Matrix isolation and computational study of the photochemistry of 1,3,2,4-benzodithiadiazine Nina P. Gritsan, Elena A. Pritchina, Thomas Bally, Alexander Yu. Makarov and Andrey V. Zibarev ------------------------------------------------------------------- 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. 1,3,2,4-benzodithiadiazine (1) -------------------------------------------------- E(RB3LYP) = -1136.838273 nuclear repulsion energy 656.861064 Zero-point correction= 0.090984 Thermal correction to Energy= 0.098870 Thermal correction to Enthalpy= 0.099814 Thermal correction to Gibbs Free Energy= 0.057430 6 0.465595 -0.775495 -0.155217 6 0.474264 0.631749 -0.045086 6 1.667475 1.311041 0.153213 6 2.887042 0.613386 0.173616 6 2.892049 -0.768934 0.034208 6 1.683629 -1.459884 -0.111066 1 1.659393 2.392322 0.266280 1 3.817011 1.161412 0.292290 1 3.828119 -1.319521 0.044579 1 1.658558 -2.542271 -0.190292 7 -2.297049 0.561540 0.275369 7 -0.702933 -1.565166 -0.223746 16 -1.033473 1.623782 -0.219730 16 -2.115498 -0.997391 0.152716 ================================================== A2. thyazil (3) 1-A' -------------------------------------------------- E(RB3LYP) = -1136.782578 nuclear repulsion energy 655.566458 Zero-point correction= 0.090411 Thermal correction to Energy= 0.098732 Thermal correction to Enthalpy= 0.099676 Thermal correction to Gibbs Free Energy= 0.056580 6 0.000000 0.903943 0.000000 6 0.889868 -0.205492 0.000000 6 2.273752 -0.008221 0.000000 6 2.779200 1.288990 0.000000 6 1.910767 2.388652 0.000000 6 0.534714 2.204583 0.000000 1 2.946300 -0.860135 0.000000 1 3.853986 1.443086 0.000000 1 2.313863 3.397067 0.000000 1 -0.151108 3.044790 0.000000 7 -1.373824 0.722742 0.000000 7 -3.155893 -1.459376 0.000000 16 0.115338 -1.788485 0.000000 16 -1.839390 -0.792959 0.000000 ================================================== A3. ortho-quinoidal acyclic product (6) -------------------------------------------------- E(RB3LYP) = -1136.780318 nuclear repulsion energy 624.453268 Zero-point correction= 0.088774 Thermal correction to Energy= 0.097939 Thermal correction to Enthalpy= 0.098883 Thermal correction to Gibbs Free Energy= 0.053256 6 -0.392158 -0.731024 -0.121007 6 -0.695838 0.742808 -0.042218 6 -2.070118 1.120685 0.139716 6 -3.071544 0.193135 0.122440 6 -2.800304 -1.214462 -0.022419 6 -1.523582 -1.657609 -0.120871 1 -2.291754 2.177327 0.245282 1 -4.103698 0.519092 0.220196 1 -3.630921 -1.914120 -0.030135 1 -1.276968 -2.710498 -0.204289 7 0.794048 -1.253720 -0.175086 7 3.522679 -0.597941 -0.355504 16 2.265796 -0.377044 0.390537 16 0.509673 1.887583 -0.156211 ================================================== A4. ortho-quinoidal acyclic product (7) -------------------------------------------------- E(RB3LYP) = -1136.776709 nuclear repulsion energy 609.416492 Zero-point correction= 0.088815 Thermal correction to Energy= 0.098129 Thermal correction to Enthalpy= 0.099073 Thermal correction to Gibbs Free Energy= 0.052108 6 0.039713 0.038776 -0.001177 6 -1.396948 -0.458856 -0.038066 6 -2.437531 0.538923 -0.172263 6 -2.157292 1.866413 -0.100851 6 -0.802146 2.334128 0.085038 6 0.247461 1.477926 0.149600 7 0.968378 -0.856345 -0.155926 16 2.718610 -0.580901 -0.108603 7 3.288628 0.774098 0.169924 16 -1.779654 -2.058314 0.132517 1 -3.456208 0.181086 -0.278927 1 -2.959094 2.596958 -0.164234 1 -0.628534 3.404381 0.161351 1 1.261965 1.836890 0.267516 ================================================== A5. thiazabenzocyclobutene (8a) -------------------------------------------------- E(RB3LYP) = -1136.784530 nuclear repulsion energy 638.829736 Zero-point correction= 0.089542 Thermal correction to Energy= 0.098310 Thermal correction to Enthalpy= 0.099254 Thermal correction to Gibbs Free Energy= 0.054470 6 -0.303316 -0.267338 0.271569 6 -1.100623 0.837677 -0.042835 6 -2.456977 0.739598 -0.283119 6 -2.986556 -0.562040 -0.222626 6 -2.185247 -1.674019 0.068095 6 -0.810605 -1.558133 0.330916 1 -3.081700 1.596070 -0.515464 1 -4.046690 -0.707078 -0.409747 1 -2.642225 -2.658952 0.097229 1 -0.193301 -2.418355 0.559827 7 0.951980 0.368170 0.475500 7 2.578117 -1.698291 -0.309549 16 2.512950 -0.226581 -0.152240 16 0.256624 2.001874 0.050647 ================================================== A6. thiazabenzocyclobutene (8b) -------------------------------------------------- E(RB3LYP) = -1136.784068 nuclear repulsion energy 636.522229 Zero-point correction= 0.089451 Thermal correction to Energy= 0.098240 Thermal correction to Enthalpy= 0.099184 Thermal correction to Gibbs Free Energy= 0.054305 6 -0.478657 -0.411184 0.226990 6 -1.017570 0.853882 -0.023154 6 -2.363144 1.058185 -0.258770 6 -3.159956 -0.101098 -0.269060 6 -2.618591 -1.370948 -0.034035 6 -1.252416 -1.561191 0.234472 1 -2.789927 2.040014 -0.437069 1 -4.224247 -0.006622 -0.464218 1 -3.275029 -2.236143 -0.049319 1 -0.846635 -2.546708 0.439558 7 0.879706 -0.052837 0.484694 7 3.477176 -0.040532 -0.423337 16 0.554886 1.696002 0.162672 16 2.318843 -0.908679 -0.111241 B.) B3LYP/6-311G(df,p) optimized geometries, energies, and thermal corrections of all the stationary points discussed in this work ================================================== B1. 1,3,2,4-benzodithiadiazine (1) -------------------------------------------------- E(RB3LYP) = -1136.993275 nuclear repulsion energy 659.187513 Zero-point correction= 0.090690 Thermal correction to Energy= 0.098566 Thermal correction to Enthalpy= 0.099510 Thermal correction to Gibbs Free Energy= 0.057148 6 0.465384 -0.774617 -0.153107 6 0.476164 0.628016 -0.046061 6 1.663952 1.305043 0.150653 6 2.879600 0.610248 0.169869 6 2.883643 -0.766845 0.033073 6 1.678948 -1.455611 -0.108811 1 1.655627 2.383845 0.263197 1 3.807413 1.156770 0.287670 1 3.817464 -1.316076 0.042810 1 1.653294 -2.535706 -0.185747 7 -2.283308 0.556805 0.264084 7 -0.704822 -1.556206 -0.221163 16 -1.032073 1.620399 -0.213444 16 -2.111867 -0.993550 0.152065 ================================================== B2. thyazil (3) 1-A' -------------------------------------------------- E(RB3LYP) = -1136.937559 nuclear repulsion energy 657.700479 Zero-point correction= 0.090086 Thermal correction to Energy= 0.098392 Thermal correction to Enthalpy= 0.099336 Thermal correction to Gibbs Free Energy= 0.056324 6 0.000000 0.901017 0.000000 6 0.885970 -0.204278 0.000000 6 2.265021 -0.009988 0.000000 6 2.771344 1.280982 0.000000 6 1.907435 2.377976 0.000000 6 0.536457 2.195804 0.000000 1 2.934959 -0.860725 0.000000 1 3.843707 1.433083 0.000000 1 2.311177 3.383283 0.000000 1 -0.147473 3.034459 0.000000 7 -1.368865 0.719497 0.000000 7 -3.146691 -1.447434 0.000000 16 -1.836738 -0.786149 0.000000 16 0.116060 -1.785327 0.000000 ================================================== B3. ortho-quinoidal acyclic product (6) -------------------------------------------------- E(RB3LYP) = -1136.929864 nuclear repulsion energy 628.846965 Zero-point correction= 0.088395 Thermal correction to Energy= 0.097562 Thermal correction to Enthalpy= 0.098506 Thermal correction to Gibbs Free Energy= 0.052843 6 -0.396302 -0.728052 -0.141747 6 -0.687095 0.738708 -0.054245 6 -2.049592 1.127320 0.147280 6 -3.054088 0.211042 0.136650 6 -2.794148 -1.192983 -0.011197 6 -1.526043 -1.644136 -0.119571 1 -2.262058 2.182552 0.260415 1 -4.080465 0.543125 0.245014 1 -3.627216 -1.885786 -0.012585 1 -1.287290 -2.696239 -0.204172 7 0.789982 -1.239756 -0.216331 7 3.512759 -0.586259 -0.298283 16 2.224818 -0.390196 0.383802 16 0.536524 1.863137 -0.160640 ================================================== B4. ortho-quinoidal acyclic product (7) -------------------------------------------------- E(RB3LYP) = -1136.927994 nuclear repulsion energy 611.871995 Zero-point correction= 0.088528 Thermal correction to Energy= 0.097800 Thermal correction to Enthalpy= 0.098744 Thermal correction to Gibbs Free Energy= 0.052101 6 0.040998 0.040118 -0.004027 6 -1.388809 -0.462765 -0.049743 6 -2.426758 0.526117 -0.221905 6 -2.155307 1.847693 -0.129814 6 -0.813301 2.319022 0.110993 6 0.234912 1.472399 0.192934 1 -3.437781 0.165529 -0.362062 1 -2.955940 2.573686 -0.213140 1 -0.650222 3.386312 0.211978 1 1.242575 1.830791 0.345233 16 2.709567 -0.567992 -0.140202 16 -1.759906 -2.053321 0.170979 7 0.971087 -0.832854 -0.201269 7 3.265540 0.765594 0.220544 ================================================== B5. thiazabenzocyclobutene (8a) -------------------------------------------------- E(RB3LYP) = -1136.939039 nuclear repulsion energy 640.382105 Zero-point correction= 0.089396 Thermal correction to Energy= 0.098156 Thermal correction to Enthalpy= 0.099101 Thermal correction to Gibbs Free Energy= 0.054226 6 -0.300898 -0.271837 0.204762 6 -1.122836 0.829458 -0.034238 6 -2.482249 0.721939 -0.212756 6 -2.993504 -0.582362 -0.166944 6 -2.170070 -1.688805 0.050085 6 -0.790387 -1.564816 0.249317 1 -3.125521 1.574986 -0.387178 1 -4.057056 -0.734400 -0.307458 1 -2.613813 -2.677058 0.070966 1 -0.152190 -2.420299 0.417569 7 0.945081 0.374647 0.362949 7 2.617990 -1.675433 -0.234463 16 2.535028 -0.207994 -0.114418 16 0.225393 2.001795 0.037252 ================================================== B6. thiazabenzocyclobutene (8b) -------------------------------------------------- E(RB3LYP) = -1136.938752 nuclear repulsion energy 638.455662 Zero-point correction= 0.089269 Thermal correction to Energy= 0.098045 Thermal correction to Enthalpy= 0.098989 Thermal correction to Gibbs Free Energy= 0.054061 6 0.476731 -0.411327 0.186750 6 1.029706 0.850657 -0.021949 6 2.377062 1.049210 -0.216226 6 3.165000 -0.110126 -0.223976 6 2.611423 -1.375910 -0.028365 6 1.241464 -1.561088 0.195931 1 2.813819 2.028859 -0.363056 1 4.232394 -0.019436 -0.385975 1 3.261692 -2.242442 -0.039638 1 0.825809 -2.545622 0.369261 7 -0.878240 -0.046656 0.405021 7 -3.493558 -0.035054 -0.353638 16 -0.541807 1.694621 0.136046 16 -2.329408 -0.900739 -0.091876 C.) Results of CASSCF/CASPT2-calculations 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. 1,3,2,4-benzodithiadiazine (1) ----------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-11 are averaged. Summary of the calculation (Description of the excited states is presented in Table S1): CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.537757 -1334.840836 65.8% 2A -1333.431514 -1334.778687 63.7% 1.69 eV 733 nm 0.0232 3A -1333.384357 -1334.726609 61.4% 3.11 eV 399 nm 0.0609 4A -1333.377972 -1334.723052 61.4% 3.21 eV 387 nm 0.0013 5A -1333.353873 -1334.689692 49.6% 4.11 eV 301 nm 0.0090 6A -1333.329796 -1334.681958 12.1% 4.32 eV 287 nm 0.0055 7A -1333.317304 -1334.686998 44.8% 4.19 eV 296 nm 0.3351 8A -1333.310321 -1334.627290 0.0% 5.81 eV 213 nm 0.1048 9A -1333.302202 -1334.656386 0.0% 5.02 eV 247 nm 0.0360 10A -1333.294568 -1334.668368 0.3% 4.69 eV 264 nm 0.0128 11A -1333.290476 -1334.691288 0.0% 4.07 eV 305 nm 0.0023 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.537757 -1334.828778 70.6% 2A -1333.431514 -1334.764341 69.2% 1.75 eV 707 nm 0.0240 3A -1333.384357 -1334.710324 69.0% 3.22 eV 385 nm 0.0631 4A -1333.377972 -1334.707185 68.9% 3.31 eV 375 nm 0.0014 5A -1333.353873 -1334.671926 69.3% 4.27 eV 290 nm 0.0093 6A -1333.329796 -1334.680467 67.4% 4.04 eV 307 nm 0.0051 7A -1333.317304 -1334.671085 67.9% 4.29 eV 289 nm 0.3435 8A -1333.310321 -1334.676178 66.5% 4.15 eV 299 nm 0.0749 9A -1333.302202 -1334.661692 67.2% 4.55 eV 273 nm 0.0326 10A -1333.294568 -1334.642604 67.9% 5.07 eV 245 nm 0.0138 11A -1333.290476 -1334.647882 67.3% 4.92 eV 252 nm 0.0028 --------------------------------------------------------------------------- | A ------------------+---------- Inactive Orbitals | 25 Ras2 Orbitals | 12 Frozen Orbitals | 10 Orbitals 36-47 of Symmetry A are active States: ---------- root 1: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1 222222220000 0.90294 0.81531 Natural orbitals and occupation numbers for root 1 sym 1: 1.998061 1.993336 1.968288 1.987980 1.990226 1.942909 1.936263 1.810767 0.206128 0.066890 0.063911 0.035239 root 2: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 0.84557 0.71498 Natural orbitals and occupation numbers for root 2 sym 1: 1.984995 1.989983 1.994433 1.960684 1.961650 1.964464 1.934523 1.085058 0.951769 0.062626 0.066355 0.043459 root 3: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 -0.42031 0.17666 4 222222202000 0.59370 0.35248 Natural orbitals and occupation numbers for root 3 sym 1: 1.975776 1.985811 1.984462 1.958306 1.927142 1.893518 1.620083 0.928920 1.362454 0.193219 0.117331 0.052979 root 4: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 0.45859 0.21031 4 222222202000 0.43535 0.18953 7 2222222u0d00 0.41522 0.17241 Natural orbitals and occupation numbers for root 4 sym 1: 1.965113 1.984455 1.996236 1.955757 1.963700 1.906055 1.567447 0.987588 1.186136 0.349677 0.094292 0.043544 root 5: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 316 2222u222d000 0.74197 0.55051 317 2222u22d2000 -0.32046 0.10269 Natural orbitals and occupation numbers for root 5 sym 1: 1.990533 1.992695 1.976940 1.986887 0.844910 1.895431 1.937714 1.833765 1.274224 0.072639 0.150481 0.043782 root 6: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 21 2222222u00d0 -0.42801 0.18319 106 22222u22d000 -0.41460 0.17189 Natural orbitals and occupation numbers for root 6 sym 1: 1.965535 1.977437 1.985093 1.949514 1.932533 1.630929 1.818354 1.249319 0.786285 0.092063 0.419012 0.193927 root 7: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 0.39419 0.15538 7 2222222u0d00 -0.42963 0.18458 526 222u2222d000 -0.33455 0.11192 Natural orbitals and occupation numbers for root 7 sym 1: 1.957216 1.979788 1.991192 1.853077 1.946262 1.927413 1.539114 1.342390 0.811214 0.412164 0.178993 0.061177 root 8: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 9 22222220ud00 -0.34952 0.12217 51 2222222u000d -0.40689 0.16556 Natural orbitals and occupation numbers for root 8 sym 1: 1.949271 1.994922 1.978582 1.922172 1.967333 1.668691 1.883144 1.054498 0.707278 0.399715 0.093113 0.381283 root 9: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 7 2222222u0d00 0.32537 0.10586 51 2222222u000d 0.37585 0.14127 526 222u2222d000 -0.38170 0.14569 Natural orbitals and occupation numbers for root 9 sym 1: 1.966834 1.993863 1.978761 1.790557 1.958180 1.880410 1.603694 1.283344 0.764619 0.397189 0.209910 0.172640 root 10: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 10 222222udud00 0.42234 0.17837 Natural orbitals and occupation numbers for root 10 sym 1: 1.947736 1.993328 1.977775 1.899475 1.958407 1.725502 1.372113 1.362589 0.908977 0.592227 0.206489 0.055381 root 11: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 9 22222220ud00 -0.38293 0.14664 106 22222u22d000 0.37133 0.13788 Natural orbitals and occupation numbers for root 11 sym 1: 1.897080 1.992986 1.973158 1.932849 1.962171 1.527675 1.787620 1.263221 0.940293 0.427359 0.212103 0.083485 =============================================== C2. thyazil (3) ----------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-8 symmetry A' are averaged. State averaging: States 1-5 symmetry A" are averaged. Summary of the calculation: CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A' -1333.472501 -1334.799166 64.8% 1A" -1333.391427 -1334.716711 64.2% 2.24 eV 553 nm 0.0000 2A" -1333.340318 -1334.683334 63.0% 3.15 eV 393 nm 0.0002 2A' -1333.322204 -1334.674991 35.3% 3.38 eV 367 nm 0.0102 3A" -1333.285110 -1334.636222 63.0% 4.43 eV 280 nm 0.0000 3A' -1333.284396 -1334.653384 59.0% 3.97 eV 313 nm 0.4400 4A' -1333.279255 -1334.660281 11.6% 3.78 eV 328 nm 0.0707 4A" -1333.272043 -1334.631438 19.4% 4.56 eV 272 nm 0.0035 5A" -1333.268127 -1334.622421 45.4% 4.81 eV 258 nm 0.0002 5A' -1333.263433 -1334.598900 63.2% 5.45 eV 228 nm 0.0333 6A' -1333.236017 -1334.629609 49.0% 4.61 eV 269 nm 0.1485 7A' -1333.217591 -1334.593122 33.6% 5.61 eV 221 nm 0.0197 8A' -1333.210246 -1334.577165 6.3% 6.04 eV 205 nm 0.0013 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A' -1333.472501 -1334.786154 69.9% 1A" -1333.391427 -1334.702768 69.6% 2.27 eV 546 nm 0.0000 2A" -1333.340318 -1334.667924 69.0% 3.22 eV 385 nm 0.0002 2A' -1333.322204 -1334.663282 68.7% 3.34 eV 371 nm 0.0101 3A" -1333.285110 -1334.620935 68.9% 4.50 eV 276 nm 0.0000 3A' -1333.284396 -1334.636521 68.0% 4.07 eV 304 nm 0.4517 4A' -1333.279255 -1334.637911 67.6% 4.03 eV 307 nm 0.0755 4A" -1333.272043 -1334.608594 68.5% 4.83 eV 257 nm 0.0037 5A" -1333.268127 -1334.603846 68.5% 4.96 eV 250 nm 0.0002 5A' -1333.263433 -1334.583623 69.3% 5.51 eV 225 nm 0.0337 6A' -1333.236017 -1334.606246 67.1% 4.90 eV 253 nm 0.1576 7A' -1333.217591 -1334.589108 66.5% 5.36 eV 231 nm 0.0189 8A' -1333.210246 -1334.566372 67.7% 5.98 eV 207 nm 0.0013 --------------------------------------------------------------------------- | A' A" ------------------+---------- Inactive Orbitals | 23 2 Ras2 Orbitals | 4 8 Frozen Orbitals | 10 0 Orbitals 34-37 of Symmetry A' and 3-10 of Symmetry A' are active A' States: ---------- root 1: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15149 2200 22222200 0.91046 0.82893 Natural orbitals and occupation numbers for root 1 sym 1: 1.972594 1.920046 0.083751 0.028654 sym 2: 1.989262 1.998540 1.994222 1.964538 1.978642 1.876162 0.145046 0.048542 root 2: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15150 2200 22222ud0 0.45443 0.20651 15254 2ud0 22222200 0.67476 0.45530 Natural orbitals and occupation numbers for root 2 sym 1: 1.969539 1.300566 0.704358 0.032276 sym 2: 1.980163 1.997217 1.989838 1.960610 1.930287 1.612533 0.467427 0.055185 root 3: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15150 2200 22222ud0 0.61046 0.37266 15151 2200 2222u2d0 -0.39812 0.15850 Natural orbitals and occupation numbers for root 3 sym 1: 1.967799 1.858446 0.157622 0.059492 sym 2: 1.974015 1.994127 1.992693 1.958861 1.902124 1.493890 0.561804 0.079126 root 4: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15151 2200 2222u2d0 0.59484 0.35384 Natural orbitals and occupation numbers for root 4 sym 1: 1.943270 1.737417 0.414720 0.044780 sym 2: 1.976170 1.995716 1.957546 1.970824 1.285252 1.700565 0.850353 0.123385 root 5: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 1051 2220 22222000 0.67527 0.45598 1052 2220 2222ud00 0.42723 0.18252 Natural orbitals and occupation numbers for root 5 sym 1: 1.988061 1.901093 1.816830 0.053290 sym 2: 1.945544 1.996092 1.985011 1.914620 1.626022 0.534164 0.174450 0.064822 root 6: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15150 2200 22222ud0 -0.31891 0.10170 15153 2200 22u222d0 0.36817 0.13555 15164 2200 22222u0d 0.39936 0.15949 Natural orbitals and occupation numbers for root 6 sym 1: 1.954320 1.832691 0.169255 0.071092 sym 2: 1.989374 1.995987 1.742500 1.956565 1.940246 1.210272 0.842418 0.295280 root 7: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 15153 2200 22u222d0 -0.56435 0.31849 21827 2uu0 22222dd0 -0.35567 0.12650 Natural orbitals and occupation numbers for root 7 sym 1: 1.933909 1.658969 0.414554 0.045378 sym 2: 1.971131 1.994647 1.433989 1.942840 1.862564 1.605468 1.002815 0.133736 root 8: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 21827 2uu0 22222dd0 0.78169 0.61104 Natural orbitals and occupation numbers for root 8 sym 1: 1.949113 1.198465 0.827808 0.038636 sym 2: 1.974345 1.994995 1.961515 1.819266 1.921793 1.213976 0.995472 0.104615 A" States: ---------- root 1: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 7113 22u0 22222d00 -0.90137 0.81247 Natural orbitals and occupation numbers for root 1 sym 1: 1.984934 1.957429 1.014197 0.041252 sym 2: 1.911696 1.996165 1.991588 1.981999 1.940773 1.017694 0.113672 0.048600 root 2: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 7114 22u0 2222d200 0.87643 0.76813 Natural orbitals and occupation numbers for root 2 sym 1: 1.978757 1.934514 1.039897 0.045612 sym 2: 1.964750 1.995643 1.979824 1.952917 1.047315 1.861226 0.134469 0.065077 root 3: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 29065 2u00 222222d0 0.90974 0.82764 Natural orbitals and occupation numbers for root 3 sym 1: 1.963845 1.010307 0.053366 0.017823 sym 2: 1.988476 1.998654 1.995182 1.968051 1.990011 1.952084 1.010626 0.051574 root 4: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 7115 22u0 222d2200 0.80240 0.64384 Natural orbitals and occupation numbers for root 4 sym 1: 1.983865 1.950290 1.016788 0.045469 sym 2: 1.971663 1.989911 1.994594 1.166142 1.908364 1.659344 0.211407 0.102163 root 5: dominant CSFs: Symmetry: A' A" conf/sym 1111 22222222 Coeff Weight 7116 22u0 22d22200 -0.77879 0.60651 Natural orbitals and occupation numbers for root 5 sym 1: 1.980141 1.858598 1.103987 0.044855 sym 2: 1.969018 1.993543 1.201070 1.947504 1.834572 1.787558 0.186498 0.092656 ================================================== C3. ortho-quinoidal acyclic product (6) -------------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-20 are averaged. Summary of the calculation: CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.481877 -1334.776617 65.3% 2A -1333.438546 -1334.758443 63.9% 0.50 eV 2507 nm 0.0004 3A -1333.418656 -1334.741068 61.4% 0.97 eV 1282 nm 0.0004 4A -1333.387521 -1334.714087 63.0% 1.70 eV 729 nm 0.0005 5A -1333.371286 -1334.695801 58.4% 2.20 eV 564 nm 0.0076 6A -1333.367034 -1334.698670 61.4% 2.12 eV 585 nm 0.0044 7A -1333.352789 -1334.687355 54.6% 2.43 eV 510 nm 0.0016 8A -1333.341325 -1334.686212 60.9% 2.46 eV 504 nm 0.0340 9A -1333.336462 -1334.671341 56.2% 2.87 eV 433 nm 0.0087 10A -1333.331101 -1334.668152 40.4% 2.95 eV 420 nm 0.0021 11A -1333.327052 -1334.678721 38.2% 2.66 eV 465 nm 0.0024 12A -1333.322705 -1334.670805 39.1% 2.88 eV 431 nm 0.0129 13A -1333.320351 -1334.663222 19.9% 3.09 eV 402 nm 0.0030 14A -1333.314007 -1334.658674 33.0% 3.21 eV 386 nm 0.0004 15A -1333.307727 -1334.635851 53.9% 3.83 eV 324 nm 0.0013 16A -1333.300852 -1334.658556 18.6% 3.21 eV 386 nm 0.0048 17A -1333.294911 -1334.635465 41.0% 3.84 eV 323 nm 0.0420 18A -1333.289303 -1334.661190 0.5% 3.14 eV 395 nm 0.0003 19A -1333.282217 -1334.628159 3.0% 4.04 eV 307 nm 0.0039 20A -1333.278928 -1334.648019 4.1% 3.50 eV 354 nm 0.0040 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.481877 -1334.763880 70.4% 2A -1333.438546 -1334.744198 69.5% 0.54 eV 2315 nm 0.0004 3A -1333.418656 -1334.726354 69.3% 1.02 eV 1214 nm 0.0004 4A -1333.387521 -1334.698837 69.1% 1.77 eV 701 nm 0.0005 5A -1333.371286 -1334.679500 69.1% 2.30 eV 540 nm 0.0079 6A -1333.367034 -1334.683157 68.9% 2.20 eV 564 nm 0.0046 7A -1333.352789 -1334.670262 68.8% 2.55 eV 487 nm 0.0017 8A -1333.341325 -1334.669286 68.6% 2.57 eV 482 nm 0.0355 9A -1333.336462 -1334.653931 68.7% 2.99 eV 414 nm 0.0091 10A -1333.331101 -1334.652706 68.6% 3.03 eV 410 nm 0.0022 11A -1333.327052 -1334.656949 68.3% 2.91 eV 426 nm 0.0027 12A -1333.322705 -1334.653208 68.3% 3.01 eV 412 nm 0.0135 13A -1333.320351 -1334.650675 68.3% 3.08 eV 402 nm 0.0030 14A -1333.314007 -1334.639260 68.4% 3.39 eV 366 nm 0.0004 15A -1333.307727 -1334.621305 68.7% 3.88 eV 320 nm 0.0014 16A -1333.300852 -1334.645634 67.5% 3.22 eV 385 nm 0.0048 17A -1333.294911 -1334.621439 67.8% 3.88 eV 320 nm 0.0424 18A -1333.289303 -1334.609715 67.8% 4.20 eV 296 nm 0.0005 19A -1333.282217 -1334.622617 67.4% 3.84 eV 323 nm 0.0037 20A -1333.278928 -1334.620560 67.4% 3.90 eV 318 nm 0.0045 --------------------------------------------------------------------------- | A ------------------+---------- Inactive Orbitals | 25 Ras2 Orbitals | 12 Frozen Orbitals | 10 Orbitals 36-47 of Symmetry A are active States: ---------- root 1: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1 222222220000 0.84029 0.70608 Natural orbitals and occupation numbers for root 1 sym 1: 1.992878 1.996239 1.918690 1.993430 1.907203 1.935448 1.986523 1.786101 0.230953 0.109963 0.064841 0.077731 root 2: dominant CSFs: conf/sym 111111111111 Coeff Weight 3 222222u2d000 -0.75017 0.56275 Natural orbitals and occupation numbers for root 2 sym 1: 1.992490 1.924832 1.968188 1.953137 1.950631 1.868544 1.108118 1.825006 1.069004 0.181073 0.073043 0.085934 root 3: dominant CSFs: conf/sym 111111111111 Coeff Weight 2 2222222ud000 0.35779 0.12801 106 22222u22d000 0.59948 0.35937 Natural orbitals and occupation numbers for root 3 sym 1: 1.991842 1.955204 1.939867 1.950505 1.914761 1.339712 1.580915 1.820300 1.125419 0.218766 0.072535 0.090174 root 4: dominant CSFs: conf/sym 111111111111 Coeff Weight 5 222222ud2000 0.54771 0.29998 Natural orbitals and occupation numbers for root 4 sym 1: 1.992188 1.969488 1.940396 1.959274 1.839241 1.909955 1.049070 1.227802 1.635985 0.306105 0.074486 0.096010 root 5: dominant CSFs: conf/sym 111111111111 Coeff Weight 8 222222u20d00 -0.67860 0.46050 109 22222u220d00 0.32404 0.10500 Natural orbitals and occupation numbers for root 5 sym 1: 1.991577 1.978151 1.922257 1.964514 1.882356 1.934138 1.133338 1.774338 0.364596 0.895666 0.069831 0.089238 root 6: dominant CSFs: conf/sym 111111111111 Coeff Weight 6 222222022000 -0.34357 0.11804 316 2222u222d000 -0.34232 0.11719 Natural orbitals and occupation numbers for root 6 sym 1: 1.990063 1.945449 1.950119 1.971393 1.684235 1.068908 1.566581 1.915711 1.445601 0.284088 0.074979 0.102872 root 7: dominant CSFs: conf/sym 111111111111 Coeff Weight 10 222222udud00 -0.43003 0.18493 12 222222uudd00 0.33530 0.11243 Natural orbitals and occupation numbers for root 7 sym 1: 1.988444 1.973956 1.936935 1.932341 1.904997 1.750465 1.374208 1.232878 1.072069 0.648598 0.078343 0.106765 root 8: dominant CSFs: conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.45790 0.20967 526 222u2222d000 0.36010 0.12968 Natural orbitals and occupation numbers for root 8 sym 1: 1.972141 1.949778 1.959913 1.884619 1.917870 1.272993 1.701399 1.929811 0.985911 0.224214 0.075723 0.125629 root 9: dominant CSFs: conf/sym 111111111111 Coeff Weight 4 222222202000 0.45046 0.20291 Natural orbitals and occupation numbers for root 9 sym 1: 1.982233 1.909470 1.960854 1.803655 1.850185 1.749911 1.743365 0.917285 1.570322 0.258928 0.102779 0.151012 root 10: dominant CSFs: conf/sym 111111111111 Coeff Weight 11 22222202ud00 0.28305 0.08012 113 22222uu2dd00 -0.29474 0.08687 318 2222u2d22000 -0.29772 0.08864 Natural orbitals and occupation numbers for root 10 sym 1: 1.986811 1.951336 1.889358 1.918063 1.799048 1.545198 1.123073 1.625319 1.438090 0.498975 0.095297 0.129433 root 11: dominant CSFs: conf/sym 111111111111 Coeff Weight 2 2222222ud000 0.17084 0.02919 5 222222ud2000 0.31641 0.10012 Natural orbitals and occupation numbers for root 11 sym 1: 1.979100 1.926888 1.949409 1.875941 1.850561 1.749556 1.194836 1.477716 1.345404 0.370711 0.166264 0.113614 root 12: dominant CSFs: conf/sym 111111111111 Coeff Weight 11 22222202ud00 0.34867 0.12157 Natural orbitals and occupation numbers for root 12 sym 1: 1.973429 1.920648 1.651230 1.937253 1.892191 1.619273 1.297858 1.752510 1.258833 0.453986 0.076338 0.166451 root 13: dominant CSFs: conf/sym 111111111111 Coeff Weight 10 222222udud00 -0.24602 0.06053 107 22222u2d2000 0.25377 0.06440 117 22222u022d00 0.24472 0.05989 Natural orbitals and occupation numbers for root 13 sym 1: 1.982406 1.931174 1.862706 1.917741 1.807177 1.387106 1.189640 1.617308 1.577750 0.488491 0.090011 0.148491 root 14: dominant CSFs: conf/sym 111111111111 Coeff Weight 111 22222ud2ud00 -0.25285 0.06393 117 22222u022d00 0.31211 0.09741 8926 22220u222d00 0.08121 0.00660 Natural orbitals and occupation numbers for root 14 sym 1: 1.987098 1.953253 1.861430 1.934982 1.672942 1.632604 1.066745 1.768016 1.271230 0.584385 0.107230 0.160084 root 15: dominant CSFs: conf/sym 111111111111 Coeff Weight 52 222222u2000d 0.27406 0.07511 737 22u2222d2000 0.24924 0.06212 738 22u222d22000 0.26916 0.07245 1891 22u22d222000 0.24800 0.06150 Natural orbitals and occupation numbers for root 15 sym 1: 1.982969 1.932890 1.814820 1.943413 1.837095 1.557333 1.170140 1.772869 1.213142 0.371623 0.106543 0.297162 root 16: dominant CSFs: conf/sym 111111111111 Coeff Weight 52 222222u2000d 0.27163 0.07378 107 22222u2d2000 0.26577 0.07064 Natural orbitals and occupation numbers for root 16 sym 1: 1.975106 1.936843 1.910379 1.859838 1.832229 1.648931 1.199285 1.589217 1.144064 0.496020 0.122290 0.285798 root 17: dominant CSFs: conf/sym 111111111111 Coeff Weight 317 2222u22d2000 0.35666 0.12721 Natural orbitals and occupation numbers for root 17 sym 1: 1.981172 1.967769 1.806346 1.908948 1.600941 1.735751 1.862804 1.380353 1.112084 0.339268 0.207309 0.097255 root 18: dominant CSFs: conf/sym 111111111111 Coeff Weight 320 2222u22dud00 0.24253 0.05882 737 22u2222d2000 -0.26227 0.06879 950 2u22222dud00 0.27488 0.07556 Natural orbitals and occupation numbers for root 18 sym 1: 1.981372 1.510176 1.925118 1.892756 1.793060 1.852211 1.722283 1.303524 1.150491 0.592350 0.113364 0.163294 root 19: dominant CSFs: conf/sym 111111111111 Coeff Weight 11 22222202ud00 -0.23472 0.05510 52 222222u2000d 0.22391 0.05013 323 2222u2u2dd00 -0.24301 0.05905 Natural orbitals and occupation numbers for root 19 sym 1: 1.983917 1.928477 1.840271 1.864313 1.708187 1.814312 1.194436 1.590206 0.984671 0.759721 0.105316 0.226172 root 20: dominant CSFs: conf/sym 111111111111 Coeff Weight 528 222u22d22000 -0.35126 0.12339 Natural orbitals and occupation numbers for root 20 sym 1: 1.974030 1.860561 1.911059 1.707916 1.788601 1.586295 1.211815 1.612398 1.485767 0.546414 0.106166 0.208979 ================================================== C4. ortho-quinoidal acyclic product (7) -------------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-20 are averaged. Summary of the calculation: CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.490154 -1334.771151 65.8% 2A -1333.438573 -1334.734101 65.0% 1.00 eV 1230 nm 0.0001 3A -1333.430343 -1334.748409 63.5% 0.62 eV 2003 nm 0.0003 4A -1333.413693 -1334.730654 63.7% 1.10 eV 1125 nm 0.0000 5A -1333.390916 -1334.706354 63.3% 1.76 eV 703 nm 0.0004 6A -1333.358081 -1334.682444 32.5% 2.41 eV 514 nm 0.0034 7A -1333.356188 -1334.679358 62.4% 2.50 eV 496 nm 0.0001 8A -1333.352293 -1334.658620 63.2% 2.79 eV 444 nm 0.0097 9A -1333.348271 -1334.670212 60.4% 2.75 eV 451 nm 0.0008 10A -1333.341221 -1334.677608 54.2% 2.55 eV 487 nm 0.0786 11A -1333.335771 -1334.662311 61.6% 2.96 eV 419 nm 0.0005 12A -1333.330102 -1333.408449 0.0% - eV - nm - 13A -1333.326305 -1334.656274 53.1% 3.13 eV 397 nm 0.0004 14A -1333.323205 -1334.645440 56.6% 3.42 eV 362 nm 0.0039 15A -1333.306743 -1334.641546 53.3% 3.53 eV 352 nm 0.0671 16A -1333.301613 -1334.649606 11.3% 3.31 eV 375 nm 0.0064 17A -1333.295597 -1334.641302 58.9% 3.53 eV 351 nm 0.0002 18A -1333.292278 -1334.613778 63.1% 4.28 eV 290 nm 0.0025 19A -1333.288944 -1334.635494 17.3% 3.69 eV 336 nm 0.1059 20A -1333.284320 -1334.616265 7.9% 4.22 eV 294 nm 0.0216 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.490154 -1334.758833 70.7% 2A -1333.438573 -1334.720969 70.2% 1.03 eV 1203 nm 0.0001 3A -1333.430343 -1334.733547 69.3% 0.69 eV 1802 nm 0.0003 4A -1333.413693 -1334.716026 69.4% 1.17 eV 1064 nm 0.0000 5A -1333.390916 -1334.691229 69.3% 1.84 eV 674 nm 0.0004 6A -1333.358081 -1334.671086 68.7% 2.39 eV 519 nm 0.0033 7A -1333.356188 -1334.663544 69.1% 2.59 eV 478 nm 0.0001 8A -1333.352293 -1334.653718 69.5% 2.86 eV 433 nm 0.0099 9A -1333.348271 -1334.654901 69.2% 2.83 eV 438 nm 0.0008 10A -1333.341221 -1334.661999 68.8% 2.64 eV 471 nm 0.0814 11A -1333.335771 -1334.645921 68.9% 3.07 eV 404 nm 0.0006 12A -1333.330102 -1334.643153 68.7% 3.15 eV 394 nm 0.0006 13A -1333.326305 -1334.640031 68.6% 3.23 eV 384 nm 0.0004 14A -1333.323205 -1334.628157 69.1% 3.56 eV 349 nm 0.0041 15A -1333.306743 -1334.622197 68.6% 3.72 eV 333 nm 0.0708 16A -1333.301613 -1334.638628 67.7% 3.27 eV 379 nm 0.0064 17A -1333.295597 -1334.623623 68.2% 3.68 eV 337 nm 0.0002 18A -1333.292278 -1334.598467 69.1% 4.36 eV 284 nm 0.0026 19A -1333.288944 -1334.615190 68.3% 3.91 eV 317 nm 0.1121 20A -1333.284320 -1334.605364 68.2% 4.18 eV 297 nm 0.0214 --------------------------------------------------------------------------- | A ------------------+---------- Inactive Orbitals | 25 Ras2 Orbitals | 12 Frozen Orbitals | 10 Orbitals 36-47 of Symmetry A are active States: ---------- root 1: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1 222222220000 0.86185 0.74279 Natural orbitals and occupation numbers for root 1 sym 1: 1.998876 1.937790 1.998592 1.918270 1.905926 1.990704 1.992567 1.805743 0.210701 0.095581 0.082758 0.062491 root 2: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.18804 0.03536 3 222222u2d000 -0.75345 0.56769 Natural orbitals and occupation numbers for root 2 sym 1: 1.991480 1.941691 1.993876 1.892502 1.981689 1.963545 1.039368 1.919369 1.006917 0.115477 0.089874 0.064211 root 3: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 106 22222u22d000 0.61510 0.37835 107 22222u2d2000 -0.39782 0.15826 Natural orbitals and occupation numbers for root 3 sym 1: 1.991418 1.974060 1.969229 1.933248 1.938319 1.101281 1.915198 1.772965 0.997130 0.246668 0.092637 0.067846 root 4: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 108 22222ud22000 0.72089 0.51968 Natural orbitals and occupation numbers for root 4 sym 1: 1.993118 1.983775 1.942551 1.952042 1.997615 0.989197 1.062581 1.914099 1.667935 0.339001 0.092986 0.065099 root 5: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 107 22222u2d2000 -0.35344 0.12492 109 22222u220d00 0.61951 0.38380 Natural orbitals and occupation numbers for root 5 sym 1: 1.986371 1.988006 1.965619 1.927655 1.900827 1.033900 1.998294 1.477530 0.594641 0.954384 0.102520 0.070253 root 6: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 736 22u22222d000 -0.46838 0.21938 Natural orbitals and occupation numbers for root 6 sym 1: 1.985815 1.950958 1.409721 1.926619 1.923686 1.716932 1.881355 1.587502 1.054399 0.371072 0.115903 0.076040 root 7: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 113 22222uu2dd00 0.72981 0.53262 Natural orbitals and occupation numbers for root 7 sym 1: 1.991670 1.976365 1.928423 1.938068 1.986761 1.028716 1.002844 1.854841 1.259985 0.842334 0.119849 0.070144 root 8: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 4 222222202000 0.53699 0.28836 316 2222u222d000 0.34051 0.11594 Natural orbitals and occupation numbers for root 8 sym 1: 1.971038 1.930942 1.996551 1.892208 1.715871 1.969977 1.963089 0.781463 1.368040 0.124695 0.207729 0.078399 root 9: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 5 222222ud2000 0.48656 0.23674 Natural orbitals and occupation numbers for root 9 sym 1: 1.979253 1.936294 1.950905 1.867910 1.883347 1.923346 1.039802 1.500903 1.349353 0.317865 0.164713 0.086309 root 10: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.59694 0.35633 526 222u2222d000 0.32738 0.10717 Natural orbitals and occupation numbers for root 10 sym 1: 1.969984 1.904191 1.985422 1.813217 1.868247 1.922433 1.940252 1.223008 0.984209 0.222304 0.106071 0.060663 root 11: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1367 22222022ud00 0.56570 0.32002 Natural orbitals and occupation numbers for root 11 sym 1: 1.987295 1.983261 1.712318 1.944540 1.921695 0.517434 1.893128 1.864872 1.435326 0.554971 0.110983 0.074178 root 12: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 111 22222ud2ud00 -0.44325 0.19647 738 22u222d22000 0.54038 0.29201 Natural orbitals and occupation numbers for root 12 sym 1: 1.991393 1.964682 1.628669 1.930227 1.958112 1.314889 1.090977 1.901770 1.532269 0.492107 0.123542 0.071364 root 13: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1541 2222ud222000 -0.43922 0.19291 Natural orbitals and occupation numbers for root 13 sym 1: 1.986997 1.983677 1.915472 1.930486 1.489020 0.931217 1.995751 1.712978 1.191437 0.441788 0.325252 0.095924 root 14: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 8 222222u20d00 -0.37080 0.13750 528 222u22d22000 0.48703 0.23720 Natural orbitals and occupation numbers for root 14 sym 1: 1.988936 1.925437 1.994225 1.555711 1.973897 1.981628 1.022812 1.813927 1.001272 0.557410 0.107557 0.077189 root 15: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.26735 0.07148 7 2222222u0d00 -0.28906 0.08356 Natural orbitals and occupation numbers for root 15 sym 1: 1.969148 1.877169 1.987308 1.518285 1.869340 1.914844 1.994174 1.234140 0.983599 0.447014 0.121700 0.083279 root 16: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1716 222u2d222000 -0.34930 0.12201 Natural orbitals and occupation numbers for root 16 sym 1: 1.962476 1.938714 1.821752 1.674420 1.894308 1.331560 1.977950 1.522182 1.155581 0.465284 0.147868 0.107903 root 17: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 115 22222udu2d00 -0.50086 0.25086 Natural orbitals and occupation numbers for root 17 sym 1: 1.989189 1.983838 1.909478 1.926587 1.971447 1.075493 1.025838 1.322491 1.510368 0.907639 0.283038 0.094594 root 18: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1369 222220u22d00 0.72276 0.52238 Natural orbitals and occupation numbers for root 18 sym 1: 1.991033 1.985220 1.733106 1.902200 1.986981 0.471266 1.043351 1.922760 1.844451 0.945696 0.102510 0.071426 root 19: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 526 222u2222d000 -0.44459 0.19766 Natural orbitals and occupation numbers for root 19 sym 1: 1.960875 1.897108 1.974260 1.643870 1.771479 1.883710 1.923725 1.295569 1.125109 0.282421 0.136366 0.105509 root 20: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 528 222u22d22000 0.40634 0.16511 948 2u2222d22000 0.35737 0.12771 Natural orbitals and occupation numbers for root 20 sym 1: 1.967312 1.865508 1.928486 1.469134 1.896426 1.805022 1.161273 1.834027 1.391530 0.375090 0.204103 0.102091 ================================================== C5. thiazabenzocyclobutene (8a) -------------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-10 are averaged. Summary of the calculation: CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.473110 -1334.779096 65.7% 2A -1333.364426 -1334.689691 64.1% 2.43 eV 510 nm 0.0102 3A -1333.332281 -1334.682877 59.2% 2.62 eV 474 nm 0.0115 4A -1333.316845 -1334.683101 48.3% 2.61 eV 475 nm 0.0445 5A -1333.314125 -1334.676527 47.9% 2.79 eV 444 nm 0.0019 6A -1333.300406 -1334.659795 56.3% 3.25 eV 382 nm 0.0457 7A -1333.269413 -1334.423788 0.1% - eV - nm - 8A -1333.255199 -1334.623618 0.9% 4.23 eV 293 nm 0.1080 9A -1333.243805 -1334.619501 45.8% 4.34 eV 285 nm 0.0028 10A -1333.236891 -1334.611306 16.8% 4.57 eV 272 nm 0.0475 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.473110 -1334.766963 70.5% 2A -1333.364426 -1334.675649 69.6% 2.49 eV 499 nm 0.0104 3A -1333.332281 -1334.667366 68.8% 2.71 eV 457 nm 0.0119 4A -1333.316845 -1334.664445 68.3% 2.79 eV 444 nm 0.0475 5A -1333.314125 -1334.660896 68.4% 2.89 eV 430 nm 0.0020 6A -1333.300406 -1334.642114 68.6% 3.40 eV 365 nm 0.0479 7A -1333.269413 -1334.624282 67.7% 3.88 eV 319 nm 0.0237 8A -1333.255199 -1334.622816 66.9% 3.92 eV 316 nm 0.1001 9A -1333.243805 -1334.600408 67.8% 4.53 eV 274 nm 0.0030 10A -1333.236891 -1334.601389 67.4% 4.51 eV 275 nm 0.0469 --------------------------------------------------------------------------- | A ------------------+---------- Inactive Orbitals | 25 Ras2 Orbitals | 12 Frozen Orbitals | 10 Orbitals 36-47 of Symmetry A are active States: ---------- root 1: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1 222222220000 0.92152 0.84920 Natural orbitals and occupation numbers for root 1 sym 1: 1.965306 1.994217 1.996353 1.899267 1.990090 1.946004 1.939354 1.987047 0.108906 0.046001 0.067191 0.060263 root 2: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.61282 0.37555 316 2222u222d000 -0.58088 0.33742 Natural orbitals and occupation numbers for root 2 sym 1: 1.972911 1.993647 1.995049 1.991278 1.024393 1.963345 1.939846 1.931945 0.999419 0.058893 0.067611 0.061662 root 3: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.47805 0.22853 3 222222u2d000 -0.33724 0.11373 7 2222222u0d00 -0.41710 0.17397 316 2222u222d000 0.39911 0.15929 Natural orbitals and occupation numbers for root 3 sym 1: 1.969822 1.991640 1.975163 1.946735 1.792741 1.933058 1.916190 1.140228 0.889397 0.306419 0.072375 0.066233 root 4: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 -0.36608 0.13402 8 222222u20d00 -0.48131 0.23166 319 2222u2220d00 0.41483 0.17208 Natural orbitals and occupation numbers for root 4 sym 1: 1.968688 1.987459 1.976474 1.945360 1.902917 1.927398 1.386571 1.581551 0.494281 0.683609 0.074660 0.071031 root 5: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 -0.64887 0.42103 7 2222222u0d00 0.35470 0.12581 Natural orbitals and occupation numbers for root 5 sym 1: 1.972198 1.982959 1.974762 1.952481 1.855409 1.937611 1.250225 1.718473 0.818896 0.388784 0.075511 0.072690 root 6: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 7 2222222u0d00 -0.48663 0.23681 8 222222u20d00 0.64442 0.41528 319 2222u2220d00 0.31715 0.10059 Natural orbitals and occupation numbers for root 6 sym 1: 1.967751 1.983875 1.980555 1.904560 1.930524 1.954964 1.085993 1.928881 0.180226 0.936275 0.075114 0.071282 root 7: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 106 22222u22d000 -0.43467 0.18893 Natural orbitals and occupation numbers for root 7 sym 1: 1.971681 1.970697 1.978635 1.952322 1.759887 1.545257 1.831492 1.397330 0.894228 0.371353 0.216817 0.110300 root 8: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 22 222222u200d0 -0.39964 0.15972 Natural orbitals and occupation numbers for root 8 sym 1: 1.965797 1.967748 1.975631 1.911798 1.768431 1.836914 1.658070 1.396694 0.572180 0.350554 0.422734 0.173447 root 9: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 5 222222ud2000 0.42024 0.17660 Natural orbitals and occupation numbers for root 9 sym 1: 1.962556 1.984552 1.981863 1.924147 1.742947 1.856776 1.472650 1.256491 1.021514 0.573030 0.129819 0.093656 root 10: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 106 22222u22d000 -0.51613 0.26639 109 22222u220d00 -0.41814 0.17484 Natural orbitals and occupation numbers for root 10 sym 1: 1.962429 1.967921 1.979901 1.916074 1.849142 1.353972 1.825235 1.615835 0.924124 0.316327 0.163099 0.125938 ================================================== C6. thiazabenzocyclobutene (8b) -------------------------------------------------- Active space: 16 electrons in 12 Orbitals Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-10 are averaged. Summary of the calculation: CAS(16/12) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.470887 -1334.778545 65.7% 2A -1333.361980 -1334.690700 63.9% 2.39 eV 519 nm 0.0128 3A -1333.323032 -1334.680529 59.8% 2.67 eV 465 nm 0.0219 4A -1333.308170 -1334.675465 37.6% 2.81 eV 442 nm 0.0530 5A -1333.303434 -1334.668783 58.7% 2.99 eV 415 nm 0.0054 6A -1333.286887 -1334.654554 54.5% 3.37 eV 367 nm 0.0592 7A -1333.264695 -1334.636514 31.3% 3.87 eV 321 nm 0.0076 8A -1333.253475 -1334.683039 2.4% 2.60 eV 477 nm 0.0638 9A -1333.236234 -1334.615417 46.6% 4.45 eV 279 nm 0.0054 10A -1333.228978 -1334.618369 12.1% 4.36 eV 284 nm 0.0527 --------------------------------------------------------------------------- CAS(16/12) + CASPT2 (0.25 h level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w deltaE (in eV) deltaE (in nm) osc --------------------------------------------------------------------------- 1A -1333.470887 -1334.766378 70.5% 2A -1333.361980 -1334.676428 69.5% 2.45 eV 507 nm 0.0131 3A -1333.323032 -1334.663835 68.6% 2.79 eV 444 nm 0.0229 4A -1333.308170 -1334.657734 68.2% 2.96 eV 419 nm 0.0558 5A -1333.303434 -1334.652443 68.3% 3.10 eV 400 nm 0.0056 6A -1333.286887 -1334.635437 68.2% 3.56 eV 348 nm 0.0625 7A -1333.264695 -1334.625003 67.4% 3.85 eV 322 nm 0.0076 8A -1333.253475 -1334.621216 67.0% 3.95 eV 314 nm 0.0969 9A -1333.236234 -1334.597678 67.4% 4.59 eV 270 nm 0.0056 10A -1333.228978 -1334.599724 67.1% 4.54 eV 273 nm 0.0548 --------------------------------------------------------------------------- | A ------------------+---------- Inactive Orbitals | 25 Ras2 Orbitals | 12 Frozen Orbitals | 10 Orbitals 36-47 of Symmetry A are active States: ---------- root 1: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 1 222222220000 0.92400 0.85378 Natural orbitals and occupation numbers for root 1 sym 1: 1.994388 1.995821 1.966892 1.899036 1.991401 1.939098 1.990094 1.945122 0.109011 0.040482 0.067502 0.061152 root 2: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 -0.65436 0.42819 316 2222u222d000 -0.60370 0.36445 Natural orbitals and occupation numbers for root 2 sym 1: 1.993830 1.995383 1.965583 1.991782 1.932716 1.938664 1.976514 1.029855 0.996425 0.048996 0.068148 0.062103 root 3: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 0.51193 0.26207 7 2222222u0d00 0.37268 0.13889 8 222222u20d00 -0.33890 0.11485 316 2222u222d000 0.33544 0.11252 Natural orbitals and occupation numbers for root 3 sym 1: 1.973085 1.991732 1.971900 1.947442 1.919041 1.931003 1.117322 1.810492 0.895808 0.301032 0.073202 0.067940 root 4: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 2 2222222ud000 0.33136 0.10980 8 222222u20d00 -0.63828 0.40740 316 2222u222d000 -0.34110 0.11635 Natural orbitals and occupation numbers for root 4 sym 1: 1.976895 1.988849 1.969404 1.941883 1.910067 1.925174 1.313546 1.649642 0.438230 0.737924 0.077180 0.071205 root 5: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 3 222222u2d000 -0.60803 0.36970 Natural orbitals and occupation numbers for root 5 sym 1: 1.974644 1.982322 1.970884 1.952936 1.897903 1.936946 1.230353 1.733782 0.845594 0.321647 0.078539 0.074450 root 6: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 7 2222222u0d00 0.65728 0.43202 8 222222u20d00 0.40433 0.16349 Natural orbitals and occupation numbers for root 6 sym 1: 1.963104 1.985385 1.977294 1.947902 1.897294 1.955952 1.871208 1.104181 0.235129 0.908284 0.080422 0.073846 root 7: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 106 22222u22d000 0.36585 0.13385 Natural orbitals and occupation numbers for root 7 sym 1: 1.977858 1.969345 1.968572 1.946293 1.617523 1.696931 1.794486 1.445794 0.771366 0.405526 0.270983 0.135323 root 8: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 21 2222222u00d0 0.35181 0.12377 22 222222u200d0 0.35983 0.12948 Natural orbitals and occupation numbers for root 8 sym 1: 1.978578 1.968006 1.963801 1.924996 1.775583 1.841115 1.608511 1.441871 0.521005 0.278228 0.489637 0.208670 root 9: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 10 222222udud00 -0.38163 0.14564 106 22222u22d000 -0.36388 0.13241 Natural orbitals and occupation numbers for root 9 sym 1: 1.977596 1.983432 1.965201 1.927808 1.829267 1.677119 1.484528 1.283230 1.062803 0.460441 0.229714 0.118861 root 10: dominant CSFs: Symmetry: A conf/sym 111111111111 Coeff Weight 106 22222u22d000 -0.47537 0.22598 Natural orbitals and occupation numbers for root 10 sym 1: 1.971624 1.970717 1.966072 1.930909 1.765763 1.532356 1.802678 1.394417 0.960058 0.354463 0.196479 0.154464