Matrix isolation, time-resolved IR, and computational study of the photochemistry of benzoyl azide ------------------------------------------------------------- E.A. Pritchina, N.P. Gritsan, A. Maltsev, T. Bally, T. Autrey, Y. Liu, Y. Wang, and J.P. Toscano SUPPORTING INFORMATION, Part 1 ============================== A.) B3LYP/6-31G* optimized geometries, energies, and thermal corrections of all the stationary points discussed in this work [The results of the CASSCF/CASPT2-calculations on singlet and triplet formylnitrene, benzoylnitrene follow at the end of this file] ================================================== A1. triplet formylnitrene (HCON), 3-A" -------------------------------------------------- E(UB3LYP) = -168.551714, S**2 =2.0328 nuclear repulsion energy 56.587627 Zero-point correction= 0.018806 Thermal correction to Energy= 0.021982 Thermal correction to Enthalpy= 0.022926 Thermal correction to Gibbs Free Energy= -0.006110 6 0.000000 0.384816 0.000000 1 0.023919 1.491241 0.000000 7 1.206654 -0.248447 0.000000 8 -1.058812 -0.257627 0.000000 ================================================== A2. singlet formylnitrene (HCON), 1-A' -------------------------------------------------- E(RB3LYP) = -168.538747, S**2 =0.0000 nuclear repulsion energy 60.230184 Zero-point correction= 0.020077 Thermal correction to Energy= 0.023213 Thermal correction to Enthalpy= 0.024157 Thermal correction to Gibbs Free Energy= -0.003697 6 0.000000 0.581757 0.000000 1 -0.183058 1.654738 0.000000 7 0.958542 -0.235479 0.000000 8 -0.815842 -0.437116 0.000000 ================================================== A3. benzoyl azide (1b) -------------------------------------------------- E(RB3LYP) = -509.169330, S**2 =0.0000 nuclear repulsion energy 537.741255 Zero-point correction= 0.113737 Thermal correction to Energy= 0.122542 Thermal correction to Enthalpy= 0.123486 Thermal correction to Gibbs Free Energy= 0.078828 6 -2.555231 0.600663 0.568273 6 -2.818113 -0.674662 0.060190 6 -1.799797 -1.406565 -0.552854 6 -0.513168 -0.876261 -0.642470 6 -0.242729 0.398895 -0.125420 6 -1.277065 1.141424 0.464890 6 1.095496 1.057321 -0.229099 1 -3.348558 1.174640 1.038605 1 -3.817534 -1.094277 0.135625 1 -2.006407 -2.389686 -0.965829 1 0.262292 -1.446419 -1.144272 1 -1.058658 2.137524 0.835604 7 2.286596 0.246074 -0.235283 8 1.235399 2.253873 -0.334170 7 2.266029 -0.883023 0.282088 7 2.411562 -1.914146 0.740706 ================================================== A4. phenylizocyanate (2b), 1-A' -------------------------------------------------- State=1-A' E(RB3LYP) = -399.732507, S**2 =0.0000 nuclear repulsion energy 372.959931 Zero-point correction= 0.104062 Thermal correction to Energy= 0.111165 Thermal correction to Enthalpy= 0.112109 Thermal correction to Gibbs Free Energy= 0.071668 6 -1.136145 -1.862675 0.000000 6 -2.371686 -1.210928 0.000000 6 -2.415216 0.184541 0.000000 6 -1.236278 0.927936 0.000000 6 0.000000 0.271214 0.000000 6 0.049093 -1.130737 0.000000 7 1.161553 1.049757 0.000000 1 -1.091603 -2.948322 0.000000 1 -3.292482 -1.786894 0.000000 1 -3.371386 0.700386 0.000000 1 -1.256127 2.012905 0.000000 1 1.011351 -1.635176 0.000000 6 2.364561 0.929789 0.000000 8 3.542925 0.956745 0.000000 ================================================== A5. triplet benzoylnitrene, 3-A" -------------------------------------------------- State=3-A" E(UB3LYP) = -399.620892, S**2 = 2.0263 nuclear repulsion energy 379.081040 Zero-point correction= 0.101597 Thermal correction to Energy= 0.108717 Thermal correction to Enthalpy= 0.109661 Thermal correction to Gibbs Free Energy= 0.068491 6 -1.149218 -1.834699 0.000000 6 0.084339 -2.495255 0.000000 6 1.274846 -1.764522 0.000000 6 1.236193 -0.371538 0.000000 6 0.000000 0.292723 0.000000 6 -1.193572 -0.444183 0.000000 6 -0.071463 1.775004 0.000000 1 -2.072620 -2.406862 0.000000 1 0.116348 -3.581445 0.000000 1 2.231077 -2.279670 0.000000 1 2.158675 0.201946 0.000000 1 -2.138485 0.089888 0.000000 7 1.093548 2.517473 0.000000 8 -1.129572 2.426082 0.000000 ================================================== A6. singlet benzoylnitrene (3b), 1-A' -------------------------------------------------- State=1-A' E(RB+HF-LYP) = -399.612945, S**2 =0.0000 nuclear repulsion energy 380.243525 Zero-point correction= 0.102311 Thermal correction to Energy= 0.109523 Thermal correction to Enthalpy= 0.110467 Thermal correction to Gibbs Free Energy= 0.070116 6 -0.764577 -2.042395 0.000000 6 0.564165 -2.475064 0.000000 6 1.612325 -1.548444 0.000000 6 1.334647 -0.184962 0.000000 6 0.000000 0.246436 0.000000 6 -1.051555 -0.679307 0.000000 6 -0.316364 1.662551 0.000000 1 -1.573763 -2.766680 0.000000 1 0.785358 -3.538852 0.000000 1 2.642689 -1.891471 0.000000 1 2.138373 0.545982 0.000000 1 -2.076744 -0.321184 0.000000 7 0.220182 2.809961 0.000000 8 -1.466130 2.303699 0.000000 =================================================== A7. 4-acetylbenzoylazide (1c) anti- --------------------------------------------------- E(RB3LYP) = -661.814450, S**2 =0.0000 nuclear repulsion energy 790.865837 Zero-point correction= 0.151136 Thermal correction to Energy= 0.163510 Thermal correction to Enthalpy= 0.164455 Thermal correction to Gibbs Free Energy= 0.111084 6 -1.287664 1.206969 0.393852 6 -1.790752 -0.020663 -0.063266 6 -0.902401 -0.966775 -0.594675 6 0.461466 -0.704708 -0.651551 6 0.961376 0.520599 -0.183599 6 0.074229 1.480724 0.323000 6 2.408231 0.900315 -0.259633 1 -1.956522 1.958217 0.801283 1 -1.307588 -1.903550 -0.962121 1 1.125518 -1.442928 -1.089928 1 0.468525 2.435138 0.655540 7 3.415765 -0.116922 -0.141128 8 2.775510 2.037783 -0.442718 7 3.146633 -1.189125 0.428164 7 3.064870 -2.199064 0.944447 6 -3.253999 -0.370707 -0.020115 6 -4.234212 0.640988 0.545798 1 -5.239161 0.218923 0.496369 1 -4.206095 1.578297 -0.022839 1 -3.993363 0.883184 1.587886 8 -3.637989 -1.451777 -0.435462 =================================================== A8. 4-acetylbenzoylazide (1c) syn- --------------------------------------------------- E(RB3LYP) = -661.814282, S**2 =0.0000 nuclear repulsion energy 791.015816 Zero-point correction= 0.151119 Thermal correction to Energy= 0.163502 Thermal correction to Enthalpy= 0.164447 Thermal correction to Gibbs Free Energy= 0.111040 6 1.231944 -1.308729 0.433525 6 1.795566 -0.103363 -0.015517 6 0.958643 0.878498 -0.562511 6 -0.417504 0.672626 -0.640803 6 -0.974533 -0.528048 -0.181386 6 -0.135201 -1.526181 0.340062 6 -2.435152 -0.842498 -0.282663 1 1.893196 -2.062692 0.847189 1 1.372396 1.809971 -0.934860 1 -1.042259 1.438485 -1.089285 1 -0.575249 -2.462716 0.666408 7 -3.398011 0.219637 -0.170824 8 -2.850502 -1.960193 -0.480862 7 -3.088755 1.272943 0.412198 7 -2.966234 2.274530 0.937079 6 3.285423 0.071739 0.107064 6 3.917418 1.360649 -0.387160 1 4.993392 1.311095 -0.213184 1 3.504748 2.230160 0.138426 1 3.730221 1.506217 -1.457939 8 3.967368 -0.813362 0.597162 =================================================== A9. 4-acetylphenylizocyanate (2c) anti- --------------------------------------------------- E(RB3LYP) = -552.379721, S**2 =0.0000 nuclear repulsion energy 601.951793 Zero-point correction= 0.141600 Thermal correction to Energy= 0.152227 Thermal correction to Enthalpy= 0.153172 Thermal correction to Gibbs Free Energy= 0.104097 6 1.148080 0.438461 0.000000 6 1.063249 -0.962420 0.000000 6 -0.207128 -1.560622 0.000000 6 -1.360165 -0.788793 0.000000 6 -1.262566 0.610408 0.000000 6 0.000000 1.223168 0.000000 7 -2.442012 1.353495 0.000000 1 2.115515 0.930812 0.000000 1 -0.263171 -2.644076 0.000000 1 -2.343425 -1.247673 0.000000 1 0.072648 2.306980 0.000000 6 -2.814833 2.505219 0.000000 8 -3.312216 3.571833 0.000000 6 2.267569 -1.853438 0.000000 6 3.649783 -1.221004 0.000000 1 3.794997 -0.588040 0.883566 1 3.794997 -0.588040 -0.883566 1 4.396935 -2.016081 0.000000 8 2.139922 -3.068609 0.000000 =================================================== A10. 4-acetylphenylizocyanate (2c) syn- --------------------------------------------------- E(RB3LYP) = -552.379868, S**2 =0.0000 nuclear repulsion energy 601.973825 Zero-point correction= 0.141574 Thermal correction to Energy= 0.152204 Thermal correction to Enthalpy= 0.153148 Thermal correction to Gibbs Free Energy= 0.104076 6 -1.165053 0.522569 0.000000 6 -1.120983 -0.881746 0.000000 6 0.130278 -1.515715 0.000000 6 1.306784 -0.772889 0.000000 6 1.247593 0.626068 0.000000 6 0.000000 1.274228 0.000000 7 2.447585 1.335705 0.000000 1 -2.137165 1.004635 0.000000 1 0.196926 -2.599077 0.000000 1 2.276301 -1.259753 0.000000 1 -0.041590 2.359861 0.000000 6 2.846025 2.479321 0.000000 8 3.368630 3.533551 0.000000 6 -2.418169 -1.630779 0.000000 6 -2.388825 -3.150743 0.000000 1 -1.866135 -3.536169 0.883750 1 -1.866135 -3.536169 -0.883750 1 -3.416170 -3.518681 0.000000 8 -3.481758 -1.029358 0.000000 =================================================== A11. 4-acetylbenzoylnitrene anti-, triplet --------------------------------------------------- E(UB3LYP) = -552.265833, S**2 =2.0278 nuclear repulsion energy 609.460227 Zero-point correction= 0.139008 Thermal correction to Energy= 0.149672 Thermal correction to Enthalpy= 0.150616 Thermal correction to Gibbs Free Energy= 0.100757 6 0.558106 -1.252837 -0.000019 6 1.304215 -0.061525 -0.000008 6 0.632824 1.169773 -0.000021 6 -0.759260 1.212550 -0.000043 6 -1.495275 0.019180 -0.000055 6 -0.828583 -1.216142 -0.000041 6 -2.981503 0.037553 -0.000083 1 1.096306 -2.194744 -0.000009 1 1.190384 2.100697 -0.000013 1 -1.275227 2.168180 -0.000052 1 -1.415299 -2.129174 -0.000051 7 -3.650680 1.245088 0.000075 8 -3.690202 -0.982439 0.000080 6 2.806003 -0.168642 0.000016 8 3.340886 -1.265321 0.000027 6 3.634537 1.103283 0.000029 1 3.417815 1.715414 -0.883565 1 3.417787 1.715415 0.883615 1 4.691136 0.831511 0.000046 =================================================== A12. 4-acetylbenzoylnitrene syn-, triplet --------------------------------------------------- E(UB3LYP) = -552.265762, S**2 =2.0277 nuclear repulsion energy 609.461924 Zero-point correction= 0.139005 Thermal correction to Energy= 0.149672 Thermal correction to Enthalpy= 0.150616 Thermal correction to Gibbs Free Energy= 0.100770 6 0.620546 -1.160954 -0.000025 6 1.304383 0.066019 -0.000010 6 0.570447 1.262167 -0.000022 6 -0.818531 1.236783 -0.000049 6 -1.495620 0.006244 -0.000066 6 -0.769670 -1.192309 -0.000053 6 -2.980803 -0.053432 -0.000102 1 1.171126 -2.096168 -0.000016 1 1.115863 2.199794 -0.000010 1 -1.382145 2.165262 -0.000059 1 -1.309783 -2.133561 -0.000066 7 -3.712570 1.117187 0.000098 8 -3.635010 -1.109516 0.000090 6 2.807201 0.159811 0.000020 8 3.352353 1.251469 0.000033 6 3.623621 -1.119843 0.000034 1 3.400976 -1.730020 0.883529 1 3.401012 -1.730015 -0.883473 1 4.682763 -0.858145 0.000056 =================================================== A13. 4-acetylbenzoylnitrene (3c) anti-, singlet --------------------------------------------------- E(RB3LYP) = -552.257516, S**2 =0.0000 nuclear repulsion energy 610.211708 Zero-point correction= 0.139677 Thermal correction to Energy= 0.150445 Thermal correction to Enthalpy= 0.151389 Thermal correction to Gibbs Free Energy= 0.102328 6 -0.631135 -1.143981 -0.000211 6 -1.335891 0.068780 -0.000148 6 -0.626395 1.282010 -0.000051 6 0.760757 1.286997 -0.000023 6 1.455123 0.066802 -0.000056 6 0.761105 -1.148640 -0.000161 6 2.907084 0.039974 0.000069 1 -1.163469 -2.089366 -0.000345 1 -1.192489 2.207183 -0.000024 1 1.311891 2.223078 0.000026 1 1.316762 -2.081430 -0.000179 7 3.922278 0.796142 0.000199 8 3.763868 -0.959361 0.000036 6 -2.841284 0.134376 -0.000064 8 -3.404361 1.216495 -0.000033 6 -3.633763 -1.159754 0.000283 1 -3.400914 -1.765101 0.884582 1 -3.399875 -1.766426 -0.882814 1 -4.697503 -0.917400 -0.000484 =================================================== A14. 4-acetylbenzoylnitrene (3c) syn-, singlet --------------------------------------------------- E(RB3LYP) = -552.257366, S**2 =0.0000 nuclear repulsion energy 610.167548 Zero-point correction= 0.139705 Thermal correction to Energy= 0.150454 Thermal correction to Enthalpy= 0.151398 Thermal correction to Gibbs Free Energy= 0.102399 6 -0.572999 -1.234726 -0.000001 6 -1.335166 -0.055842 -0.000004 6 -0.684306 1.188639 -0.000005 6 0.704721 1.256366 -0.000003 6 1.453161 0.071598 0.000000 6 0.814557 -1.176686 0.000000 6 2.904802 0.118400 0.000002 1 -1.096556 -2.184649 0.000000 1 -1.258520 2.109211 -0.000008 1 1.211391 2.217125 -0.000004 1 1.413115 -2.082674 0.000003 7 3.878958 0.927050 0.000002 8 3.812590 -0.834257 0.000005 6 -2.836406 -0.187238 -0.000007 8 -3.351898 -1.292681 -0.000006 6 -3.684418 1.071282 -0.000010 1 -3.477201 1.686770 -0.883676 1 -3.477460 1.686561 0.883856 1 -4.736671 0.783053 -0.000011 =================================================== A15. 4-aminobenzoylnitrene triplet --------------------------------------------------- E(UB3LYP) = -454.979606, S**2 =2.0206 nuclear repulsion energy 460.305124 Zero-point correction= 0.118286 Thermal correction to Energy= 0.126862 Thermal correction to Enthalpy= 0.127806 Thermal correction to Gibbs Free Energy= 0.083695 6 -1.325078 -1.214486 -0.005100 6 -2.051077 -0.001924 -0.005498 6 -1.339812 1.215926 -0.004830 6 0.045634 1.218303 -0.003892 6 0.767586 0.011157 -0.002354 6 0.057675 -1.202876 -0.003654 6 2.239466 -0.010538 0.002887 1 -1.864659 -2.158686 -0.009481 1 -1.887344 2.155269 -0.008862 1 0.579689 2.164222 -0.001465 1 0.618829 -2.132184 -0.000993 7 2.932422 1.189579 0.005978 8 2.934823 -1.041399 0.005400 7 -3.429539 -0.012350 -0.054028 1 -3.899077 -0.862532 0.225661 1 -3.912575 0.831131 0.222934 =================================================== A16. 4-aminobenzoylnitrene singlet --------------------------------------------------- E(RB3LYP) = -454.971211, S**2 =0.0000 nuclear repulsion energy 461.178050 Zero-point correction= 0.118941 Thermal correction to Energy= 0.127591 Thermal correction to Enthalpy= 0.128535 Thermal correction to Gibbs Free Energy= 0.085272 6 -1.335416 -1.212004 -0.005129 6 -2.091029 -0.020649 -0.005272 6 -1.411850 1.217494 -0.004304 6 -0.028604 1.259310 -0.003768 6 0.718345 0.069043 -0.003301 6 0.048718 -1.164849 -0.004727 6 2.159155 0.091453 0.001981 1 -1.848568 -2.170384 -0.009306 1 -1.984893 2.141278 -0.008172 1 0.484899 2.216856 -0.001015 1 0.628804 -2.083042 -0.002650 7 3.160300 0.871493 0.006006 8 3.052086 -0.880525 0.006481 7 -3.469778 -0.063146 -0.055331 1 -3.916709 -0.924259 0.228356 1 -3.969780 0.766541 0.233329 =================================================== A17. 4-nitrobenzoylnitrene triplet --------------------------------------------------- E(UB3LYP) = -604.117624, S**2 =2.0292 nuclear repulsion energy 622.019622 Zero-point correction= 0.103988 Thermal correction to Energy= 0.113640 Thermal correction to Enthalpy= 0.114585 Thermal correction to Gibbs Free Energy= 0.066538 6 0.646930 -1.217593 -0.000074 6 1.324012 0.002032 0.000012 6 0.661067 1.227173 0.000099 6 -0.730652 1.228616 0.000115 6 -1.434703 0.014838 0.000017 6 -0.742725 -1.205060 -0.000081 6 -2.924414 -0.006934 0.000000 1 1.210601 -2.142201 -0.000127 1 1.233467 2.146251 0.000154 1 -1.269994 2.170755 0.000195 1 -1.307672 -2.131188 -0.000165 7 -3.624920 1.180787 0.000113 8 -3.598945 -1.049126 -0.000136 7 2.801341 -0.005496 -0.000009 8 3.362441 -1.099072 0.000339 8 3.374200 1.082061 -0.000367 =================================================== A18. 4-nitrobenzoylnitrene singlet --------------------------------------------------- E(RB3LYP) = -604.108593, S**2 =0.0000 nuclear repulsion energy 622.747997 Zero-point correction= 0.104670 Thermal correction to Energy= 0.114425 Thermal correction to Enthalpy= 0.115369 Thermal correction to Gibbs Free Energy= 0.068137 6 0.659092 -1.202217 -0.000215 6 1.355046 0.004808 0.000019 6 0.715053 1.244283 0.000243 6 -0.674271 1.273528 0.000292 6 -1.393456 0.069153 0.000024 6 -0.731688 -1.165740 -0.000219 6 -2.847830 0.079645 0.000011 1 1.206779 -2.136232 -0.000354 1 1.305874 2.151552 0.000393 1 -1.202644 2.222008 0.000510 1 -1.310174 -2.084103 -0.000423 7 -3.838962 0.866122 0.000190 8 -3.728314 -0.896331 -0.000241 7 2.832933 -0.028810 -0.000004 8 3.373890 -1.132043 0.000756 8 3.423262 1.048978 -0.000810 =================================================== A19. Ylide 4b --------------------------------------------------- E (B3LYP) =-532.278779 Zero-point correction= .152828 Thermal correction to Energy= .164075 Thermal correction to Enthalpy= .165019 Thermal correction to Gibbs Free Energy= .113386 6 3.327597 .980440 -.001083 6 3.824697 -.325663 .000186 6 2.941331 -1.407875 .000737 6 1.564587 -1.188054 .000141 6 1.061836 .120580 -.000872 6 1.952694 1.202630 -.001492 6 -.403211 .419798 .000121 7 -1.197141 -.735410 -.001603 8 -.846053 1.564890 .002939 7 -2.446919 -.462091 .002085 6 -3.592778 -.274392 .000161 6 -5.033497 -.064100 -.001133 1 4.012932 1.824017 -.001586 1 4.897789 -.499514 .000920 1 3.325970 -2.424410 .001950 1 .871070 -2.021799 .000880 1 1.542526 2.207238 -.002134 1 -5.489599 -.461105 .912845 1 -5.498549 -.550458 -.866145 1 -5.244840 1.009245 -.054203 =================================================== A20. Azirine 5b ---------------------------------------------------- E (B3LYP) =-532.256759 Zero-point correction= .152194 Thermal correction to Energy= .162940 Thermal correction to Enthalpy= .163885 Thermal correction to Gibbs Free Energy= .114524 6 -2.701716 -1.387910 .171356 6 -3.586004 -.307077 .161908 6 -3.098162 .999632 .054190 6 -1.728988 1.223511 -.042785 6 -.834737 .140512 -.033125 6 -1.328229 -1.169103 .075548 6 .617620 .429893 -.148016 7 1.455239 -.743163 -.013822 8 1.072757 1.552537 -.296086 6 2.834179 -.385957 -.029740 7 2.644518 -.724999 -1.210299 6 3.827603 .113417 .938747 1 -3.082511 -2.402206 .252626 1 -4.656240 -.481244 .237275 1 -3.787608 1.839320 .045294 1 -1.327095 2.227674 -.130596 1 -.630925 -1.998674 .081209 1 3.537604 1.123042 1.247607 1 4.824128 .138122 .490966 1 3.832908 -.530696 1.824657 =================================================== A21. Amide 8b --------------------------------------------------- E (B3LYP) =-1359.262242 Zero-point correction= .137008 Thermal correction to Energy= .148154 Thermal correction to Enthalpy= .149098 Thermal correction to Gibbs Free Energy= .097438 6 -3.639055 .696299 -.271312 6 -3.887026 -.479520 .441026 6 -2.822428 -1.219211 .959516 6 -1.509173 -.801954 .747552 6 -1.256415 .372071 .024501 6 -2.330070 1.130679 -.463485 6 .110371 .951506 -.135318 7 1.185220 .118453 -.500557 8 .336333 2.137746 .043090 6 2.531624 .580133 -.454981 17 3.463879 -.049486 .997850 17 .973224 -1.494826 -1.107844 1 -4.465464 1.280017 -.666735 1 -4.908690 -.813840 .599668 1 -3.013120 -2.122593 1.531855 1 -.687373 -1.375284 1.163208 1 -2.124905 2.058530 -.987879 1 2.505728 1.662912 -.366030 1 3.088897 .252397 -1.330015 A22. Amide 9b --------------------------------------------------------------------- E (B3LYP) =-1359.310185 Zero-point correction= .137895 Thermal correction to Energy= .148911 Thermal correction to Enthalpy= .149855 Thermal correction to Gibbs Free Energy= .098257 6 -3.951468 -.758515 -.032525 6 -4.261120 .523739 .428455 6 -3.250968 1.476685 .571687 6 -1.930546 1.145992 .269192 6 -1.612804 -.143112 -.183256 6 -2.635491 -1.088460 -.344512 6 -.225410 -.574532 -.537736 7 .803610 .168508 .037435 8 .008190 -1.517784 -1.278284 6 2.149038 -.159606 -.195909 17 3.104390 1.286452 -.732739 17 2.947488 -.879745 1.276727 1 -4.736973 -1.499452 -.150945 1 -5.288775 .782408 .668447 1 -3.490970 2.480179 .911273 1 -1.163543 1.911724 .350503 1 -2.375108 -2.074574 -.714234 1 .599731 .822802 .780661 1 2.195525 -.907527 -.981656 --------------------------------------------------------------------- A23. Nitrene 3b-Dichloromethane Chloro-Ylide --------------------------------------------------------------------- E (B3LYP) =-1398.473462 Zero-point correction= .163415 Thermal correction to Energy= .176412 Thermal correction to Enthalpy= .177356 Thermal correction to Gibbs Free Energy= .120785 6 3.843978 -1.655000 .179966 6 4.721991 -.704934 -.346262 6 4.259010 .577846 -.649309 6 2.923566 .912409 -.429830 6 2.038965 -.040558 .096990 6 2.508137 -1.324875 .400659 6 .577834 .237961 .371592 7 .222449 1.455078 -.130424 8 -.134519 -.597935 .945199 17 -1.460699 1.807194 .371247 6 -2.670373 .689687 -.514293 6 -3.140403 -.415325 .408235 17 -4.339430 -1.410614 -.520723 1 4.200266 -2.653520 .419400 1 5.764101 -.961999 -.517951 1 4.940254 1.320734 -1.055879 1 2.564308 1.909094 -.661535 1 1.808974 -2.044690 .812458 1 -3.468035 1.363386 -.832180 1 -2.099642 .330676 -1.370908 1 -3.658004 -.023284 1.284779 1 -2.307246 -1.047578 .707802 --------------------------------------------------------------------- ****************************************************************** B.) Results of CASSCF/CASPT2-calculations on triplet formylnitrene ****************************************************************** Geometry: B3LYP/6-31G* Active space: 8 electrons in 7 Orbitals (3/4 a" + 5/3 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-3 of A', 1-3 of A" are averaged Summary of the calculation (Description of the excited states is presented in Table T1, MOs are in Figure S1): CAS(8/7) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc ---------------------------------------------------------------------------- 1-A" -167.748073 -168.126230 88.2% 1-A' -167.708592 -168.086161 87.9% 1.09 eV 1137 nm 0.0003 2-A" -167.628376 -168.022022 87.2% 2.84 eV 437 nm 0.0025 2-A' -167.594586 -167.984981 86.5% 3.84 eV 323 nm 0.0072 3-A" -167.597746 -167.970755 87.6% 4.23 eV 293 nm 0.0182 3-A' -167.557131 -167.920169 88.1% 5.61 eV 221 nm 0.0000 ---------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 4 0 Ras2 Orbitals | 3 4 Frozen Orbitals | 3 0 Orbitals 8-10 of Symmetry A' are active (see Figure S2) Orbitals 1-4 of Symmetry A" are active (see Figure S2) A"-States: --------- root 1: (ground state) CASSCF energy: -167.7480731038 CASPT2 energy: -168.1262300497 Reference weight: 0.88226 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 1 22u 2u00 -0.94020 0.88398 Natural orbitals and occupation numbers for root 1 sym 1: 1.995742 1.997450 1.003260 sym 2: 1.893494 1.002902 0.104978 0.002175 root 2: CASSCF energy: -167.6283762169 CASPT2 energy: -168.0220218223 Reference weight: 0.87184 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 4 2u2 2u00 0.92035 0.84704 Natural orbitals and occupation numbers for root 2 sym 1: 1.899856 1.098385 1.980285 sym 2: 1.907488 0.993703 0.114153 0.006130 root 3: CASSCF energy: -167.5977463794 CASPT2 energy: -167.9707547531 Reference weight: 0.87590 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 2 22u 20u0 -0.45196 0.20427 19 22u u200 0.79628 0.63406 Natural orbitals and occupation numbers for root 3 sym 1: 1.999189 1.988567 1.009877 sym 2: 1.145263 1.461205 0.391526 0.004372 A'-States: --------- root 1: CASSCF energy: -167.7085917755 CASPT2 energy: -168.0861607922 Reference weight: 0.87913 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 25 2uu 2200 0.91375 0.83494 Natural orbitals and occupation numbers for root 1 sym 1: 1.963107 1.035210 0.999940 sym 2: 1.974587 1.872333 0.145401 0.009422 root 2: CASSCF energy: -167.5945861573 CASPT2 energy: -167.9849810765 Reference weight: 0.86506 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 34 u2u 2200 -0.85520 0.73136 Natural orbitals and occupation numbers for root 2 sym 1: 1.129385 1.869966 0.999809 sym 2: 1.949044 1.830331 0.215912 0.005554 root 3: CASSCF energy: -167.5571307039 CASPT2 energy: -167.9201694705 Reference weight: 0.88081 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 7 220 2uu0 -0.41971 0.17616 10 2ud 2uu0 0.64537 0.41650 26 2uu 2du0 -0.40197 0.16158 27 2uu 2ud0 0.32886 0.10815 Natural orbitals and occupation numbers for root 3 sym 1: 1.991212 1.163495 0.847094 sym 2: 1.981376 1.012841 0.994600 0.009382 ****************************************************************** C.) Result of CASSCF/CASPT2-calculation on singlet formylnitrene ****************************************************************** Geometry: B3LYP/6-31G* Active space: 8 electrons in 7 Orbitals (4/4 a" + 4/3 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-3 of A', 1-3 of A" are averaged Summary of the calculation (Description of the excited states is presented in Table T2, MOs are in Figure S2): CAS(8/7) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc --------------------------------------------------------------------------- 1-A' -167.736575 -168.114771 88.7% 1-A" -167.644327 -168.029378 88.1% 2.32 eV 534 nm 0.0002 2-A' -167.560861 -167.939120 85.9% 4.78 eV 259 nm 0.0041 3-A' -167.523007 -167.902892 87.5% 5.77 eV 215 nm 0.0030 2-A" -167.510877 -167.900225 85.4% 5.84 eV 212 nm 0.0000 3-A" -167.474388 -167.855221 86.1% 7.06 eV 176 nm 0.0000 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 4 0 Ras2 Orbitals | 3 4 Frozen Orbitals | 3 0 Orbitals 8-10 of Symmetry A' are active (see Figure S1) Orbitals 1-4 of Symmetry A" are active (see Figure S1) A'-States: ---------- root 1: (ground state) CASSCF energy: -167.7365753085 CASPT2 energy: -168.1147714306 Reference weight: 0.88651 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 11 220 2200 0.89078 0.79348 Natural orbitals and occupation numbers for root 1 sym 1: 1.991077 1.825611 0.188674 sym 2: 1.979539 1.908510 0.101465 0.005123 root 2: CASSCF energy: -167.5608611283 CASPT2 energy: -167.9391196026 Reference weight: 0.85923 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 1 222 2000 -0.43897 0.19270 12 220 2ud0 0.64830 0.42029 31 2ud 2200 -0.44313 0.19636 Natural orbitals and occupation numbers for root 2 sym 1: 1.988850 1.784382 0.662155 sym 2: 1.857277 1.151608 0.546978 0.008750 root 3: CASSCF energy: -167.5230068532 CASPT2 energy: -167.9028922454 Reference weight: 0.87472 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 1 222 2000 0.82912 0.68744 12 220 2ud0 0.33693 0.11352 Natural orbitals and occupation numbers for root 3 sym 1: 1.963140 1.937018 1.608222 sym 2: 1.855556 0.428222 0.203229 0.004612 A"-States: ---------- root 1: CASSCF energy: -167.6443267340 CASPT2 energy: -168.0293779504 Reference weight: 0.88073 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 1 22u 2d00 -0.90042 0.81076 2 22u d200 0.31975 0.10224 Natural orbitals and occupation numbers for root 1 sym 1: 1.993763 1.960799 1.033580 sym 2: 1.904457 1.026014 0.077412 0.003974 root 2: CASSCF energy: -167.5108772931 CASPT2 energy: -167.9002254151 Reference weight: 0.85433 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 2 22u d200 0.65637 0.43083 3 22u 20d0 0.41519 0.17239 21 2u2 2d00 0.41080 0.16876 Natural orbitals and occupation numbers for root 2 sym 1: 1.993756 1.755084 1.164918 sym 2: 1.512400 1.202301 0.366305 0.005237 root 3: CASSCF energy: -167.4743875881 CASPT2 energy: -167.8552207015 Reference weight: 0.86091 dominant CSFs: Symmetry: A' A" conf/sym 111 2222 Coeff Weight 3 22u 20d0 -0.61264 0.37532 21 2u2 2d00 0.42408 0.17985 61 2u0 22d0 0.51234 0.26249 Natural orbitals and occupation numbers for root 3 sym 1: 1.992192 1.439969 0.945241 sym 2: 1.859226 0.935112 0.821434 0.006826 ****************************************************************** D.) Result of CASSCF/CASPT2-calculation on triplet benzoylnitrene ****************************************************************** Geometry: B3LYP/6-31G* Active space: 12 electrons in 11 Orbitals (7/8 a" + 5/3 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-3 of A', 1-7 of A" are averaged Summary of the calculation: *************************** CAS(12/11) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc --------------------------------------------------------------------------- 1-A" -397.355979 -398.456137 70.9% 1-A' -397.339436 -398.396656 71.7% 1.62 eV 766 nm 0.0001 2-A" -397.238087 -398.342861 65.4% 3.08 eV 402 nm 0.0150 3-A" -397.217956 -398.345397 68.9% 3.01 eV 411 nm 0.0055 4-A" -397.216159 -398.339915 68.4% 3.16 eV 392 nm 0.0045 5-A" -397.196430 -398.317860 20.1% 3.76 eV 330 nm 0.0257 6-A" -397.186663 -398.300386 59.1% 4.24 eV 293 nm 0.0063 7-A" -397.172829 -398.294458 61.6% 4.40 eV 282 nm 0.0221 2-A' -397.231745 -398.291843 68.3% 4.47 eV 277 nm 0.0001 3-A' -397.207979 -398.266949 59.4% 5.15 eV 241 nm 0.0000 --------------------------------------------------------------------------- CAS(12/11) + CASPT2 (0.25 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc --------------------------------------------------------------------------- 1-A" -397.355979 -398.446967 75.1% 1-A' -397.339436 -398.388141 76.1% 1.60 eV 775 nm 0.0001 2-A" -397.238087 -398.339438 74.3% 2.93 eV 424 nm 0.0143 3-A" -397.217956 -398.335108 74.1% 3.04 eV 407 nm 0.0056 4-A" -397.216159 -398.329060 74.2% 3.21 eV 386 nm 0.0046 5-A" -397.196430 -398.309074 73.6% 3.75 eV 330 nm 0.0256 6-A" -397.186663 -398.288207 74.3% 4.32 eV 287 nm 0.0064 7-A" -397.172829 -398.284384 73.7% 4.42 eV 280 nm 0.0222 2-A' -397.231745 -398.282307 75.6% 4.48 eV 277 nm 0.0001 3-A' -397.207979 -398.257706 75.6% 5.15 eV 241 nm 0.0000 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 15 1 Ras2 Orbitals | 3 8 Frozen Orbitals | 9 0 Orbitals 23, 26, 27 of Symmetry A' are active (see Figures 5) Orbitals 2-9 of Symmetry A" are active (see Figurse 5) A"-States: ---------- root 1: (ground state) CASSCF energy: -397.3559788078 CASPT2 energy: -398.4561373678 Reference weight: 0.70914 CASPT2 energy: -398.4469668985 (shift = 0.25) Reference weight: 0.75146 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 181 22u 222u0000 -0.91028 0.82861 Natural orbitals and occupation numbers for root 1 sym 1: 1.998191 1.996671 1.001412 sym 2: 1.958719 1.897446 1.893938 1.000667 0.105264 0.103905 0.005764 0.038022 root 2: CASSCF energy: -397.2380870445 CASPT2 energy: -398.3428609109 Reference weight: 0.65379 CASPT2 energy: -398.3394385637 (shift = 0.25) Reference weight: 0.74264 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 106 22u 22u20000 0.57966 0.33601 781 22u 22uud000 0.45978 0.21140 Natural orbitals and occupation numbers for root 2 sym 1: 1.987561 1.996125 1.012908 sym 2: 1.918574 1.800002 1.124595 1.455998 0.420402 0.195088 0.018385 0.070362 root 3: CASSCF energy: -397.2179556854 CASPT2 energy: -398.3453974925 Reference weight: 0.68948 CASPT2 energy: -398.3351076491 (shift = 0.25) Reference weight: 0.74111 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 231 u22 222u0000 -0.84926 0.72125 Natural orbitals and occupation numbers for root 3 sym 1: 1.155645 1.968518 1.866034 sym 2: 1.952555 1.791925 1.888247 1.039787 0.149167 0.109154 0.029986 0.048983 root 4: CASSCF energy: -397.2161590459 CASPT2 energy: -398.3399154766 Reference weight: 0.68402 CASPT2 energy: -398.3290601579 (shift = 0.25) Reference weight: 0.74188 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 1 22u 2u220000 -0.66096 0.43687 183 22u 2u2ud000 0.31988 0.10232 Natural orbitals and occupation numbers for root 4 sym 1: 1.887028 1.993530 1.115848 sym 2: 1.920201 1.180266 1.832602 1.573464 0.259340 0.148559 0.026047 0.063116 root 5: CASSCF energy: -397.1964301321 CASPT2 energy: -398.3178601244 Reference weight: 0.20076 CASPT2 energy: -398.3090738505 (shift = 0.25) Reference weight: 0.73597 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 106 22u 22u20000 0.44801 0.20071 185 22u 2d2u0u00 -0.50387 0.25388 187 22u 2u2u0d00 0.33590 0.11283 Natural orbitals and occupation numbers for root 5 sym 1: 1.995533 1.997391 1.003600 sym 2: 1.906822 1.317503 1.607688 1.226419 0.156405 0.657910 0.045248 0.085481 root 6: CASSCF energy: -397.1866634800 CASPT2 energy: -398.3003863578 Reference weight: 0.59088 CASPT2 energy: -398.2882071369 (shift = 0.25) Reference weight: 0.74312 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 182 22u 2d2uu000 0.60596 0.36718 4244 22u 22uu0d00 -0.43967 0.19331 Natural orbitals and occupation numbers for root 6 sym 1: 1.996529 1.998368 1.001859 sym 2: 1.875512 1.297180 1.600083 1.010044 0.683213 0.427980 0.010610 0.098622 root 7: CASSCF energy: -397.1728293519 CASPT2 energy: -398.2944581530 Reference weight: 0.61595 CASPT2 energy: -398.2843840422 (shift = 0.25) Reference weight: 0.73733 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 481 22u 22udu000 0.45605 0.20798 781 22u 22duu000 -0.41211 0.16984 Natural orbitals and occupation numbers for root 7 sym 1: 1.887028 1.993530 1.115848 sym 2: 1.920201 1.573464 1.832602 1.180266 0.259340 0.148559 0.026047 0.063116 A'-States: ---------- root 1: CASSCF energy: -397.3394363366 CASPT2 energy: -398.3966557598 Reference weight: 0.71691 CASPT2 energy: -398.3881408374 (shift = 0.25) Reference weight: 0.76073 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 211 2uu 22220000 0.89632 0.80339 Natural orbitals and occupation numbers for root 1 sym 1: 1.993829 1.004891 0.999386 sym 2: 1.959337 1.895598 1.909232 1.852525 0.159096 0.105311 0.083358 0.037437 root 2: CASSCF energy: -397.2317447545 CASPT2 energy: -398.2918434000 Reference weight: 0.68339 CASPT2 energy: -398.2823073324 (shift = 0.25) Reference weight: 0.75624 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 1136 220 222uu000 0.59547 0.35459 1286 202 222uu000 -0.40964 0.16780 Natural orbitals and occupation numbers for root 2 sym 1: 1.995979 1.269627 0.733607 sym 2: 1.936659 1.817765 1.842913 1.152828 0.853207 0.183849 0.153535 0.060030 root 3: CASSCF energy: -397.2079789111 CASPT2 energy: -398.2669488590 Reference weight: 0.59412 CASPT2 energy: -398.2577057384 (shift = 0.25) Reference weight: 0.75636 dominant CSFs: Symmetry: A' A" conf/sym 111 22222222 Coeff Weight 1436 2uu 222du000 0.51709 0.26738 4801 2uu 222ud000 -0.39888 0.15910 Natural orbitals and occupation numbers for root 3 sym 1: 1.992966 1.107042 0.898600 sym 2: 1.921858 1.696432 1.848703 1.268324 0.750366 0.305396 0.137971 0.072341 E.) Result of CASSCF/CASPT2-calculation on singlet benzoylnitrene ****************************************************************** Geometry: B3LYP/6-31G* Active space: 12 electrons in 11 Orbitals (10/9 a" + 2/2 a') Basis: ANO-S, [3s2p1d] on C, O, N and [2s] on H State averaging: States 1-3 of A', 1-3 of A" are averaged Summary of the calculation: *************************** CAS(12/11) + CASPT2 --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc --------------------------------------------------------------------------- 1-A' -397.386757 -398.439233 72.8% 1-A" -397.285370 -398.350749 72.2% 2.41 eV 515 nm 0.0001 3-A' -397.208108 -398.286699 35.7% 4.15 eV 299 nm 0.0303 2-A' -397.213593 -398.285664 60.1% 4.18 eV 297 nm 0.0048 2-A" -397.183753 -398.257641 61.2% 4.94 eV 251 nm 0.0000 3-A" -397.165954 -398.249223 33.2% 5.17 eV 240 nm 0.0000 --------------------------------------------------------------------------- CAS(12/11) + CASPT2 (0.25 a.u. level shift) --------------------------------------------------------------------------- State CASSCF CASPT2 % w DE (in eV) DE (in nm) osc --------------------------------------------------------------------------- 1-A' -397.386757 -398.431418 76.5% 1-A" -397.285370 -398.342507 76.0% 2.42 eV 513 nm 0.0001 3-A' -397.208108 -398.282331 74.9% 4.06 eV 306 nm 0.0296 2-A' -397.213593 -398.274384 75.3% 4.27 eV 290 nm 0.0049 2-A" -397.183753 -398.248815 75.3% 4.97 eV 250 nm 0.0000 3-A" -397.165954 -398.244385 74.9% 5.09 eV 244 nm 0.0000 --------------------------------------------------------------------------- | A' A" ------------------+----------- Inactive Orbitals | 16 0 Ras2 Orbitals | 2 9 Frozen Orbitals | 9 0 Orbitals 26, 27 of Symmetry A' are active (see Figure 4) Orbitals 1-9 of Symmetry A" are active (see Figure 4) A'-States: ---------- root 1: (ground state) CASSCF energy: -397.3867572386 CASPT2 energy: -398.4392330022 Reference weight: 0.72768 CASPT2 energy: -398.4314178979 (shift = 0.25) Reference weight: 0.76454 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 862 20 222220000 0.86630 0.75048 Natural orbitals and occupation numbers for root 1 sym 1: 1.843676 0.161968 sym 2: 1.984975 1.960034 1.888260 1.924298 1.895766 0.127190 0.104149 0.073331 0.036353 root 2: CASSCF energy: -397.2135933579 CASPT2 energy: -398.2856636770 Reference weight: 0.60060 CASPT2 energy: -398.2743844173 (shift = 0.25) Reference weight: 0.75290 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 863 20 2222ud000 -0.54466 0.29666 2650 20 222u20d00 -0.39168 0.15341 Natural orbitals and occupation numbers for root 2 sym 1: 1.834786 0.174804 sym 2: 1.971958 1.857976 1.541124 1.895093 1.386359 0.688304 0.445797 0.128977 0.074823 root 3: CASSCF energy: -397.2081080901 CASPT2 energy: -398.2866987143 Reference weight: 0.35736 CASPT2 energy: -398.2823307890 (shift = 0.25) Reference weight: 0.74899 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 864 20 22u22d000 -0.63778 0.40676 Natural orbitals and occupation numbers for root 3 sym 1: 1.821562 0.218271 sym 2: 1.949379 1.922606 1.295376 1.818748 1.857700 0.796883 0.160055 0.110830 0.048589 A"-States: ---------- root 1: CASSCF energy: -397.2853704931 CASPT2 energy: -398.3507494876 Reference weight: 0.72164 CASPT2 energy: -398.3425067456 (shift = 0.25) Reference weight: 0.76027 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 141 2u 222d20000 0.88098 0.77613 Natural orbitals and occupation numbers for root 1 sym 1: 1.963642 1.033185 sym 2: 1.922208 1.959918 1.879045 1.025112 1.894934 0.119633 0.104832 0.061517 0.035974 root 2: CASSCF energy: -397.1837530369 CASPT2 energy: -398.2576405304 Reference weight: 0.61226 CASPT2 energy: -398.2488145943 (shift = 0.25) Reference weight: 0.75260 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 772 2u 22du2d000 0.46097 0.21250 774 2u 222ud0d00 -0.54664 0.29882 Natural orbitals and occupation numbers for root 2 sym 1: 1.945520 1.047008 sym 2: 1.894305 1.920352 1.411447 1.100455 1.564884 0.515769 0.437252 0.098223 0.064786 root 3: CASSCF energy: -397.1659544713 CASPT2 energy: -398.2492226269 Reference weight: 0.33198 CASPT2 energy: -398.2443853987 (shift = 0.25) Reference weight: 0.74868 dominant CSFs: Symmetry: A' A" conf/sym 11 222222222 Coeff Weight 2 2u 22d220000 -0.58442 0.34155 1401 2u 22202d000 -0.38210 0.14600 Natural orbitals and occupation numbers for root 3 sym 1: 1.907118 1.085234 sym 2: 1.906071 1.954100 1.403027 1.210555 1.843938 0.409964 0.152712 0.087437 0.039844 ------------------- end of Supporting Information ------------------