"The Role of Conformation and Electronic Structure in the Chemistry of Ground and Excited State o-Pyrazolylphenylnitrenes" Claudio Carra, Thomas Bally, and Angelo Albini ========================================================== SUPPORTING INFORMATION ========================================================== All stationary points listed in this file were located by the CASSCF(14,12) method. The active space contains the 12 pi-Mos (6 on the phenyl, 6 on the pyrazolyl ring) plus two sigma-Mos. In the nitrenes 2 these include the singly occupied in-plane-p-AO on the and the in-plane sp2 lone pair on the same atom. In the transition states the former AO turns into the incipient C-N or N-N bonding MO while in the final products this MO is usually replaced by a higher-lying sigma(C-C) MO. Natural orbitals and occupation numbers : density matrix relative to the natural active MO's ---------------------------------------------------------- 2-(1-pyrazolyl)-phenylnitrene 2a and products thereof ---------------------------------------------------------- 2a (NN) triplet CASSCF energy: -508.2488007928 CASPT2 energy: -509.7120016737 Reference weight: 0.66652 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.90955 0.82727 Natural orbitals and occupation numbers for root 1 1.993743 1.931306 1.909491 1.987893 1.916471 1.950372 1.001751 0.999990 0.069922 0.086183 0.096186 0.056693 C -1.927762 0.925480 -0.684203 C -2.972554 -0.619507 0.479854 C -3.187737 0.471273 -0.400152 C 0.347456 0.238450 0.039687 C 0.935415 1.451660 0.271468 C 2.328472 1.586208 0.291089 C 3.141259 0.471925 0.092834 C 2.562828 -0.770032 -0.139409 C 1.156528 -0.914151 -0.186004 N 0.630657 -2.121548 -0.475757 N -1.057632 0.129701 -0.003302 N -1.692432 -0.809308 0.708790 H 4.210701 0.570271 0.119177 H 2.763518 2.550265 0.477959 H 0.313615 2.307698 0.458546 H -3.696501 -1.255900 0.944919 H -4.116908 0.848354 -0.771099 H -1.580294 1.709806 -1.321381 H 3.168911 -1.641217 -0.303944 ---------------------------------------------------------- 2a (NH) triplet CASSCF energy: -508.2530970025 CASPT2 energy: -509.7161407403 Reference weight: 0.66659 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 6151 2222u02u0200 -0.90855 0.82547 Natural orbitals and occupation numbers for root 1 1.994067 1.950659 1.916703 1.931704 1.000044 0.056111 1.909351 1.002099 0.097947 1.987168 0.065567 0.088578 C 3.056589 -0.696165 -0.287439 C 3.142700 0.652890 0.138605 C 1.840647 1.036254 0.309137 C -0.336872 -0.175201 0.051837 C -0.891160 -1.431401 0.314960 C -2.268277 -1.593271 0.378968 C -3.126256 -0.492001 0.190495 C -2.608217 0.735512 -0.069076 C -1.198290 0.936238 -0.162002 N 1.808494 -1.095620 -0.366709 N 1.062955 -0.039135 -0.010788 N -0.747693 2.161507 -0.469483 H -4.190818 -0.626277 0.250514 H -2.677854 -2.564310 0.585781 H -0.234694 -2.264709 0.462143 H 3.848482 -1.371660 -0.537005 H 4.020274 1.242702 0.296409 H 1.417532 1.960951 0.629896 H -3.244092 1.587288 -0.224705 ---------------------------------------------------------- 2a (NH) triplet, Cs symmetry CASSCF energy: -508.2517380339 CASPT2 energy: -509.7171155568 Reference weight: 0.66611 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 1 22222222222 Coeff Weight 1 u 222222u0000 0.91218 0.83207 Natural orbitals and occupation numbers for root 1 sym 1: 1.000000 sym 2: 1.987573 1.992578 1.950665 1.931310 1.917961 1.914151 1.003541 0.074438 0.071682 0.099741 0.056361 C -2.006467 -2.435344 0.000000 C -0.770734 -3.129655 0.000000 C 0.172909 -2.141066 0.000000 C -0.001326 0.372724 0.000000 C 1.391886 0.667126 0.000000 C 1.804796 2.031816 0.000000 C 0.883156 3.053088 0.000000 C -0.483943 2.738257 0.000000 C -0.911133 1.433600 0.000000 N -1.824919 -1.137571 0.000000 N -0.494635 -0.945480 0.000000 N 2.357742 -0.268372 0.000000 H -1.214455 3.526358 0.000000 H -0.603524 -4.185540 0.000000 H 2.860028 2.231791 0.000000 H 1.206047 4.077489 0.000000 H -3.000023 -2.833428 0.000000 H -1.957010 1.208354 0.000000 H 1.235975 -2.198724 0.000000 ---------------------------------------------------------- 2a TS: (NN) <--> (NH) triplet CASSCF energy: -508.2483564789 CASPT2 energy: -509.7084375852 Reference weight: 0.66742 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 106 2222u22u0000 0.90970 0.82756 Natural orbitals and occupation numbers for root 1 1.993448 1.987720 1.908663 1.931316 1.000029 1.950696 1.918024 1.001790 0.071132 0.087448 0.093468 0.056267 C 3.002500 -0.041757 -0.762989 C 3.155926 -0.210188 0.634991 C 1.870930 -0.299113 1.103387 C -0.366247 -0.217678 0.013877 C -1.094445 0.996195 0.066685 C -2.513147 0.940927 0.044902 C -3.160002 -0.258382 -0.019128 C -2.434117 -1.459098 -0.066529 C -1.041190 -1.431961 -0.052037 N 1.733777 -0.031434 -1.112665 N 1.050928 -0.189695 0.026304 N -0.471906 2.190017 0.144962 H -2.951216 -2.399036 -0.116548 H 4.062227 -0.252961 1.200687 H -3.060113 1.864813 0.081943 H -4.234376 -0.286000 -0.034064 H 3.761443 0.069112 -1.509632 H -0.472581 -2.341739 -0.099893 H 1.476914 -0.422515 2.089464 ---------------------------------------------------------- 2a (NN) open-shell singlet CASSCF energy: -508.2196854559 CASPT2 energy: -509.6788014029 Reference weight: 0.66395 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.67771 0.45929 3 222222020000 -0.60682 0.36824 Natural orbitals and occupation numbers for root 1 sym 1: 1.996100 1.927785 1.903139 1.988916 1.915875 1.950340 1.104836 0.899756 0.069715 0.086937 0.099884 0.056717 C -1.952911 0.922741 -0.680282 C -2.980877 -0.624368 0.496261 C -3.207791 0.459791 -0.389788 C 0.326643 0.264571 0.055517 C 0.915340 1.440170 0.280194 C 2.355808 1.582505 0.280206 C 3.171971 0.446799 0.100225 C 2.610650 -0.792194 -0.093197 C 1.147283 -0.945388 -0.202953 N 0.649530 -2.055694 -0.573172 N -1.074150 0.138024 0.002938 N -1.699062 -0.802486 0.722553 H 4.240954 0.549875 0.136698 H 2.788014 2.548140 0.455155 H 0.310146 2.306464 0.475643 H -3.698463 -1.265594 0.964634 H -4.141082 0.824424 -0.762883 H -1.612414 1.704367 -1.324268 H 3.208943 -1.671754 -0.229880 ---------------------------------------------------------- 2a TS: (NN) <--> (NH) open-shell singlet CASSCF energy: -508.2192486007 CASPT2 energy: -509.6751690570 Reference weight: 0.66424 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 15 222222000020 0.64532 0.41644 484 222220020020 -0.63406 0.40203 Natural orbitals and occupation numbers for root 1 sym 1: 1.988165 1.996456 1.903003 1.950529 1.917188 1.018402 0.087774 0.985706 0.098026 0.070277 1.928059 0.056415 C 3.011082 -0.033052 -0.767154 C 3.168812 -0.180968 0.633310 C 1.887221 -0.295437 1.103628 C -0.348396 -0.251395 0.014833 C -1.082991 1.032980 0.073712 C -2.558661 0.961262 0.039643 C -3.183818 -0.212558 -0.023995 C -2.445157 -1.460468 -0.070665 C -1.034083 -1.438841 -0.054458 N 1.743065 -0.056794 -1.116482 N 1.064185 -0.224311 0.024563 N -0.485821 2.152674 0.165770 H -2.971418 -2.393090 -0.125561 H 4.076261 -0.197305 1.198502 H -3.096076 1.890103 0.071715 H -4.257889 -0.251046 -0.045126 H 3.767320 0.086462 -1.515191 H -0.478860 -2.356902 -0.105460 H 1.496882 -0.415760 2.091516 ---------------------------------------------------------- 2a (NH) open-shell singlet CASSCF energy: -508.2234973241 CASPT2 energy: -509.6864128358 Reference weight: 0.66473 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 -0.61747 0.38127 442 222220220000 0.67004 0.44896 Natural orbitals and occupation numbers for root 1 sym 1: 1.987996 1.930054 1.950513 1.906505 1.915899 0.927571 1.995687 1.079887 0.096305 0.068562 0.084546 0.056475 C -1.877191 0.910388 0.424720 C -3.043301 -0.836457 -0.227232 C -3.167328 0.478279 0.288412 C 0.333506 -0.194928 0.027780 C 1.135625 1.043661 -0.102539 C 2.599806 0.904938 -0.026734 C 3.183858 -0.330448 0.061343 C 2.381105 -1.490898 0.136805 C 0.951686 -1.380762 0.135578 N -1.068683 -0.105959 -0.001061 N -1.785104 -1.172721 -0.388227 N 0.622481 2.192170 -0.314979 H 2.830369 -2.461376 0.217927 H -4.061255 1.018414 0.516547 H 3.178175 1.806230 -0.088512 H 4.254395 -0.418384 0.085829 H -3.816542 -1.529392 -0.487530 H 0.357518 -2.269816 0.208851 H -1.480587 1.833183 0.781533 ---------------------------------------------------------- 2a (NH) symmetry Cs open-shell singlet CASSCF energy: -508.2245744045 CASPT2 energy: -509.6888753913 Reference weight: 0.66565 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 1 22222222222 Coeff Weight 1 u 222222d0000 0.90264 0.81476 Natural orbitals and occupation numbers for root 1 sym 1: 1.000000 sym 2: 1.987617 1.930740 1.950442 1.998567 1.915796 1.886007 1.005743 0.119308 0.083195 0.066246 0.056338 C -2.003390 -2.457820 0.000000 C -0.759395 -3.138289 0.000000 C 0.173814 -2.140107 0.000000 C -0.034828 0.367232 0.000000 C 1.422006 0.642818 0.000000 C 1.835963 2.059906 0.000000 C 0.919425 3.063309 0.000000 C -0.478513 2.762755 0.000000 C -0.922061 1.428745 0.000000 N -1.837717 -1.157969 0.000000 N -0.508822 -0.952061 0.000000 N 2.313974 -0.242745 0.000000 H -1.199092 3.557555 0.000000 H -0.580804 -4.192276 0.000000 H 2.892067 2.247562 0.000000 H 1.243787 4.087627 0.000000 H -2.992215 -2.867674 0.000000 H -1.970884 1.216654 0.000000 H 1.237608 -2.180609 0.000000 ---------------------------------------------------------- TS: 13a (NN) <--> 2a (NN) (diradicaloid) singlet CASSCF energy: -508.2098849779 CASPT2 energy: -509.6653330577 Reference weight: 0.66762 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.83640 0.69957 3 222222020000 -0.35901 0.12889 Natural orbitals and occupation numbers for root 1 sym 1: 1.921658 1.987843 1.949824 1.914442 1.913217 1.994146 1.649206 0.358603 0.092485 0.078233 0.083327 0.057016 C -2.498613 0.163107 1.018207 C -3.052399 -0.565502 0.054746 C -2.347937 -0.838954 -1.209503 C -1.011836 -0.583018 -1.352357 C -0.313085 -0.015236 -0.236767 C -1.163066 0.716238 0.724681 C 2.919741 -0.340377 0.874494 C 3.232795 -0.072108 -0.485036 C 2.013526 0.086676 -1.082878 N 1.069843 -0.092827 -0.115216 N -0.726408 1.897174 0.736808 N 1.623460 -0.346317 1.079230 H -4.041458 -0.969460 0.174924 H -2.891885 -1.315087 -2.003569 H -0.484045 -0.906801 -2.230744 H 3.589110 -0.529102 1.688038 H 4.198060 0.000046 -0.938974 H 1.741883 0.326639 -2.088022 H -2.996822 0.390449 1.941625 ---------------------------------------------------------- TS: 13a (NH) <--> 2a (NH) (diradicaloid) singlet CASSCF energy: -508.2116780065 CASPT2 energy: -509.6690929979 Reference weight: 0.66707 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.85494 0.73093 3 222222020000 -0.33037 0.10914 Natural orbitals and occupation numbers for root 1 sym 1: 1.993778 1.988014 1.930927 1.949291 1.914452 1.903910 1.718341 0.292139 0.101828 0.082695 0.067241 0.057384 C 2.533745 0.973251 -0.375817 C 3.052250 -0.266776 -0.504676 C 2.295237 -1.456316 -0.081257 C 0.994847 -1.404742 0.225435 C 0.321747 -0.125494 0.086620 C 1.183352 1.062831 0.207181 C -3.043826 -0.797368 0.019726 C -3.120437 0.531875 -0.478753 C -1.824023 0.959895 -0.500571 N -1.056372 -0.073137 -0.040724 N 0.726808 1.787172 1.134213 N -1.805317 -1.140949 0.279632 H 4.050646 -0.406261 -0.876935 H 2.817692 -2.394674 -0.039812 H 0.435633 -2.281235 0.484926 H -3.838127 -1.493416 0.192755 H -3.992291 1.078139 -0.769135 H -1.390380 1.896432 -0.769893 H 3.087849 1.863773 -0.605831 ---------------------------------------------------------- 13a (NH) CASSCF energy: -508.2231875685 CASPT2 energy: -509.6902445927 Reference weight: 0.67074 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89790 0.80623 Natural orbitals and occupation numbers for root 1 sym 1: 1.933088 1.996614 1.904568 1.988018 1.918314 1.887671 1.951334 0.119686 0.095598 0.085569 0.063559 0.055982 C -2.402036 0.466307 1.152344 C -2.928065 -0.552636 0.429175 C -2.281488 -1.070459 -0.788745 C -1.036787 -0.708796 -1.195218 C -0.303356 0.282896 -0.372881 C -1.183969 0.965261 0.535466 C 2.749396 -0.909464 0.747629 C 3.259812 0.098203 -0.107470 C 2.139696 0.692223 -0.629695 N 1.070198 0.055217 -0.089880 N -0.765370 1.706679 -0.397397 N 1.432929 -0.922638 0.745238 H 2.011330 1.505686 -1.310605 H -2.827581 0.862770 2.052105 H 3.289352 -1.606865 1.354578 H 4.281945 0.347059 -0.299293 H -3.853511 -1.006133 0.734538 H -2.825386 -1.809451 -1.348792 H -0.564675 -1.185055 -2.035351 ---------------------------------------------------------- 13a (NN) CASSCF energy: -508.2209644054 CASPT2 energy: -509.6876082381 Reference weight: 0.67076 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89683 0.80431 Natural orbitals and occupation numbers for root 1 sym 1: 1.932740 1.988121 1.901445 1.996465 1.887078 1.951081 1.918105 0.119867 0.098703 0.086324 0.063813 0.056260 C -2.433459 0.133172 1.214749 C -2.917470 -0.728167 0.286834 C -2.244497 -0.955378 -1.006356 C -1.010935 -0.476669 -1.310875 C -0.314410 0.332807 -0.279860 C -1.220375 0.785403 0.737770 C 3.117993 -0.055995 -0.462399 C 2.960688 -0.582746 0.843611 C 1.613394 -0.492350 1.078294 N 1.055328 0.059536 -0.029451 N -0.831171 1.717733 -0.021386 N 1.965195 0.323649 -0.970446 H 1.018651 -0.767409 1.922942 H -2.891444 0.330533 2.163300 H 4.016541 0.055959 -1.033421 H 3.714992 -0.964449 1.498381 H -3.831942 -1.261421 0.473864 H -2.764606 -1.568134 -1.720363 H -0.521114 -0.726947 -2.233209 ---------------------------------------------------------- TS: 2a (NN) <--> 14a (NN) (diradicaloid) singlet CASSCF energy: -508.2148138626 CASPT2 energy: -509.6707145485 Reference weight: 0.66801 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.85718 0.73475 Natural orbitals and occupation numbers for root 1 sym 1: 1.923988 1.990169 1.949481 1.917190 1.913735 1.723276 1.993266 0.281719 0.090306 0.082336 0.077289 0.057245 C -2.077504 1.093893 -0.311037 C -2.982811 -0.813666 0.310660 C -3.295021 0.496857 -0.139756 C 0.256322 0.308187 0.046034 C 0.914835 1.466829 0.087142 C 2.381992 1.515011 0.032026 C 3.152195 0.392043 0.160993 C 2.478665 -0.854329 0.375727 C 1.092672 -0.902088 -0.060996 N -1.131936 0.167863 0.022234 N -1.686729 -0.993190 0.402147 N 1.122250 -1.848269 -0.893849 H 4.223914 0.461080 0.200765 H 2.841673 2.481568 -0.058158 H 0.385806 2.400107 0.144708 H -3.650810 -1.611108 0.561525 H -4.259815 0.919444 -0.323311 H -1.811088 2.063985 -0.668450 H 2.963759 -1.748250 0.703013 ---------------------------------------------------------- TS: 2a (NH) <--> 14a (NH) (diradicaloid) singlet CASSCF energy: -508.2182931677 CASPT2 energy: -509.6760747864 Reference weight: 0.66772 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.86357 0.74576 Natural orbitals and occupation numbers for root 1 sym 1: 1.925846 1.989879 1.919426 1.950220 1.914275 1.744058 1.993348 0.261088 0.080882 0.089494 0.074812 0.056672 C 1.838307 1.072043 0.069373 C 3.160480 -0.684479 -0.000662 C 3.162296 0.734884 0.047040 C -0.253556 -0.256503 0.013334 C -0.890335 -1.422285 -0.106395 C -2.354441 -1.488673 -0.142714 C -3.149290 -0.412088 0.144393 C -2.497303 0.805365 0.520366 C -1.119011 0.936940 0.075153 N -1.198301 1.989070 -0.615495 N 1.131046 -0.097155 0.036458 N 1.939891 -1.165156 -0.006360 H -4.218444 -0.509632 0.188903 H -2.797310 -2.442847 -0.359986 H -0.328287 -2.329939 -0.204835 H 3.996274 -1.352592 -0.027420 H 4.003367 1.394359 0.064666 H 1.351343 2.021282 0.105608 H -2.987687 1.632488 0.985887 ---------------------------------------------------------- 14a (NN) CASSCF energy: -508.2186691044 CASPT2 energy: -509.6835716774 Reference weight: 0.67074 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89633 0.80341 Natural orbitals and occupation numbers for root 1 sym 1: 1.935438 1.987960 1.898265 1.949765 1.996523 1.915120 1.890078 0.120602 0.103725 0.084880 0.056582 0.061062 C -2.145166 1.142506 0.164085 C -3.069332 -0.845145 -0.035370 C -3.369134 0.532631 0.132226 C 0.176313 0.277704 -0.046892 C 0.885893 1.415515 -0.245426 C 2.356457 1.422971 -0.204011 C 3.115186 0.367442 0.191428 C 2.422468 -0.886506 0.564670 C 1.047688 -0.879784 0.125256 N 1.753089 -1.667435 -0.558259 N -1.211020 0.160113 0.018851 N -1.774383 -1.049410 -0.100927 H 4.181572 0.468026 0.286826 H 2.832935 2.350081 -0.467416 H 0.388233 2.346064 -0.445939 H -3.744184 -1.672768 -0.103413 H -4.329487 0.992814 0.226879 H -1.869316 2.165819 0.293626 H 2.750308 -1.456600 1.415045 ---------------------------------------------------------- 14a (NH) CASSCF energy: -508.2211684628 CASPT2 energy: -509.6862222337 Reference weight: 0.67082 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89636 0.80346 Natural orbitals and occupation numbers for root 1 sym 1: 1.934593 1.987641 1.899337 1.950389 1.996480 1.916202 1.888688 0.122553 0.102580 0.084438 0.056127 0.060972 C -1.945405 -1.026533 0.065397 C -3.209830 0.772897 0.063367 C -3.259114 -0.645120 0.085224 C 0.185473 0.221944 -0.024742 C 0.896792 1.347262 -0.274470 C 2.368329 1.332248 -0.295223 C 3.132754 0.276800 0.090208 C 2.439427 -0.948149 0.552693 C 1.052235 -0.934968 0.169374 N 1.709315 -1.784052 -0.493420 N -1.203518 0.117170 0.037959 N -1.971862 1.212172 0.034472 H 4.204051 0.360668 0.126549 H 2.845488 2.242732 -0.610247 H 0.385184 2.267569 -0.476900 H -4.022232 1.469575 0.071936 H -4.121528 -1.276113 0.111968 H -1.483883 -1.990368 0.062982 H 2.789728 -1.475812 1.421386 ---------------------------------------------------------- TS: 2a (NN) <--> 5a CASSCF energy: -508.1965375392 CASPT2 energy: -509.6731795513 Reference weight: 0.66540 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.88456 0.78245 Natural orbitals and occupation numbers for root 1 sym 1: 1.982486 1.985583 1.954552 1.948389 1.919591 1.902299 1.833201 0.174032 0.111699 0.048994 0.081726 0.057450 C 1.782509 2.692367 -0.018113 C 0.458318 2.313205 -0.017229 C 2.509424 1.487384 -0.120693 C -0.560945 -0.002491 -0.010158 C 0.007969 -1.295955 0.178308 C -0.868192 -2.414768 0.097171 C -2.239505 -2.205836 0.034665 C -2.771614 -0.915556 -0.113520 C -1.919939 0.193596 -0.180137 N 0.440045 0.962244 -0.117708 N 1.675657 0.467288 -0.199721 N 1.273987 -1.435045 0.478351 H -2.316195 1.175943 -0.361702 H -3.830921 -0.779264 -0.225378 H -0.453006 -3.401709 0.166754 H -2.901639 -3.052485 0.047390 H 3.564629 1.328352 -0.177444 H -0.441962 2.880507 0.071310 H 2.169671 3.688127 0.025686 ---------------------------------------------------------- 5a CASSCF energy: -508.2643814524 CASPT2 energy: -509.7513396026 Reference weight: 0.67094 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 222222222222 Coeff Weight 1 222222200000 0.90578 0.82043 Natural orbitals and occupation numbers for root 1 sym 2: 1.988517 1.967066 1.974783 1.948153 1.929833 1.914516 1.890974 0.118901 0.087788 0.081625 0.061574 0.036268 C 0.552197 2.359030 0.000000 C -0.686005 0.059946 0.000000 C -2.096984 -2.286674 0.000000 C 0.017586 -1.156234 0.000000 C -2.081123 0.150420 0.000000 C -2.781216 -1.045050 0.000000 C -0.716482 -2.363494 0.000000 C 2.497437 1.227120 0.000000 C 1.927522 2.508087 0.000000 N 1.358966 -0.969991 0.000000 N 1.476168 0.352822 0.000000 N 0.309171 1.017476 0.000000 H -2.586815 1.098412 0.000000 H -3.855439 -1.033073 0.000000 H -0.205198 -3.307561 0.000000 H -2.672953 -3.194531 0.000000 H 3.507003 0.886490 0.000000 H -0.246048 3.065920 0.000000 H 2.462506 3.433578 0.000000 ---------------------------------------------------------- TS: 2a (NH) <--> 17 CASSCF energy: -508.1927272444 CASPT2 energy: -509.6739713310 Reference weight: 0.66090 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.86020 0.73994 Natural orbitals and occupation numbers for root 1 sym 1: 1.944038 1.978691 1.918948 1.948459 1.874717 1.991624 1.767306 0.250296 0.132059 0.063224 0.075889 0.054749 C -1.913485 0.252231 0.085041 C -0.523547 0.001929 0.087774 C 0.022548 -1.328069 -0.035010 C -0.930295 -2.429588 -0.047751 C -2.262223 -2.155770 -0.090359 C -2.756237 -0.799578 -0.013092 C 1.770491 0.490061 0.450837 C 2.576066 1.584998 0.091416 C 1.680528 2.573439 -0.297602 N 1.296043 -1.500079 -0.217133 N 0.459761 0.927506 0.201289 N 0.399872 2.172748 -0.238179 H -2.267144 1.263047 0.155101 H -3.818201 -0.637262 -0.011286 H -0.551630 -3.432861 -0.090079 H -2.973465 -2.959256 -0.148968 H 3.636286 1.662916 0.198481 H 1.893508 3.571641 -0.620597 H 1.945122 -0.146117 1.293320 ---------------------------------------------------------- 17 CASSCF energy: -508.2450979211 CASPT2 energy: -509.7241830636 Reference weight: 0.66786 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.85489 0.73085 Natural orbitals and occupation numbers for root 1 sym 1: 1.952539 1.998190 1.983342 1.924216 1.916228 1.895994 1.739082 0.278098 0.096941 0.090661 0.081515 0.043193 C 1.796745 2.434165 -0.296314 C 1.616600 0.275317 0.362892 C 2.529592 1.289686 -0.256855 C -0.636401 0.086802 0.165750 C 0.042884 -1.183714 0.038837 C -0.765400 -2.369696 -0.121378 C -2.120597 -2.227368 -0.189255 C -2.767994 -0.935337 -0.100099 C -2.043758 0.216773 0.070673 N 0.445447 2.264049 -0.014388 N 0.344657 0.992144 0.263279 N 1.349487 -1.096136 0.031847 H -2.508987 1.182110 0.129343 H -3.838728 -0.890494 -0.172481 H -0.288224 -3.328281 -0.196458 H -2.739884 -3.096777 -0.316318 H 3.591250 1.194025 -0.342606 H 2.134166 3.419488 -0.544143 H 1.883338 0.242973 1.420620 ---------------------------------------------------------- TS: 17 <--> 7 CASSCF energy: -508.2044682657 CASPT2 energy: -509.7015678245 Reference weight: 0.66577 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89633 0.80341 Natural orbitals and occupation numbers for root 1 sym 1: 1.962659 1.980985 1.993632 1.945609 1.917636 1.907262 1.866679 0.143595 0.091437 0.088067 0.065679 0.036760 C -3.007300 -0.657456 -0.091963 C -1.387131 0.826243 0.089766 C -2.788953 0.721254 -0.106935 C 0.434864 -0.471523 0.030054 C 0.796571 0.887248 -0.012583 C 2.161187 1.249003 -0.026798 C 3.098877 0.235067 -0.043347 C 2.713826 -1.132035 -0.018439 C 1.383652 -1.506770 0.026348 N -1.886230 -1.389442 0.012837 N -0.929905 -0.480390 0.110608 N -0.292714 1.732016 -0.040305 H 1.078672 -2.535166 0.054039 H 3.476376 -1.889007 -0.030796 H 2.444995 2.284331 -0.044469 H 4.144882 0.479552 -0.074642 H -3.504188 1.512120 -0.159092 H -3.949065 -1.162651 -0.153450 H -1.046056 1.427374 1.085664 ---------------------------------------------------------- 7 CASSCF energy: -508.3258996474 CASPT2 energy: -509.7993455955 Reference weight: 0.67535 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 222222222222 Coeff Weight 1 222222200000 0.91233 0.83235 Natural orbitals and occupation numbers for root 1 sym 2: 1.986178 1.994380 1.963990 1.959036 1.927889 1.903049 1.906782 0.104367 0.094535 0.074234 0.049422 0.036138 C -0.880214 -0.829315 0.000000 C 1.146852 -2.720108 0.000000 C -1.232546 -2.173278 0.000000 C 0.471430 -0.442233 0.000000 C 1.503377 -1.367886 0.000000 C -0.196822 -3.113844 0.000000 C -0.815428 1.410799 0.000000 C -0.747704 2.784392 0.000000 C 0.657041 3.019317 0.000000 N -1.658140 0.325021 0.000000 N 0.454160 0.944305 0.000000 N 1.377371 1.911479 0.000000 H -2.261904 -2.482587 0.000000 H 2.528492 -1.050590 0.000000 H -0.440593 -4.160501 0.000000 H 1.917681 -3.468600 0.000000 H -2.648503 0.363030 0.000000 H -1.538676 3.502282 0.000000 H 1.153765 3.967855 0.000000 -------------------------------------------------------------- 2-[1-(3,5-dimethylpyrazolyl]phenylnitrene 2b and products -------------------------------------------------------------- 2b (NN) triplet CASSCF energy: -586.3282557094 CASPT2 energy: -588.0536350051 Reference weight: 0.62954 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.91059 0.82918 Natural orbitals and occupation numbers for root 1 sym 1: 1.989546 1.993641 1.931322 1.909079 1.918622 1.951815 1.001698 1.000021 0.093982 0.085032 0.070440 0.054802 C -0.755871 2.360498 1.160086 C 0.783878 0.074400 -0.199776 C -2.634251 -0.454959 -0.340808 C -3.784458 -1.319959 -0.759650 C -2.671153 0.787853 0.350685 C -1.362177 1.165669 0.490856 C 3.570413 -0.157433 -0.381587 C 1.464536 -0.906609 0.578628 C 1.489742 0.899173 -1.027870 C 2.884746 0.801329 -1.124789 C 2.869890 -1.010815 0.463906 N -1.394784 -0.801886 -0.599457 N -0.623588 0.181189 -0.102890 N 0.802366 -1.714882 1.430354 H -3.533884 1.316614 0.700501 H -3.416557 -2.208132 -1.257200 H -4.444591 -0.792364 -1.441445 H -4.374524 -1.627027 0.098269 H -0.250494 3.010153 0.453345 H -0.034374 2.068000 1.915688 H -1.535335 2.935203 1.644075 H 0.958486 1.621189 -1.620228 H 3.417787 1.460406 -1.784432 H 3.379688 -1.754296 1.047688 H 4.638721 -0.239528 -0.461249 ---------------------------------------------------------- 2b (NMe) triplet CASSCF energy: -586.3296687432 CASPT2 energy: -588.0574655025 Reference weight: 0.62898 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 106 2222u22u0000 0.91191 0.83159 Natural orbitals and occupation numbers for root 1 sym 1: 1.989188 1.993238 1.913374 1.930716 1.000018 1.918676 1.952145 1.002033 0.092215 0.083048 0.070730 0.054620 C -2.565127 -0.575313 0.775444 C -2.751366 0.071934 -0.476574 C -1.496585 0.423539 -0.897983 C 0.760027 0.156606 0.174308 C 1.283310 0.833615 1.244647 C 2.661853 1.001283 1.384133 C 3.533978 0.486436 0.422889 C 3.027081 -0.209853 -0.664505 C 1.630766 -0.403791 -0.802701 C -3.603080 -1.168992 1.679281 C -1.063830 1.173688 -2.120458 N -1.291393 -0.609133 1.090836 N -0.638684 -0.018444 0.072617 N 1.164631 -1.133591 -1.835047 H 4.594556 0.622791 0.526941 H 3.046687 1.536381 2.232296 H 0.611297 1.228556 1.982623 H -3.674408 0.258737 -0.985798 H 3.678257 -0.629730 -1.408314 H -3.135265 -1.559922 2.573887 H -4.338637 -0.425922 1.971926 H -4.132348 -1.979355 1.187613 H -0.595346 0.522702 -2.848504 H -1.930164 1.629901 -2.582847 H -0.361565 1.963020 -1.873297 ---------------------------------------------------------- 2b (NN) open-shell singlet --> relaxes to 2b (NMe) ---------------------------------------------------------- 2b (NMe) open-shell singlet CASSCF energy: -586.3005047244 CASPT2 energy: -588.0236966449 Reference weight: 0.62669 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 -0.63600 0.40449 1072 222202220000 0.64874 0.42086 Natural orbitals and occupation numbers for root 1 sym 1: 1.990215 1.996386 1.903780 1.929278 0.983914 1.918360 1.952131 1.021111 0.098637 0.083858 0.067658 0.054672 C -2.579928 -0.580211 0.770649 C -2.763859 0.067858 -0.481629 C -1.510138 0.435199 -0.891283 C 0.740247 0.193365 0.188135 C 1.271006 0.857904 1.215023 C 2.701364 1.009011 1.370313 C 3.573213 0.464243 0.403217 C 3.075906 -0.224476 -0.674943 C 1.623254 -0.436825 -0.825057 C -3.618316 -1.189637 1.663538 C -1.071481 1.187635 -2.109808 N -1.308901 -0.599505 1.097279 N -0.655148 0.005027 0.086823 N 1.174130 -1.159505 -1.770693 H 4.634502 0.593217 0.511476 H 3.085241 1.548802 2.213569 H 0.617074 1.278990 1.955303 H -3.684638 0.241863 -0.999505 H 3.717336 -0.653685 -1.419848 H -3.152783 -1.582337 2.558588 H -4.362805 -0.455555 1.956500 H -4.136751 -2.001502 1.162872 H -0.572516 0.542078 -2.822125 H -1.937905 1.621702 -2.592878 H -0.392254 1.994298 -1.852983 ---------------------------------------------------------- TS 2b (NMe) <--> 13b (NMe) (diradicaloid) singlet CASSCF energy: -586.2929381669 CASPT2 energy: -588.0111481069 Reference weight: 0.63086 printout of CI-coefficients larger than 0.05 for root 1 energy= -586.292938 conf/sym 111111111111 Coeff Weight 1 222222200000 0.82159 0.67501 3 222222020000 -0.37330 0.13935 Natural orbitals and occupation numbers for root 1 sym 1: 1.936909 1.995779 1.915010 1.886558 1.935303 1.994091 1.608499 0.398463 0.117465 0.067021 0.084382 0.060519 C 2.484723 -0.379549 0.930245 C 2.797730 0.070232 -0.389277 C 1.605189 0.225658 -1.008144 C -0.742257 -0.091594 -0.213160 C -1.464939 -0.925766 -1.114119 C -2.808722 -1.121312 -0.898792 C -3.496350 -0.513730 0.241122 C -2.903946 0.440178 0.995480 C -1.565415 0.870892 0.557483 C 3.433017 -0.701520 2.044339 C 1.280080 0.722240 -2.381165 N 1.191652 -0.482847 1.087136 N 0.648915 -0.130727 -0.102861 N -1.104428 2.014411 0.299458 H -4.495366 -0.840841 0.464880 H -3.358600 -1.796341 -1.527577 H -0.945590 -1.488344 -1.867867 H 3.767416 0.255944 -0.803098 H -3.389900 0.914941 1.826237 H 2.186709 1.054869 -2.869495 H 0.832328 -0.051604 -2.996168 H 0.589010 1.556704 -2.335646 H 2.884909 -1.061683 2.905467 H 4.144688 -1.464309 1.743830 H 3.998239 0.177349 2.339515 ---------------------------------------------------------- 13b (NMe) CASSCF energy: -586.3006295904 CASPT2 energy: -588.0308788702 Reference weight: 0.63298 printout of CI-coefficients larger than 0.05 for root 1 energy= -586.300630 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89793 0.80628 Natural orbitals and occupation numbers for root 1 sym 1: 1.933106 1.989904 1.901591 1.996473 1.887572 1.952199 1.918811 0.119094 0.098895 0.084054 0.063557 0.054744 C 0.464743 0.081120 -1.584599 C -1.602593 -0.384875 -2.246806 C -0.274480 -0.168487 -2.710108 C -0.149952 0.114696 0.852369 C -0.019697 -1.144563 1.628193 C 0.987825 -1.230480 2.535105 C 1.962059 -0.151378 2.782293 C 1.822820 1.086524 2.247842 C 0.600912 1.182076 1.460063 C -2.827495 -0.699102 -3.051718 C 1.924248 0.376248 -1.425890 N -0.410870 0.024020 -0.538039 N -1.657338 -0.271807 -0.940239 N -0.646600 1.323000 1.589618 H 2.797439 -0.369464 3.422821 H 1.123657 -2.140877 3.090674 H -0.661960 -1.980848 1.422124 H 0.078530 -0.191759 -3.720743 H 2.506912 1.897456 2.399297 H 2.420645 0.260336 -2.381116 H 2.094917 1.392524 -1.084731 H 2.395529 -0.297818 -0.718572 H -3.053015 0.100706 -3.750497 H -2.695626 -1.610391 -3.627187 H -3.678098 -0.828003 -2.394645 ---------------------------------------------------------- 13b (NN) CASSCF energy: -586.3016589895 CASPT2 energy: -588.0321627503 Reference weight: 0.63303 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89877 0.80779 Natural orbitals and occupation numbers for root 1 sym 1: 1.932916 1.989380 1.904697 1.996630 1.887232 1.952652 1.919762 0.120047 0.095225 0.083110 0.063779 0.054571 C 2.302708 -0.855067 0.787129 C 2.820436 0.004992 -0.218101 C 1.724750 0.616731 -0.772272 C -0.731378 0.387565 -0.328818 C -1.469969 -0.435228 -1.320105 C -2.684957 -0.923651 -0.959981 C -3.298504 -0.698710 0.360865 C -2.775668 0.167022 1.262844 C -1.599945 0.832588 0.724402 C 1.628079 1.631848 -1.873735 C 3.056540 -1.761665 1.713109 N 0.991995 -0.770926 0.835538 N 0.643725 0.123085 -0.103179 N -1.244603 1.770203 -0.040549 H -3.177018 0.351393 2.238890 H 3.846680 0.154670 -0.485350 H -4.195017 -1.243640 0.594736 H -3.227013 -1.549639 -1.645731 H -1.021199 -0.706213 -2.259024 H 0.601540 1.896275 -2.087136 H 2.150089 2.542207 -1.600229 H 2.078631 1.251174 -2.784094 H 2.365469 -2.290476 2.357340 H 3.637038 -2.493194 1.159186 H 3.745615 -1.200444 2.336931 ---------------------------------------------------------- TS: 2b (NMe) <--> 14b (NMe) CASSCF energy: -586.2962499734 CASPT2 energy: -588.0176047937 Reference weight: 0.63183 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.85594 0.73264 Natural orbitals and occupation numbers for root 1 sym 1: 1.937000 1.993179 1.917676 1.892607 1.938757 1.995756 1.730214 0.276810 0.112302 0.067156 0.081473 0.057071 C -2.561971 -0.789795 0.516137 C -2.840649 0.377152 -0.254418 C -1.636986 0.945805 -0.502448 C 0.693147 0.259255 0.136083 C 1.386089 1.393744 0.391310 C 2.849877 1.428684 0.300588 C 3.598662 0.289095 0.182955 C 2.906889 -0.969276 0.174744 C 1.511481 -0.909153 -0.223876 C -3.531463 -1.793295 1.060874 C -1.306762 2.167783 -1.302333 N -1.275223 -0.910531 0.713906 N -0.705263 0.152552 0.103007 N 1.538214 -1.668005 -1.231119 H 4.672400 0.333891 0.201968 H 3.330350 2.385891 0.384482 H 0.870634 2.300887 0.643634 H -3.795659 0.726266 -0.589302 H 3.380370 -1.912193 0.341351 H -2.169954 2.450212 -1.890860 H -1.046418 3.009210 -0.669098 H -0.478137 1.987214 -1.977400 H -2.998488 -2.577637 1.582589 H -4.226377 -1.328686 1.753735 H -4.113889 -2.243964 0.263298 ---------------------------------------------------------- 14b (NN) CASSCF energy: -586.2969300386 CASPT2 energy: -588.0257966915 Reference weight: 0.63281 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89803 0.80646 Natural orbitals and occupation numbers for root 1 sym 1: 1.935557 1.989466 1.899156 1.951195 1.996523 1.917449 1.890865 0.118120 0.102533 0.083042 0.061147 0.054945 C -2.619778 -0.880222 -0.129431 C -2.911779 0.467419 0.227240 C -1.702707 1.104784 0.286824 C 0.625253 0.243318 -0.124298 C 1.362614 1.314164 -0.510721 C 2.832975 1.298373 -0.468203 C 3.571474 0.307787 0.097355 C 2.854988 -0.855837 0.664026 C 1.478924 -0.890650 0.224024 C -3.574873 -2.017765 -0.326799 C -1.393184 2.522763 0.658403 N -1.328265 -1.044109 -0.274114 N -0.764334 0.154725 -0.032709 N 2.167647 -1.791337 -0.321359 H 4.639513 0.403293 0.180123 H 3.327517 2.160045 -0.879510 H 0.885883 2.205628 -0.868756 H -3.871570 0.896325 0.429722 H 3.172756 -1.289996 1.594854 H -3.029651 -2.919125 -0.575014 H -4.153902 -2.201506 0.572875 H -4.273215 -1.805684 -1.130360 H -0.556342 2.583947 1.344442 H -1.162945 3.132200 -0.209087 H -2.258836 2.955659 1.143592 ---------------------------------------------------------- 14b (NMe) CASSCF energy: -586.2997304073 CASPT2 energy: -588.0292639837 Reference weight: 0.63279 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89778 0.80600 Natural orbitals and occupation numbers for root 1 sym 1: 1.934720 1.989428 1.900097 1.951485 1.996556 1.917843 1.889103 0.120864 0.101215 0.082808 0.061368 0.054514 C 0.962451 -0.492906 1.431786 C -0.163175 -0.005812 0.635294 C -1.234528 0.270542 1.419807 C -1.211247 0.045077 2.871994 C -0.219757 -0.610628 3.530913 C 0.926374 -1.105893 2.737039 C 0.911058 0.372353 -1.592026 C 0.380483 0.449967 -2.850113 C -1.015152 0.214274 -2.692647 C -2.075937 0.178071 -3.750419 C 2.325909 0.556372 -1.134059 N -0.142819 0.091906 -0.757982 N -1.305865 0.008510 -1.431440 N 1.890562 -0.071071 2.172942 H -0.306543 -0.822928 4.581449 H -2.067344 0.396323 3.419558 H -2.130574 0.655275 0.973844 H 0.911571 0.649473 -3.757880 H 1.335335 -2.082540 2.924010 H -2.128151 1.122802 -4.282603 H -1.873439 -0.599694 -4.480132 H -3.041225 -0.016813 -3.301015 H 2.918943 0.915652 -1.965526 H 2.400698 1.278346 -0.329299 H 2.764837 -0.372600 -0.787665 ---------------------------------------------------------- TS: 2b (NN) <--> 5b CASSCF energy: -586.2762653258 CASPT2 energy: -588.0170051871 Reference weight: 0.62790 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.88305 0.77978 Natural orbitals and occupation numbers for root 1 sym 1: 1.986977 1.983559 1.954773 1.948811 1.920201 1.902145 1.823836 0.183575 0.109891 0.081247 0.055767 0.049217 C 2.249258 1.168921 -0.169080 C 1.513197 2.364638 0.009632 C 0.185604 2.002301 0.042007 C -0.815453 -0.343817 -0.003364 C -0.212536 -1.630570 0.175705 C -1.054305 -2.775796 0.103758 C -2.433323 -2.612597 0.063836 C -3.000087 -1.340011 -0.081978 C -2.182766 -0.202418 -0.164732 C 3.727739 0.966222 -0.295064 C -1.028736 2.852731 0.246995 N 1.407257 0.161987 -0.262976 N 0.163605 0.647759 -0.122000 N 1.054560 -1.745366 0.466292 H -2.623463 0.756237 -0.352874 H -4.063946 -1.232193 -0.183165 H -0.603782 -3.747781 0.164385 H -3.069720 -3.478600 0.087039 H 1.901046 3.359832 0.084871 H 3.951982 -0.091172 -0.346534 H 4.114330 1.444290 -1.189614 H 4.249159 1.386823 0.558236 H -0.715820 3.863502 0.475521 H -1.652220 2.890961 -0.640050 H -1.633495 2.494569 1.073023 ---------------------------------------------------------- 5b (heteropentalene) CASSCF energy: -586.3460905008 CASPT2 energy: -588.0976229563 Reference weight: 0.63287 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 222222222222 Coeff Weight 1 222222200000 0.90670 0.82210 Natural orbitals and occupation numbers for root 1 sym 2: 1.989173 1.967435 1.975492 1.949059 1.930725 1.914074 1.891750 0.117266 0.087854 0.081520 0.059625 0.036027 C -2.341403 -0.172738 0.000000 C -0.945927 -0.253422 0.000000 C -0.237831 -1.469419 0.000000 C -0.968079 -2.678218 0.000000 C -2.349648 -2.608916 0.000000 C -3.037972 -1.371666 0.000000 C 2.247506 0.905693 0.000000 C 1.668679 2.186920 0.000000 C 0.289764 2.054022 0.000000 C -0.811237 3.063356 0.000000 C 3.662529 0.431252 0.000000 N 1.102989 -1.283181 0.000000 N 1.218432 0.044443 0.000000 N 0.049732 0.709972 0.000000 H -2.854874 0.770218 0.000000 H -4.112312 -1.362463 0.000000 H -0.452213 -3.619935 0.000000 H -2.921045 -3.519816 0.000000 H 2.206043 3.112454 0.000000 H 4.333632 1.281247 0.000000 H 3.873075 -0.173843 0.875614 H 3.873075 -0.173843 -0.875614 H -0.385859 4.058957 0.000000 H -1.442394 2.969791 0.878806 H -1.442394 2.969791 -0.878806 ---------------------------------------------------------- TS: 2b (NMe) <--> 18 singlet CASSCF energy: -586.2413513891 CASPT2 energy: -588.0000277920 Reference weight: 0.62471 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.89446 0.80006 Natural orbitals and occupation numbers for root 1 sym 1: 1.939250 1.989175 1.986759 1.950494 1.913941 1.929422 1.858507 0.166788 0.084903 0.067821 0.054421 0.058519 C -1.311577 1.103314 0.253095 C -2.650719 0.825432 0.197051 C -2.725170 -0.570397 -0.078691 C 0.730409 -0.314207 0.019648 C 1.641285 0.758139 -0.263561 C 3.023331 0.494480 -0.138872 C 3.494061 -0.800404 0.084512 C 2.586417 -1.818607 0.333673 C 1.205728 -1.551963 0.338002 C -0.580591 2.363535 0.503658 C -3.949258 -1.415844 -0.258964 N -1.522162 -1.081687 -0.184777 N -0.658436 -0.069241 0.005925 N 1.325741 1.954992 -0.790201 H 4.551133 -0.992248 0.110194 H 2.927847 -2.813977 0.549933 H 0.507948 -2.335319 0.558992 H -3.459878 1.513413 0.328985 H 3.697347 1.315406 -0.293233 H -3.664340 -2.441245 -0.456053 H -4.571994 -1.396056 0.629992 H -4.550184 -1.060933 -1.090303 H 0.207348 2.422680 -0.444616 H -0.014244 2.398839 1.420761 H -1.183883 3.249414 0.367271 ---------------------------------------------------------- TS: 2b (NMe) <--> 18 triplet CASSCF energy: -586.2541781905 CASPT2 energy: -588.0269106621 Reference weight: 0.61779 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.90412 0.81743 Natural orbitals and occupation numbers for root 1 sym 1: 1.987046 1.989912 1.907889 1.949870 1.918129 1.929771 1.003977 1.011558 0.087863 0.095250 0.063657 0.055077 C -1.377084 1.145200 0.293728 C -2.694587 0.813725 0.103561 C -2.695908 -0.588574 -0.128878 C 0.731126 -0.226950 0.131314 C 1.675269 0.761625 -0.308421 C 3.053782 0.348592 -0.425734 C 3.466709 -0.890840 -0.099040 C 2.526288 -1.847571 0.366959 C 1.189705 -1.512367 0.469776 C -0.723133 2.420865 0.585380 C -3.868342 -1.486332 -0.384634 N -1.473246 -1.061975 -0.098764 N -0.661708 -0.014674 0.153906 N 1.441105 2.032810 -0.639865 H 4.503802 -1.159144 -0.186938 H 2.849192 -2.836005 0.635439 H 0.471715 -2.238556 0.791419 H -3.535798 1.473496 0.151229 H 3.740810 1.094836 -0.777628 H -3.527954 -2.497419 -0.567419 H -4.543300 -1.499156 0.465571 H -4.433390 -1.151727 -1.248736 H 0.374232 2.392687 -0.218577 H -0.243277 2.492374 1.551269 H -1.301729 3.295897 0.336850 ---------------------------------------------------------- 18 open-shell singlet CASSCF energy: -586.3089004085 CASPT2 energy: -588.0502329713 Reference weight: 0.62738 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.64059 0.41035 3 222222020000 -0.61450 0.37762 Natural orbitals and occupation numbers for root 1 sym 1: 1.989413 1.903917 1.941539 1.906302 1.994285 1.929778 1.038893 0.966794 0.070397 0.100072 0.096008 0.062602 C -2.984784 -0.986358 0.244346 C -3.260764 -0.312819 1.456669 C -2.306464 0.441804 2.050827 C -0.996383 0.594221 1.480636 C -0.722272 -0.126991 0.272627 C -1.722173 -0.889065 -0.330476 C 1.775396 -0.416712 0.099871 C 2.638837 -0.208791 -0.983456 C 1.834503 0.274819 -2.030036 C 2.241863 0.670472 -3.417782 C 2.058797 -0.963885 1.358032 N -0.060526 1.381211 2.004751 N 0.571263 0.366018 -1.643728 N 0.532296 -0.027922 -0.362005 H -3.745842 -1.580019 -0.226446 H -4.235166 -0.399771 1.902579 H -2.519505 0.962691 2.968372 H -1.499914 -1.395341 -1.249850 H 3.693300 -0.392152 -0.994744 H 2.727812 -0.151969 -3.933505 H 1.370556 0.965789 -3.988365 H 2.936604 1.504336 -3.399377 H 1.311762 -1.084586 2.113867 H 3.067217 -1.243862 1.588462 H -0.412238 1.826702 2.836287 ---------------------------------------------------------- 18 triplet CASSCF energy: -586.3087824120 CASPT2 energy: -588.0498829238 Reference weight: 0.62780 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.88906 0.79043 Natural orbitals and occupation numbers for root 1 sym 1: 1.989581 1.908472 1.941900 1.904436 1.994197 1.928902 1.004318 1.001277 0.071143 0.098989 0.094666 0.062119 C -2.990290 -0.993212 0.265655 C -3.261245 -0.293259 1.463006 C -2.302141 0.469862 2.039914 C -0.992591 0.603202 1.465542 C -0.724865 -0.141861 0.271437 C -1.727580 -0.913512 -0.312831 C 1.773344 -0.431783 0.096781 C 2.640181 -0.199078 -0.976724 C 1.834413 0.286781 -2.024144 C 2.246277 0.703850 -3.404207 C 2.053035 -0.984207 1.355427 N -0.048937 1.391003 1.976271 N 0.569253 0.352894 -1.646011 N 0.529003 -0.060848 -0.368918 H -3.754800 -1.592722 -0.191940 H -4.235324 -0.366067 1.912141 H -2.511675 1.010673 2.946688 H -1.508755 -1.439653 -1.221929 H 3.696468 -0.371746 -0.985615 H 2.754844 -0.103132 -3.922518 H 1.374326 0.985735 -3.980575 H 2.922732 1.552211 -3.371304 H 1.298795 -1.123412 2.101068 H 3.063073 -1.249327 1.595858 H -0.396995 1.854775 2.799321 ---------------------------------------------------------- TS: 18 <--> 8 open-shell singlet : not found, 18 collapses Spontaneously to 8 on unconstrained optimization ---------------------------------------------------------- TS: 18 <--> 8 triplet CASSCF energy: -586.2406634836 CASPT2 energy: -587.9998866886 Reference weight: 0.62027 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.89023 0.79252 Natural orbitals and occupation numbers for root 1 sym 1: 1.983188 1.983981 1.896996 1.952334 1.919011 1.925341 1.042304 0.968452 0.117969 0.085257 0.071672 0.053494 C 0.693228 -0.408916 -0.014146 C 3.502541 -0.724784 0.121452 C 1.609124 0.732050 -0.287133 C 1.214266 -1.693091 0.126908 C 2.593961 -1.880070 0.161192 C 3.033710 0.507223 -0.064882 C -0.370885 2.283428 0.474093 C -2.750639 -0.465681 -0.048572 C -4.032250 -1.228521 -0.196618 C -2.579153 0.928900 0.151367 C -1.219687 1.111606 0.250798 N -0.658178 -0.130011 0.084046 N 1.055181 1.883502 -0.655402 N -1.589233 -1.084549 -0.087512 H 0.543233 -2.520837 0.245392 H 3.002199 -2.864950 0.280850 H 3.695603 1.355571 -0.106812 H 4.556049 -0.894491 0.249689 H -3.340045 1.676081 0.240785 H 0.120334 2.337967 1.431807 H -0.810562 3.218734 0.171449 H 1.707196 2.646614 -0.685129 H -3.822077 -2.277194 -0.363901 H -4.613113 -0.856237 -1.034701 H -4.646294 -1.139545 0.694435 ---------------------------------------------------------- 8 (amine) CASSCF energy: -586.4172220039 CASPT2 energy: -588.1466224833 Reference weight: 0.63567 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222200000 0.92613 0.85772 Natural orbitals and occupation numbers for root 1 sym 1: 1.979157 1.971949 1.993222 1.955389 1.927057 1.939440 1.931984 0.089488 0.063415 0.067272 0.028613 0.053013 C 0.733984 -0.400977 0.026447 C 3.477564 -0.749829 -0.012500 C 1.567155 0.717524 -0.141200 C 1.260958 -1.674276 0.176299 C 2.646465 -1.850190 0.151567 C 2.932623 0.526770 -0.152702 C -0.273185 2.248207 0.328858 C -2.749249 -0.480366 -0.045371 C -4.045407 -1.226387 -0.151235 C -2.554831 0.919375 0.088838 C -1.193982 1.083534 0.131136 N -0.645943 -0.146738 0.032748 N 0.977986 1.969171 -0.356248 N -1.598217 -1.125580 -0.081672 H 0.593311 -2.504218 0.298300 H 3.060886 -2.835026 0.264066 H 3.580896 1.375973 -0.285433 H 4.545214 -0.872345 -0.028032 H -3.305190 1.680864 0.143345 H -0.128066 2.424340 1.396378 H -0.709994 3.142322 -0.095730 H 1.631046 2.720218 -0.291594 H -3.854678 -2.288518 -0.238263 H -4.611339 -0.908405 -1.021454 H -4.666681 -1.060749 0.723642 ---------------------------------------------------------- 8 triplet CASSCF energy: -586.2906278861 CASPT2 energy: -588.0175197288 Reference weight: 0.62917 printout of CI-coefficients larger than 0.05 for root 1 conf/sym 111111111111 Coeff Weight 1 222222uu0000 0.92128 0.84876 Natural orbitals and occupation numbers for root 1 sym 1: 1.976927 1.971364 1.997577 1.951499 1.926832 1.905626 1.028464 0.978554 0.096156 0.083682 0.029185 0.054135 C 0.708610 -0.404649 -0.226027 C 3.472235 -0.752953 0.198575 C 1.605863 0.772579 -0.153161 C 1.259543 -1.762003 -0.052742 C 2.592191 -1.907979 0.146431 C 2.911597 0.593175 0.047557 C -0.273975 2.268275 0.250435 C -2.742358 -0.485133 0.023983 C -4.040940 -1.233498 0.011217 C -2.540947 0.913214 0.154417 C -1.181222 1.085724 0.104961 N -0.632623 -0.149213 -0.041213 N 0.994612 1.999452 -0.412695 N -1.595503 -1.129771 -0.100491 H 0.586232 -2.592798 -0.108663 H 3.015823 -2.889245 0.259679 H 3.578080 1.437954 0.067749 H 4.517044 -0.874751 0.403029 H -3.288001 1.670855 0.272289 H -0.135792 2.492437 1.308669 H -0.727440 3.135491 -0.211688 H 1.631665 2.763855 -0.331479 H -3.855834 -2.292660 -0.114476 H -4.678284 -0.898573 -0.801307 H -4.586814 -1.089111 0.938589 ----------------------------------------------------------