CASPT2 energy: -340.459211 Reference weight: 0.654 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 9764 222uu000 2200 0.89104 0.79394 Natural orbitals and occupation numbers for root 2 sym 1: 1.933572 1.972158 1.995287 1.034141 0.973568 0.063643 0.021604 0.029974 sym 2: 1.887361 1.958316 0.106535 0.023840 root 3: CASSCF energy: -339.524377 CASPT2 energy: -340.452022 Reference weight: 0.737 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 9990 2u22u000 2200 0.89869 0.80764 Natural orbitals and occupation numbers for root 3 sym 1: 1.958568 0.994750 1.998007 1.903596 1.001903 0.098094 0.007120 0.039052 sym 2: 1.895366 1.974522 0.105965 0.023058 root 4: CASSCF energy: -339.484392 CASPT2 energy: -340.470241 Reference weight: 0.659 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 14 22222000 uu00 -0.56655 0.32098 3694 22220000 2uu0 0.56978 0.32465 Natural orbitals and occupation numbers for root 4 sym 1: 1.951948 1.974572 1.990751 1.790933 0.918184 0.071662 0.020341 0.041270 sym 2: 1.584691 0.992626 0.652373 0.010649 root 5: CASSCF energy: -339.475532 CASPT2 energy: -340.396714 Reference weight: 0.743 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 3696 22220000 u2u0 0.81716 0.66775 Natural orbitals and occupation numbers for root 5 sym 1: 1.888184 1.970517 1.991602 1.827578 0.267313 0.072638 0.020819 0.041360 sym 2: 1.111766 1.897996 0.887182 0.023047 A"-States: ---------- root 1: (ground state) CASSCF energy: -339.684477 CASPT2 energy: -340.604311 Reference weight: 0.749 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 442 2222u000 2u00 -0.90566 0.82021 Natural orbitals and occupation numbers for root 1 sym 1: 1.955103 1.978169 1.998093 1.897851 1.003151 0.103549 0.018597 0.041540 sym 2: 1.890404 0.994320 0.111746 0.007476 root 2: CASSCF energy: -339.564169 CASPT2 energy: -340.504202 Reference weight: 0.446 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 486 222u2000 2u00 0.69674 0.48545 662 22220u00 2u00 0.53066 0.28160 Natural orbitals and occupation numbers for root 2 sym 1: 1.925480 1.979280 1.996794 1.364604 1.210941 0.436617 0.017964 0.062637 sym 2: 1.877843 0.994441 0.126069 0.007330 root 3: CASSCF energy: -339.514546 CASPT2 energy: -340.441194 Reference weight: 0.619 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 451 2222u000 udu0 -0.68617 0.47083 454 2222u000 uud0 -0.39620 0.15698 Natural orbitals and occupation numbers for root 3 sym 1: 1.900326 1.977634 1.995814 1.827230 1.045200 0.149422 0.018949 0.083084 sym 2: 1.114641 0.994235 0.885833 0.007632 root 4: CASSCF energy: -339.503699 CASPT2 energy: -340.433844 Reference weight: 0.741 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 444 2222u000 u200 0.77185 0.59576 488 222u2000 u200 0.36278 0.13161 Natural orbitals and occupation numbers for root 4 sym 1: 1.916367 1.972602 1.998135 1.844561 0.947070 0.082186 0.021653 0.034075 sym 2: 1.066964 1.957563 0.134147 0.024676 root 5: CASSCF energy: -339.492213 CASPT2 energy: -340.769466 Reference weight: 0.0007 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 574 2u222000 2u00 0.87596 0.76731 Natural orbitals and occupation numbers for root 5 sym 1: 1.982565 1.017143 1.998515 1.953748 1.864873 0.125753 0.006358 0.042732 sym 2: 1.889731 0.995736 0.117728 0.005117 root 6: CASSCF energy: -339.491373 CASPT2 energy: -340.424788 Reference weight: 0.568 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 450 2222u000 duu0 0.47998 0.23038 451 2222u000 udu0 -0.40283 0.16227 618 u2222000 2u00 0.49133 0.24141 Natural orbitals and occupation numbers for root 6 sym 1: 1.626833 1.970463 1.994965 1.823925 1.239881 0.190932 0.019301 0.129785 sym 2: 1.427982 0.993538 0.574107 0.008288 root 7: CASSCF energy: -339.444379 CASPT2 energy: -340.436084 Reference weight: 0.347 dominant CSFs: Symmetry: A' A" conf/sym 11111111 2222 Coeff Weight 486 222u2000 2u00 -0.50679 0.25684 662 22220u00 2u00 0.55164 0.30431 Natural orbitals and occupation numbers for root 7 sym 1: 1.927343 1.974879 1.971671 1.593870 0.963577 0.480977 0.021752 0.059656 sym 2: 1.810782 0.988471 0.192976 0.014046 ================================================================== C2. Geometry: CASSCF(8,8)/6-31G(d), C2v-symmetry (planar NH2-group) ------------------------------------------------------------------ Active space: 12 electrons in 12 Orbitals (2/2 a1 + 7/6 b1 + 2/2 a2 + 1/2 b2) Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-2 of A1 are averaged State averaging: States 1-5 of B1 are averaged State averaging: States 1-5 of A2 are averaged State averaging: States 1-3 of B2 are averaged Summary of the calculation (Description of the excited states is presented in Table 1, MOs are in Figure 3, dependence of energy and reference weight of CASPT2 states on level shift - Table S3): CAS(12/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 13A2 -339.688726 -340.601508 74.9% 13B1 -339.568508 -340.498726 73.7% 2.80 eV 443 nm 0.0044 23A2 -339.568947 -340.488557 46.8% 3.07 eV 403 nm 0.0141 33B1 -339.487627 -340.467576 68.2% 3.64 eV 340 nm 0.0382 13A1 -339.546940 -340.462969 74.6% 3.77 eV 329 nm 0.0000 23B1 -339.518237 -340.448562 74.0% 4.16 eV 298 nm 0.0139 13B2 -339.489669 -340.438502 70.8% 4.44 eV 280 nm 0.0021 53A2 -339.455791 -340.425794 16.0% 4.78 eV 259 nm 0.3745 33A2 -339.518666 -340.439107 72.2% 4.42 eV 281 nm 0.0056 23B2 -339.474303 -340.431496 72.4 4.63 eV 268 nm 0.0090 33B2 -339.469349 -340.428989 73.4% 4.69 eV 264 nm 0.0000 43A2 -339.494912 -340.438401 49.9% 4.44 eV 279 nm 0.0059 43B1 -339.465995 -340.418487 70.4% 4.98 eV 249 nm 0.0165 53B1 -339.443996 -340.401337 34.8% 5.45 eV 228 nm 0.0011 23A1 -339.482166 -340.396418 74.4% 5.58 eV 222 nm 0.0000 --------------------------------------------------------------------------- CAS(12/12) + CASPT2 (0.10 h level shift for B1 states, 0.2 h - for A2 states) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 13A2 -339.688726 -340.596683 77.9% 13B1 -339.568508 -340.497135 75.6% 2.80 eV 442 nm 0.0044 23A2 -339.568947 -340.489715 77.2% 2.91 eV 426 nm 0.0134 33B1 -339.487627 -340.465083 73.5% 3.66 eV 338 nm 0.0384 23B1 -339.518237 -340.447001 75.9% 4.17 eV 297 nm 0.0139 53A2 -339.455791 -340.434337 73.6% 4.42 eV 281 nm 0.3463 33A2 -339.518666 -340.433508 77.1% 4.44 eV 279 nm 0.0057 43A2 -339.494912 -340.418413 76.4% 4.85 eV 256 nm 0.0064 43B1 -339.465995 -340.418085 73.7% 4.96 eV 250 nm 0.0164 53B1 -339.443996 -340.403779 73.0% 5.34 eV 232 nm 0.0011 --------------------------------------------------------------------------- | A1 B1 A2 B2 ------------------+-------------------- Inactive Orbitals | 8 0 0 6 Ras2 Orbitals | 2 6 2 2 Frozen Orbitals | 6 0 0 2 Orbitals 15-16 of Symmetry A1 are active (see Figure 3) Orbitals 1-6 of Symmetry B1 are active (see Figure 3) Orbitals 1-2 of Symmetry A2 are active (see Figure 3) Orbitals 9-10 of Symmetry B2 are active (see Figure 3) A1-States: ---------- root 1: CASSCF energy: -339.546940 CASPT2 energy: -340.462969 Reference weight: 0.746 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 5378 20 22uu00 20 20 0.92135 0.84888 Natural orbitals and occupation numbers for root 1 sym 1: 1.976688 0.023080 sym 2: 1.992733 1.935834 1.023305 0.982905 0.058551 0.030644 sym 3: 1.896439 0.097405 sym 4: 1.957697 0.024720 root 2: CASSCF energy: -339.482166 CASPT2 energy: -340.396418 Reference weight: 0.744 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1970 20 222000 uu 20 -0.84059 0.70659 Natural orbitals and occupation numbers for root 2 sym 1: 1.976008 0.023895 sym 2: 1.988473 1.807593 1.890988 0.267008 0.065205 0.041501 sym 3: 1.138792 0.860251 sym 4: 1.915794 0.024491 B1-States: ---------- root 1: CASSCF energy: -339.568508 CASPT2 energy: -340.498726 Reference weight: 0.737 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 69 20 222200 u0 u0 -0.54949 0.30194 3028 20 222000 2u u0 0.64973 0.42215 Natural orbitals and occupation numbers for root 1 sym 1: 1.975794 0.019666 sym 2: 1.995550 1.929781 1.858795 0.882011 0.114649 0.060758 sym 3: 1.527698 0.633081 sym 4: 0.993911 0.008306 6 root 2: CASSCF energy: -339.518237 CASPT2 energy: -340.448562 Reference weight: 0.740 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 6297 u0 222u00 20 20 -0.89459 0.80029 Natural orbitals and occupation numbers for root 2 sym 1: 0.995732 0.006918 sym 2: 1.997199 1.959301 1.902243 1.001812 0.099964 0.038559 sym 3: 1.898680 0.102838 sym 4: 1.976128 0.020627 root 3: CASSCF energy: -339.487627 CASPT2 energy: -340.467576 Reference weight: 0.682 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 69 20 222200 u0 u0 0.60405 0.36487 3028 20 222000 2u u0 0.52579 0.27645 Natural orbitals and occupation numbers for root 3 sym 1: 1.974834 0.019707 sym 2: 1.987707 1.945913 1.763364 1.050489 0.076071 0.043444 sym 3: 1.530139 0.604274 sym 4: 0.994278 0.009781 root 4: CASSCF energy: -339.465995 CASPT2 energy: -340.418487 Reference weight: 0.704 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 457 20 222uu0 u0 d0 0.34580 0.11958 8622 20 22uu00 2u d0 0.65880 0.43402 Natural orbitals and occupation numbers for root 4 sym 1: 1.977706 0.018183 sym 2: 1.992022 1.898341 1.313333 0.983957 0.294613 0.079626 sym 3: 1.661721 0.778077 sym 4: 0.994664 0.007756 root 5: CASSCF energy: -339.443996 CASPT2 energy: -340.401337 Reference weight: 0.348 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 8611 20 22uu00 2d u0 -0.64120 0.41114 Natural orbitals and occupation numbers for root 5 sym 1: 1.979506 0.016730 sym 2: 1.991356 1.846652 1.292932 0.958420 0.282571 0.092446 sym 3: 1.655895 0.881134 sym 4: 0.995570 0.006787 A2-States: ---------- root 1: (ground state) CASSCF energy: -339.688726 CASPT2 energy: -340.601508 Reference weight: 0.749 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1167 20 222u00 20 u0 -0.89652 0.80375 Natural orbitals and occupation numbers for root 1 sym 1: 1.976129 0.023481 sym 2: 1.997250 1.955205 1.896866 1.003245 0.103088 0.040972 sym 3: 1.893765 0.109326 sym 4: 0.994978 0.005695 root 2: CASSCF energy: -339.568947 CASPT2 energy: -340.488557 Reference weight: 0.468 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1431 20 22u200 20 u0 0.68709 0.47210 1927 20 2220u0 20 u0 0.54283 0.29466 Natural orbitals and occupation numbers for root 2 sym 1: 1.977128 0.022403 sym 2: 1.995673 1.926017 1.372209 1.189061 0.447587 0.062337 sym 3: 1.880934 0.126022 sym 4: 0.995134 0.005495 root 3: CASSCF energy: -339.518666 CASPT2 energy: -340.439107 Reference weight: 0.722 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1172 20 222u00 uu d0 0.76642 0.58740 Natural orbitals and occupation numbers for root 3 sym 1: 1.976181 0.023453 sym 2: 1.994125 1.895471 1.829745 1.049014 0.144566 0.085740 sym 3: 1.118133 0.882926 sym 4: 0.994833 0.005814 root 4: CASSCF energy: -339.494912 CASPT2 energy: -340.425794 Reference weight: 0.160 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1168 20 222u00 du u0 -0.48968 0.23978 1172 20 222u00 uu d0 -0.38419 0.14760 1585 20 2u2200 20 u0 0.50083 0.25084 Natural orbitals and occupation numbers for root 4 sym 1: 1.976102 0.023573 sym 2: 1.992110 1.641390 1.828257 1.217088 0.191909 0.125578 sym 3: 1.412529 0.590867 sym 4: 0.994255 0.006341 root 5: CASSCF energy: -339.455791 CASPT2 energy: -340.438401 Reference weight: 0.499 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1431 20 22u200 20 u0 0.49004 0.24014 1927 20 2220u0 20 u0 -0.61263 0.37531 Natural orbitals and occupation numbers for root 5 sym 1: 1.975109 0.024211 sym 2: 1.964005 1.933457 1.601940 0.919334 0.514667 0.058575 sym 3: 1.845490 0.161978 sym 4: 0.989749 0.011486 B2-States: ---------- root 1: CASSCF energy: -339.489669 CASPT2 energy: -340.438502 Reference weight: 0.708 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1013 2u 222000 20 u0 0.79915 0.63864 Natural orbitals and occupation numbers for root 1 sym 1: 1.995635 0.999999 sym 2: 1.950553 1.921212 1.763352 0.261656 0.072510 0.040682 sym 3: 1.892780 0.100133 sym 4: 0.995995 0.005494 root 2: CASSCF energy: -339.474303 CASPT2 energy: -340.431496 Reference weight: 0.724 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 1717 u0 222200 20 u0 -0.90134 0.81241 Natural orbitals and occupation numbers for root 2 sym 1: 1.002701 0.000335 sym 2: 1.997960 1.989724 1.960707 1.890460 0.110813 0.038166 sym 3: 1.905696 0.100040 sym 4: 0.999919 0.003479 root 3: CASSCF energy: -339.469349 CASPT2 energy: -340.428989 Reference weight: 0.734 dominant CSFs: Symmetry: A1 B1 A2 B2 conf/sym 11 222222 33 44 Coeff Weight 427 20 222u00 u0 20 -0.76245 0.58133 691 20 22u200 u0 20 -0.39104 0.15291 Natural orbitals and occupation numbers for root 3 sym 1: 1.989985 0.000416 sym 2: 1.996373 1.912222 1.873226 0.961310 0.074801 0.035306 sym 3: 1.056594 0.115051 sym 4: 1.955587 0.029130 D.) CASSCF(12,12)/6-31G(d) optimized geometries, energies of the p-aminophenylnitroso oxides Note: The states are ordered according to their CASSCF energies, not according to their occurrence in the experimental spectra or the CASPT2 energies, as in the tables of the paper. ============================================================= D1. cis-p-aminophenylnitrosooxide 1-A' (CS-symmetry) ------------------------------------------------------------- Active space: 12 electrons in 12 Orbitals (8/8 a" + 4/4 a') Basis: 6-31G(d), [3s,2p,1d] on C, O, N and [2s] on H | A' A" ------------------+----------- Inactive Orbitals | 18 2 Ras2 Orbitals | 4 8 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active. Orbitals 3-10 of Symmetry A" are active. root 1: CASSCF energy: -489.261418 dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 6657 2200 22220000 0.90954 0.82726 6660 2200 22202000 -0.15708 0.02467 Natural orbitals and occupation numbers for root 1 sym 1: 1.976059 1.966797 0.034914 0.022529 sym 2: 1.961552 1.929236 1.910067 1.884753 0.123778 0.091211 0.066165 0.032940 Nuclear repulsion energy = 489.267187 Nuclear coordinates of the final structure / bohr C1 0.6902526608 -3.1815880322 0.0000000000 C2 -1.9215184179 -3.6668108193 0.0000000000 C3 -3.5990072543 -1.6079097226 0.0000000000 C4 -2.6719359350 0.8325143465 0.0000000000 C5 -0.0527510009 1.3208688243 0.0000000000 C6 1.6410850259 -0.7424050823 0.0000000000 N1 0.3803828914 3.9571084914 0.0000000000 N2 -2.8100694404 -6.0930842550 0.0000000000 H1 1.9904887811 -4.7437532391 0.0000000000 H2 -5.6045071892 -1.9343492049 0.0000000000 H3 -3.9485563271 2.4088583332 0.0000000000 H4 3.6271364736 -0.4291736203 0.0000000000 H5 -4.6489092901 -6.4554004706 0.0000000000 H6 -1.6377978194 -7.5555424499 0.0000000000 O1 2.5793921889 4.8946710302 0.0000000000 O2 4.6286322190 3.4398518534 0.0000000000 ============================================================= D2. trans-p-aminophenylnitrosooxide 1-A' (CS-symmetry) ------------------------------------------------------------- Active space: 12 electrons in 12 Orbitals (8/8 a" + 4/4 a') Basis: 6-31G(d), [3s,2p,1d] on C, O, N and [2s] on H | A' A" ------------------+----------- Inactive Orbitals | 18 2 Ras2 Orbitals | 4 8 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active. Orbitals 3-10 of Symmetry A" are active. root 1: CASSCF energy: -489.260377 dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 6657 2200 22220000 0.90574 0.82037 6660 2200 22202000 -0.15883 0.02523 Natural orbitals and occupation numbers for root 1 sym 1: 1.975849 1.967102 0.033668 0.023544 sym 2: 1.961083 1.925178 1.906900 1.876649 0.129251 0.095407 0.071114 0.034253 Nuclear repulsion energy = 481.455091 Nuclear coordinates of the final structure / bohr C1 -0.8273930660 -3.4457288203 0.0000000000 C2 1.7814205657 -3.9929262802 0.0000000000 C3 3.5091180834 -1.9852217945 0.0000000000 C4 2.6560755837 0.4971568136 0.0000000000 C5 0.0686706927 1.0169735115 0.0000000000 C6 -1.6860883721 -0.9784041571 0.0000000000 N1 -0.5391845818 3.6398541462 0.0000000000 N2 2.5986961723 -6.4503104290 0.0000000000 H1 -2.1672168313 -4.9734776477 0.0000000000 H2 5.5040873755 -2.3692934468 0.0000000000 H3 3.9714085623 2.0421945385 0.0000000000 H4 -3.6766701977 -0.5987192538 0.0000000000 H5 4.4260611824 -6.8659199505 0.0000000000 H6 1.3854736757 -7.8784537724 0.0000000000 O1 -2.8935105629 4.0020682984 0.0000000000 O2 -3.6322005242 6.4273763520 0.0000000000 E.) Result of CASSCF/CASPT2-calculation on cis-p-aminophenylnitroso oxide Note: The states are ordered according to their CASSCF energies, not according to their occurrence in the experimental spectra or the CASPT2 energies, as in the tables of the paper. ===================================== E1. Geometry: CASSCF(12,12)/6-31G(d) ------------------------------------- Active space: 16 electrons in 14 Orbitals (12/10 a" + 4/4 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-6 of A' are averaged Summary of the calculation (Description of the excited states is presented in Table 2, MOs are in Figure 10, dependence of energy and reference weight of CASPT2 states on level shift - Table S4): CAS(16/14) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.352924 -490.619194 69.5% 1-A" -489.248957 -490.528446 69.3% 2.47 eV 502 nm 0.0000 4-A' -489.183192 -490.511776 65.9% 2.92 eV 424 nm 0.2960 3-A' -489.206009 -490.475284 65.0% 3.33 eV 372 nm 0.0180 2-A' -489.207724 -490.480913 57.3% 3.76 eV 329 nm 0.0030 5-A' -489.138197 -490.443425 54.7% 4.78 eV 259 nm 0.0089 6-A' -489.125647 -490.432613 39.1% 5.08 eV 244 nm 0.0400 --------------------------------------------------------------------------- CAS(16/14) + CASPT2 (0.2 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.352924 -490.613098 72.8% 4-A' -489.183192 -490.502874 70.6% 3.00 eV 413 nm 0.3037 2-A' -489.207724 -490.473139 72.1% 3.81 eV 326 nm 0.0035 3-A' -489.206009 -490.470035 72.1% 3.89 eV 319 nm 0.0213 5-A' -489.138197 -490.435617 70.9% 4.83 eV 257 nm 0.0090 6-A' -489.125647 -490.430968 69.4% 4.96 eV 250 nm 0.0391 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 18 0 Ras2 Orbitals | 4 10 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active (see Figure 10) Orbitals 1-10 of Symmetry A" are active (see Figure 10) A'-States: ---------- root 1: (ground state) CASSCF energy: -489.352924 CASPT2 energy: -490.619194 Reference weight: 0.695 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.82987 0.68869 73992 2200 22222ud000 -0.18016 0.03246 Natural orbitals and occupation numbers for root 1 sym 1: 1.974868 1.943847 0.057159 0.025518 sym 2: 1.971716 1.997059 1.960396 1.904816 1.912101 1.733054 0.299976 0.097989 0.085536 0.035964 root 2: CASSCF energy: -489.207724 CASPT2 energy: -490.480913 Reference weight: 0.573 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 -0.35644 0.12705 73994 2200 222u22d000 -0.33846 0.11456 74001 2200 22222u0d00 0.46616 0.21731 Natural orbitals and occupation numbers for root 2 sym 1: 1.972065 1.942963 0.057832 0.028610 sym 2: 1.973257 1.995720 1.918040 1.854826 1.446640 1.276916 0.815302 0.520004 0.129565 0.068260 root 3: CASSCF energy: -489.206009 CASPT2 energy: -490.475284 Reference weight: 0.650 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73994 2200 222u22d000 0.37021 0.13706 73995 2200 2222202000 -0.45611 0.20804 Natural orbitals and occupation numbers for root 3 sym 1: 1.971707 1.942070 0.058840 0.028861 sym 2: 1.967510 1.995438 1.923229 1.524429 1.877634 1.071185 1.123588 0.122389 0.330765 0.062352 root 4: CASSCF energy: -489.183192 CASPT2 energy: -490.511776 Reference weight: 0.659 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.25646 0.06577 73992 2200 22222ud000 0.73201 0.53584 Natural orbitals and occupation numbers for root 4 sym 1: 1.972513 1.941752 0.059775 0.028193 sym 2: 1.946384 1.986132 1.966994 1.872006 1.887853 1.395489 0.683924 0.128624 0.092720 0.037640 root 5: CASSCF energy: -489.138197 CASPT2 energy: -490.443425 Reference weight: 0.547 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 0.45142 0.20378 74001 2200 22222u0d00 0.37699 0.14212 Natural orbitals and occupation numbers for root 5 sym 1: 1.972744 1.942419 0.058508 0.027854 sym 2: 1.960680 1.990154 1.898492 1.863668 1.499286 1.261648 0.862058 0.483995 0.114514 0.063980 root 6: CASSCF energy: -489.125647 CASPT2 energy: -490.432613 Reference weight: 0.391 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 74003 2200 222u220d00 -0.48700 0.23717 Natural orbitals and occupation numbers for root 6 sym 1: 1.974693 1.940300 0.060854 0.025560 sym 2: 1.951169 1.989859 1.889697 1.440530 1.607718 1.425226 0.592746 0.733195 0.282024 0.086429 A"-States: ---------- root 1: CASSCF energy: -489.248957 CASPT2 energy: -490.528446 Reference weight: 0.693 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 323681 2u00 222222d000 0.91305 0.83365 Natural orbitals and occupation numbers for root 1 sym 1: 1.974554 1.000020 0.007014 0.025735 sym 2: 1.997920 1.991266 1.956766 1.999971 1.900909 1.896454 1.001263 0.102428 0.105499 0.040200 ============================ E2. Geometry: B3LYP/6-31G(d) ---------------------------- Active space: 16 electrons in 14 Orbitals (12/10 a" + 4/4 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-6 of A' are averaged Summary of the calculation (Description of the excited states is presented in Table S5, dependence of energy and reference weight of CASPT2 states on level shift - Table S6): CAS(16/14) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.303837 -490.632642 67.7% 4-A' -489.144498 -490.540052 63.7% 2.52 eV 492 nm 0.3356 1-A" -489.252005 -490.537592 69.1% 2.59 eV 479 nm 0.0000 2-A' -489.170642 -490.501941 63.3% 3.56 eV 349 nm 0.0201 3-A' -489.169505 -490.498361 65.0% 3.65 eV 339 nm 0.0110 5-A' -489.100142 -490.468144 56.0% 4.48 eV 277 nm 0.0150 6-A' -489.087337 -490.448990 59.7% 5.00 eV 248 nm 0.0410 2-A" -489.145033 -490.441109 27.7% 5.21 eV 238 nm 0.0000 --------------------------------------------------------------------------- CAS(16/14) + CASPT2 (0.15 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.352924 -490.628551 70.4% 4-A' -489.183192 -490.533671 67.8% 2.58 eV 480 nm 0.3438 1-A" -489.252005 -490.533903 71.7% 2.58 eV 481 nm 0.0000 3-A' -489.206009 -490.495120 69.8% 3.63 eV 341 nm 0.0107 2-A' -489.207724 -490.497912 69.5% 3.56 eV 349 nm 0.0201 5-A' -489.138197 -490.458942 68.4% 4.62 eV 269 nm 0.0154 6-A' -489.125647 -490.443611 68.5% 5.03 eV 246 nm 0.0418 2-A" -489.145033 -490.440298 70.8% 5.12 eV 242 nm 0.0000 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 18 0 Ras2 Orbitals | 4 10 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active. Orbitals 1-10 of Symmetry A" are active. A'-States: ---------- root 1: (ground state) CASSCF energy: -489.303837 CASPT2 energy: -490.632642 Reference weight: 0.677 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.80319 0.64511 73992 2200 22222ud000 -0.27796 0.07726 73995 2200 2222202000 -0.29913 0.08948 Natural orbitals and occupation numbers for root 1 sym 1: 1.977181 1.981842 0.018471 0.023057 sym 2: 1.994223 1.992520 1.959982 1.912045 1.906110 1.642203 0.372156 0.096713 0.086800 0.036697 root 2: CASSCF energy: -489.170642 CASPT2 energy: -490.501941 Reference weight: 0.633 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73994 2200 222u22d000 0.31748 0.10079 73995 2200 2222202000 -0.36579 0.13380 74001 2200 22222u0d00 -0.38834 0.15081 Natural orbitals and occupation numbers for root 2 sym 1: 1.975123 1.981728 0.018591 0.025209 sym 2: 1.993456 1.990741 1.917665 1.541975 1.887422 1.146026 0.955250 0.390377 0.108902 0.067533 root 3: CASSCF energy: -489.169505 CASPT2 energy: -490.498361 Reference weight: 0.650 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 -0.34764 0.12085 73996 2200 2222ud2000 0.31927 0.10194 74001 2200 22222u0d00 -0.38392 0.14740 Natural orbitals and occupation numbers for root 3 sym 1: 1.975487 1.981711 0.018603 0.024803 sym 2: 1.993050 1.993731 1.919196 1.893206 1.457154 1.162618 0.944884 0.454967 0.113802 0.066787 root 4: CASSCF energy: -489.144498 CASPT2 energy: -490.540052 Reference weight: 0.637 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.36357 0.13219 73992 2200 22222ud000 0.66907 0.44765 73997 2200 222u2d2000 -0.35038 0.12277 Natural orbitals and occupation numbers for root 4 sym 1: 1.975697 1.980903 0.019312 0.024552 sym 2: 1.988450 1.976328 1.944054 1.858839 1.886468 1.357939 0.734376 0.126985 0.087777 0.038320 root 5: CASSCF energy: -489.100142 CASPT2 energy: -490.468144 Reference weight: 0.560 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 -0.35660 0.12716 74001 2200 22222u0d00 0.37343 0.13945 74005 2200 2222udud00 -0.36837 0.13569 Natural orbitals and occupation numbers for root 5 sym 1: 1.975826 1.981456 0.018820 0.024471 sym 2: 1.990153 1.986268 1.902204 1.843805 1.528570 1.192792 0.883155 0.486750 0.119064 0.066665 root 6: CASSCF energy: -489.087337 CASPT2 energy: -490.448990 Reference weight: 0.597 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 0.32602 0.10629 74001 2200 22222u0d00 -0.35915 0.12899 74005 2200 2222udud00 -0.34671 0.12021 Natural orbitals and occupation numbers for root 6 sym 1: 1.975247 1.981313 0.018947 0.025120 sym 2: 1.993336 1.984757 1.909912 1.847880 1.517647 1.192105 0.847826 0.493566 0.132664 0.079678 A"-States: ---------- root 1: CASSCF energy: -489.252005 CASPT2 energy: -490.537592 Reference weight: 0.691 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 323681 2u00 222222d000 0.90560 0.82010 Natural orbitals and occupation numbers for root 1 sym 1: 1.977350 1.000018 0.006964 0.022970 sym 2: 1.998228 1.991109 1.954473 1.999974 1.900494 1.890570 1.001740 0.102862 0.111066 0.042182 root 2: CASSCF energy: -489.145033 CASPT2 energy: -490.441109 Reference weight: 0.277 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 323682 2u00 22222d2000 0.68224 0.46545 323721 2u00 22222200d0 0.58231 0.33909 Natural orbitals and occupation numbers for root 2 sym 1: 1.977988 1.000033 0.006703 0.022215 sym 2: 1.996960 1.990761 1.927494 1.999933 1.891384 1.388927 1.132640 0.113491 0.488736 0.062735 F.) Result of CASSCF/CASPT2-calculation on trans-p-aminophenylnitrosooxide Note: The states are ordered according to their CASSCF energies, not according to their occurrence in the experimental spectra or the CASPT2 energies, as in the tables of the paper. ===================================== F1. Geometry: CASSCF(12,12)/6-31G(d) ------------------------------------- Active space: 16 electrons in 14 Orbitals (12/10 a" + 4/4 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-6 of A' are averaged Summary of the calculation (Description of the excited states is presented in Table 3, dependence of energy and reference weight of CASPT2 states on level shift - Table S7): CAS(16/14) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.331104 -490.624626 68.5% 1-A" -489.261990 -490.535546 69.4% 2.42 eV 511 nm 0.0000 4-A' -489.170108 -490.524977 64.8% 2.71 eV 457 nm 0.4400 3-A' -489.191622 -490.498810 64.4% 3.42 eV 362 nm 0.0280 2-A' -489.195033 -490.489627 65.6% 3.67 eV 338 nm 0.0100 6-A' -489.115814 -490.439511 15.3% 5.04 eV 246 nm 0.0031 5-A' -489.124502 -490.438708 52.6% 5.06 eV 245 nm 0.0021 --------------------------------------------------------------------------- CAS(16/14) + CASPT2 (0.15 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.352924 -490.620685 71.1% 4-A' -489.183192 -490.519071 68.6% 2.77 eV 448 nm 0.4486 3-A' -489.206009 -490.492988 70.0% 3.48 eV 357 nm 0.0288 2-A' -489.207724 -490.487884 70.3% 3.61 eV 343 nm 0.0101 6-A' -489.125647 -490.437407 68.2% 4.99 eV 249 nm 0.0030 5-A' -489.138197 -490.433960 69.5% 5.08 eV 244 nm 0.0021 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 18 0 Ras2 Orbitals | 4 10 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active. Orbitals 1-10 of Symmetry A" are active. A'-States: ---------- root 1: (ground state) CASSCF energy: -489.331104 CASPT2 energy: -490.624626 Reference weight: 0.685 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.79270 0.62838 73992 2200 22222ud000 -0.32143 0.10331 Natural orbitals and occupation numbers for root 1 sym 1: 1.974939 1.971661 0.030151 0.023885 sym 2: 1.983879 1.997485 1.960989 1.907247 1.902303 1.681198 0.335374 0.101252 0.092611 0.037026 root 2: CASSCF energy: -489.195033 CASPT2 energy: -490.489627 Reference weight: 0.656 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73994 2200 222u22d000 -0.33319 0.11102 73995 2200 2222202000 -0.44032 0.19388 74041 2200 22222u00d0 0.39218 0.15381 Natural orbitals and occupation numbers for root 2 sym 1: 1.974633 1.971060 0.030634 0.024463 sym 2: 1.987177 1.995726 1.924707 1.572352 1.875311 0.925303 1.173334 0.131926 0.351131 0.062243 root 3: CASSCF energy: -489.191622 CASPT2 energy: -490.498810 Reference weight: 0.644 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 74001 2200 22222u0d00 0.54029 0.29191 Natural orbitals and occupation numbers for root 3 sym 1: 1.973989 1.970675 0.030911 0.025215 sym 2: 1.984931 1.995199 1.920533 1.831695 1.560306 1.179051 0.813568 0.510366 0.134472 0.069088 root 4: CASSCF energy: -489.170108 CASPT2 energy: -490.524977 Reference weight: 0.648 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 -0.39369 0.15499 73992 2200 22222ud000 -0.70176 0.49247 Natural orbitals and occupation numbers for root 4 sym 1: 1.972375 1.967265 0.033825 0.027221 sym 2: 1.971840 1.989657 1.951504 1.888819 1.912750 1.613612 0.445144 0.111783 0.077880 0.036326 root 5: CASSCF energy: -489.124502 CASPT2 energy: -490.438708 Reference weight: 0.526 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 74005 2200 2222udud00 -0.34732 0.12063 74006 2200 222u2dud00 -0.32922 0.10839 Natural orbitals and occupation numbers for root 5 sym 1: 1.974623 1.972282 0.029716 0.024094 sym 2: 1.985567 1.991299 1.862617 1.467017 1.817881 1.104657 0.965582 0.568276 0.150244 0.086144 root 6: CASSCF energy: -489.115814 CASPT2 energy: -490.439511 Reference weight: 0.153 dominant CSFs: Symmetry: A' A" 74003 2200 222u220d00 -0.37371 0.13966 74004 2200 222220ud00 -0.33176 0.11006 Natural orbitals and occupation numbers for root 6 sym 1: 1.975244 1.971993 0.029971 0.023295 sym 2: 1.981892 1.992730 1.877367 1.666087 1.414729 1.247443 0.626459 0.813400 0.292638 0.086751 A"-States: ---------- root 1: CASSCF energy: -489.261990 CASPT2 energy: -490.535546 Reference weight: 0.694 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 323681 2u00 222222d000 0.91600 0.83905 Natural orbitals and occupation numbers for root 1 sym 1: 1.974779 1.000033 0.007048 0.025457 sym 2: 1.997950 1.957902 1.991336 1.999986 1.901624 1.897238 1.001266 0.102011 0.104113 0.039256 ===================================== F2. Geometry: B3LYP/6-31G(d) ------------------------------------- Active space: 16 electrons in 14 Orbitals (12/10 a" + 4/4 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-6 of A' are averaged Summary of the calculation (Description of the excited states is presented in Table S8, dependence of energy and reference weight of CASPT2 states on level shift - Table S9): CAS(16/14) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.336251 -490.630543 68.4% 1-A" -489.266815 -490.542295 69.3% 2.40 eV 516 nm 0.0000 4-A' -489.177178 -490.526582 65.3% 2.83 eV 438 nm 0.4643 3-A' -489.203901 -490.507948 66.2% 3.34 eV 372 nm 0.0220 2-A' -489.208017 -490.505492 62.0% 3.40 eV 364 nm 0.0170 6-A' -489.123150 -490.473056 64.1% 4.29 eV 289 nm 0.0800 5-A' -489.134654 -490.464089 7.8% 4.53 eV 274 nm 0.0076 --------------------------------------------------------------------------- CAS(16/14) + CASPT2 (0.15 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.336251 -490.626605 71.1% 4-A' -489.177178 -490.521033 68.9% 2.87 eV 432 nm 0.4715 3-A' -489.203901 -490.502761 70.2% 3.37 eV 368 nm 0.0221 2-A' -489.208017 -490.505028 70.3% 3.31 eV 375 nm 0.0166 6-A' -489.123150 -490.466952 68.8% 4.34 eV 285 nm 0.0815 5-A' -489.134654 -490.446501 69.3% 4.90 eV 253 nm 0.0082 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 18 0 Ras2 Orbitals | 4 10 Frozen Orbitals | 10 0 Orbitals 29-32 of Symmetry A' are active. Orbitals 1-10 of Symmetry A" are active. A'-States: ---------- root 1: (ground state) CASSCF energy: -489.336251 CASPT2 energy: -490.630543 Reference weight: 0.684 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 0.78198 0.61150 73992 2200 22222ud000 0.31965 0.10218 73995 2200 2222202000 -0.29006 0.08413 Natural orbitals and occupation numbers for root 1 sym 1: 1.976644 1.968422 0.032984 0.022663 sym 2: 1.984784 1.997012 1.960408 1.908888 1.903881 1.634478 0.380874 0.099645 0.091992 0.037324 root 2: CASSCF energy: -489.208017 CASPT2 energy: -490.505492 Reference weight: 0.620 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73994 2200 222u22d000 0.42323 0.17912 73995 2200 2222202000 -0.46846 0.21945 73997 2200 222u2d2000 0.36061 0.13004 74041 2200 22222u00d0 -0.40652 0.16526 Natural orbitals and occupation numbers for root 2 sym 1: 1.974941 1.969871 0.031972 0.024008 sym 2: 1.986321 1.995310 1.927158 1.574777 1.889516 0.874171 1.236430 0.118047 0.338586 0.058890 root 3: CASSCF energy: -489.203901 CASPT2 energy: -490.507948 Reference weight: 0.662 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73993 2200 2222u2d000 0.39993 0.15995 73996 2200 2222ud2000 0.38264 0.14642 74001 2200 22222u0d00 0.54130 0.29301 Natural orbitals and occupation numbers for root 3 sym 1: 1.974315 1.969646 0.032017 0.024854 sym 2: 1.987473 1.995237 1.925752 1.853522 1.517106 1.164800 0.835471 0.530467 0.124020 0.065320 root 4: CASSCF energy: -489.177178 CASPT2 energy: -490.526582 Reference weight: 0.653 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 73991 2200 2222220000 -0.40834 0.16674 73992 2200 22222ud000 0.69611 0.48457 Natural orbitals and occupation numbers for root 4 sym 1: 1.974496 1.963500 0.037545 0.025257 sym 2: 1.973388 1.988517 1.951067 1.918720 1.891210 1.637058 0.421070 0.104889 0.076987 0.036299 root 5: CASSCF energy: -489.134654 CASPT2 energy: -490.464089 Reference weight: 0.078 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 74005 2200 2222udud00 -0.48810 0.23824 Natural orbitals and occupation numbers for root 5 sym 1: 1.974998 1.970334 0.031479 0.024016 sym 2: 1.986986 1.990867 1.799699 1.874715 1.498431 1.166608 0.924705 0.526720 0.138826 0.091615 root 6: CASSCF energy: -489.123150 CASPT2 energy: -490.473056 Reference weight: 0.641 dominant CSFs: Symmetry: A' A" 73993 2200 2222u2d000 0.45323 0.20542 74001 2200 22222u0d00 -0.43315 0.18762 Natural orbitals and occupation numbers for root 6 sym 1: 1.974638 1.970006 0.031829 0.024424 sym 2: 1.984131 1.988213 1.938405 1.851172 1.526075 1.187230 0.830514 0.550260 0.090577 0.052526 A"-States: ---------- root 1: CASSCF energy: -489.266815 CASPT2 energy: -490.542295 Reference weight: 0.693 dominant CSFs: Symmetry: A' A" conf/sym 1111 2222222222 Coeff Weight 323681 2u00 222222d000 0.91249 0.83263 Natural orbitals and occupation numbers for root 1 sym 1: 1.976912 1.000031 0.007030 0.023338 sym 2: 1.998320 1.991118 1.955940 1.895625 1.901308 1.999988 1.002006 0.102025 0.105686 0.040673 G.) Result of CASSCF/CASPT2-calculation on p-aminophenyldioxaziridine Note: The states are ordered according to their CASSCF energies, not according to their occurrence in the experimental spectra or the CASPT2 energies, as in the tables of the paper. Geometry: B3lYP/6-31G(d), Cs-symmetry (planar NH2-group) Active space: 12 electrons in 12 Orbitals (10/10 a" + 2/2 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-4 of A' are averaged State averaging: States 1-2 of A" are averaged Summary of the calculation (Description of the excited states is presented in Table S10, dependence of energy and reference weight of CASPT2 states on level shift - Table S11): CAS(12/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.292479 -490.537678 69.7% 3-A' -489.065833 -490.405533 3.1% 3.60 eV 345 nm 0.0525 2-A' -489.118914 -490.381358 49.8% 4.25 eV 291 nm 0.0040 4-A' -489.044948 -490.290141 8.1% 6.74 eV 184 nm 0.2268 2-A" -489.978120 -490.354769 64.0% 4.98 eV 249 nm 0.0089 1-A" -489.027880 -490.334763 67.4% 5.52 eV 225 nm 0.0120 --------------------------------------------------------------------------- CAS(12/12) + CASPT2 (0.25 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w _E (in eV) _E (in nm) osc --------------------------------------------------------------------------- 1-A' -489.292479 -490.528757 73.6% 3-A' -489.065833 -490.383927 70.7% 3.94 eV 315 nm 0.0581 2-A' -489.118914 -490.374031 72.4% 4.21 eV 294 nm 0.0039 4-A' -489.044948 -490.356055 70.6% 4.70 eV 264 nm 0.1582 2-A" -489.978120 -490.341094 70.1% 5.11 eV 243 nm 0.0090 1-A" -489.027880 -490.324314 72.0% 5.56 eV 223 nm 0.0124 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 17 3 Ras2 Orbitals | 2 10 Frozen Orbitals | 10 0 Orbitals 28-29 of Symmetry A' are active (see Figure S2). Orbitals 4-13 of Symmetry A" are active (see Figure S2). A'-States: ---------- root 1: (ground state) CASSCF energy: -489.292479 CASPT2 energy: -490.537678 Reference weight: 0.697 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 236 20 2222200000 0.90559 0.82010 Natural orbitals and occupation numbers for root 1 sym 1: 1.912377 0.016131 sym 2: 1.963062 1.996932 1.944760 1.903346 1.904506 0.100740 0.098915 0.039573 0.088115 0.031544 root 2: CASSCF energy: -489.118914 CASPT2 energy: -490.381358 Reference weight: 0.498 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 239 20 2222u0d000 0.64388 0.41458 1034 20 222u2d0000 0.42598 0.18146 Natural orbitals and occupation numbers for root 2 sym 1: 1.912456 0.016215 sym 2: 1.869988 1.996059 1.945483 1.538974 1.357953 0.474475 0.656297 0.105940 0.090181 0.035979 root 3: CASSCF energy: -489.065833 CASPT2 energy: -490.405533 Reference weight: 0.031 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 237 20 2222ud0000 -0.53957 0.29114 2364 20 2u222d0000 0.56476 0.31895 2384 20 2u222000d0 0.34330 0.11786 Natural orbitals and occupation numbers for root 3 sym 1: 1.940650 0.026759 sym 2: 1.958577 1.098903 1.944128 1.894857 1.857973 0.923855 0.111335 0.064708 0.143236 0.035019 root 4: CASSCF energy: -489.044948 CASPT2 energy: -490.290141 Reference weight: 0.081 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 237 20 2222ud0000 -0.61583 0.37925 2364 20 2u222d0000 -0.42886 0.18392 Natural orbitals and occupation numbers for root 4 sym 1: 1.924455 0.021494 sym 2: 1.936208 1.859276 1.952276 1.802998 1.178733 0.842885 0.212481 0.055392 0.175854 0.037949 A"-States: ---------- root 1: CASSCF energy: -489.027880 CASPT2 energy: -490.334763 Reference weight: 0.674 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 1 2u 2222d00000 0.89440 0.79995 Natural orbitals and occupation numbers for root 1 sym 1: 1.997541 0.999999 sym 2: 1.949354 1.898052 1.956878 1.886944 1.004810 0.048357 0.109909 0.038968 0.104367 0.004821 root 2: CASSCF energy: -488.978120 CASPT2 energy: -490.354769 Reference weight: 0.640 dominant CSFs: Symmetry: A' A" conf/sym 11 2222222222 Coeff Weight 2541 u0 22222d0000 -0.91497 0.83716 Natural orbitals and occupation numbers for root 2 sym 1: 1.000002 0.000124 sym 2: 1.981159 1.959389 1.995282 1.904230 1.897048 1.002125 0.101649 0.039529 0.103805 0.015657