"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 and characterized by B3LYP/6-31G*. Tha charge and multiplicity are indicated in the line above the cartesian coordinates. ------------------------------------------------------- 2-(1-pyrazolyl)-phenylazides 1a ------------------------------------------------------- 1a(NH) 0,1 6 -0.106292 2.075540 0.084873 6 -0.147164 0.676784 0.045699 6 1.064411 -0.044088 0.011686 6 2.281311 0.651605 0.043883 6 2.306411 2.041048 0.086350 6 1.106932 2.755488 0.099638 7 -1.415610 0.042546 0.014541 6 -1.808995 -1.153200 0.556836 6 -3.161550 -1.270578 0.331345 6 -3.511600 -0.084811 -0.355357 7 -2.466576 0.711135 -0.543658 7 0.994583 -1.459579 -0.068826 7 2.050149 -2.099044 -0.144612 7 2.939243 -2.810640 -0.217939 1 1.113352 3.840758 0.130449 1 -3.801203 -2.091522 0.621022 1 3.212191 0.091760 0.022278 1 3.260068 2.560103 0.106203 1 -4.482168 0.219283 -0.725840 1 -1.049342 2.607966 0.092798 1 -1.106211 -1.805996 1.046825 SCF Done: E(RBLYP) = -620.838140859 Sum of electronic and zero-point Energies= -620.682937 Sum of electronic and thermal Energies= -620.672195 Sum of electronic and thermal Enthalpies= -620.671250 Sum of electronic and thermal Free Energies= -620.720688 ----- TS 1a(NH) -> 1a(NN) (rotation of pyrazolyl group) 0,1 6 -1.031944 0.135133 0.014635 6 0.042494 -0.772983 0.011307 6 -0.203470 -2.144555 -0.011936 6 -1.510920 -2.629636 -0.027850 6 -2.577479 -1.728926 -0.025923 6 -2.344608 -0.355884 -0.005067 7 1.383849 -0.291052 0.020978 7 2.006906 0.030979 -1.144540 6 3.213205 0.447191 -0.767250 6 3.381815 0.401313 0.635556 6 2.178944 -0.078129 1.109492 7 -0.699807 1.508478 0.050626 7 -1.621409 2.333418 0.024730 7 -2.363044 3.199941 0.007409 1 -1.694209 -3.699402 -0.047028 1 4.250526 0.677322 1.215556 1 -3.180307 0.338373 -0.002813 1 -3.600599 -2.093748 -0.041135 1 3.923134 0.764562 -1.520408 1 0.645362 -2.820920 -0.025763 1 1.822412 -0.279697 2.109392 SCF Done: E(RBLYP) = -620.833515590 Sum of electronic and zero-point Energies= -620.678804 Sum of electronic and thermal Energies= -620.668742 Sum of electronic and thermal Enthalpies= -620.667798 Sum of electronic and thermal Free Energies= -620.715665 ----- 1a(NN) 0,1 6 -0.075949 -2.123819 -0.108571 6 0.088896 -0.739532 -0.036424 6 -1.043224 0.097825 0.019406 6 -2.320162 -0.478949 -0.024374 6 -2.471048 -1.861397 -0.095349 6 -1.349305 -2.690658 -0.128433 7 1.400184 -0.196049 -0.003204 6 2.402159 -0.526790 0.866791 6 3.510346 0.201333 0.492979 6 3.078664 0.947541 -0.629018 7 1.807390 0.708672 -0.934244 7 -0.815991 1.484983 0.154042 7 -1.793287 2.241649 0.160137 7 -2.593165 3.055522 0.182350 1 -1.462005 -3.768771 -0.187051 1 4.482813 0.201129 0.963507 1 -3.196768 0.161782 0.013892 1 -3.469613 -2.287855 -0.122759 1 3.645157 1.646674 -1.230723 1 0.810181 -2.748029 -0.168877 1 2.232063 -1.221694 1.676406 SCF Done: E(RBLYP) = -620.834176205 Sum of electronic and zero-point Energies= -620.679297 Sum of electronic and thermal Energies= -620.668442 Sum of electronic and thermal Enthalpies= -620.667498 Sum of electronic and thermal Free Energies= -620.717476 ----- TS 1a(NN) -> 1a'(NN) (rotation of azide group) 0,1 7 1.805736 -0.015943 -1.084690 7 1.126392 -0.568437 -0.043597 6 1.967445 -1.024184 0.936267 6 3.250341 -0.747443 0.519535 6 3.084525 -0.123523 -0.740078 6 -0.287690 -0.687983 -0.068373 6 -0.868833 -1.930920 0.203071 6 -2.254256 -2.078896 0.222072 6 -3.073350 -0.984327 -0.054556 6 -2.501878 0.255862 -0.335743 6 -1.114559 0.421015 -0.325634 7 -0.556671 1.700843 -0.650394 7 -0.454483 2.534627 0.256683 7 -0.295773 3.404718 0.977376 1 -2.688647 -3.051774 0.431880 1 4.169091 -0.954857 1.048577 1 -3.123125 1.117340 -0.560242 1 -4.153923 -1.092746 -0.057298 1 3.846706 0.248821 -1.412412 1 -0.219267 -2.782115 0.382105 1 1.582292 -1.472938 1.840383 SCF Done: E(RBLYP) = -620.827202028 Sum of electronic and zero-point Energies= -620.672566 Sum of electronic and thermal Energies= -620.662512 Sum of electronic and thermal Enthalpies= -620.661568 Sum of electronic and thermal Free Energies= -620.709414 ----- 1a'(NN) 0,1 6 -1.577401 -1.306666 -0.924495 7 -0.817912 -0.676291 0.021058 7 -1.553871 -0.309047 1.108652 6 -2.789937 -0.704400 0.819278 6 -2.867900 -1.339121 -0.442497 6 0.592275 -0.483585 0.009830 6 1.154463 0.810178 0.043456 6 2.552223 0.932862 0.080307 6 3.371487 -0.189683 0.047465 6 2.811479 -1.467584 -0.016824 6 1.425886 -1.604552 -0.024053 7 0.460728 2.034861 0.041754 7 -0.749513 2.118953 -0.217346 7 -1.825362 2.418433 -0.441467 1 3.444601 -2.349086 -0.041619 1 -3.738797 -1.751244 -0.930988 1 2.972094 1.932687 0.115568 1 4.450248 -0.064808 0.068002 1 -3.585588 -0.518676 1.529127 1 0.964203 -2.587305 -0.033944 1 -1.140700 -1.654625 -1.849513 SCF Done: E(RBLYP) = -620.834173791 Sum of electronic and zero-point Energies= -620.679321 Sum of electronic and thermal Energies= -620.668508 Sum of electronic and thermal Enthalpies= -620.667564 Sum of electronic and thermal Free Energies= -620.717290 ----- TS 1a'(NN) -> 1a'(NH) (rotation of pyrazolyl group) 0,1 7 1.510630 -1.093684 -1.018844 7 0.825680 -0.657533 0.074603 6 1.636202 -0.514549 1.167397 6 2.909222 -0.854437 0.765645 6 2.767522 -1.203935 -0.597775 6 -0.588073 -0.484068 0.022958 6 -1.405562 -1.609535 -0.099129 6 -2.791870 -1.482634 -0.110760 6 -3.366645 -0.214830 0.012628 6 -2.561379 0.914064 0.116157 6 -1.163520 0.799850 0.097689 7 -0.457783 2.020760 0.188128 7 0.717637 2.117775 -0.202174 7 1.774011 2.414544 -0.508197 1 -3.417112 -2.365232 -0.203804 1 3.807730 -0.849841 1.365328 1 -2.992093 1.907245 0.189062 1 -4.447013 -0.102437 0.016955 1 3.531762 -1.530769 -1.291123 1 -0.928662 -2.581111 -0.178560 1 1.238783 -0.190438 2.118679 SCF Done: E(RBLYP) = -620.833287753 Sum of electronic and zero-point Energies= -620.678617 Sum of electronic and thermal Energies= -620.668616 Sum of electronic and thermal Enthalpies= -620.667672 Sum of electronic and thermal Free Energies= -620.715019 ----- 1a'(NN) 0,1 6 -1.302867 -1.650248 -0.151507 6 -0.532741 -0.497405 0.029876 6 -1.169811 0.751844 0.168051 6 -2.568559 0.802525 0.209589 6 -3.326930 -0.353038 0.050764 6 -2.692831 -1.581222 -0.151006 7 0.882098 -0.621796 0.080111 6 1.731848 -0.143223 1.042086 6 2.984602 -0.631606 0.746517 6 2.793711 -1.415385 -0.415557 7 1.526433 -1.419771 -0.816273 7 -0.501841 1.999410 0.324907 7 0.521316 2.242832 -0.333969 7 1.459098 2.634044 -0.849282 1 -3.276812 -2.486150 -0.288964 1 3.901291 -0.448771 1.287948 1 -3.039682 1.771484 0.338396 1 -4.410994 -0.291069 0.071045 1 3.529868 -1.972847 -0.980150 1 -0.784329 -2.593140 -0.284498 1 1.372399 0.484009 1.844891 SCF Done: E(RBLYP) = -620.833524090 Sum of electronic and zero-point Energies= -620.678636 Sum of electronic and thermal Energies= -620.667811 Sum of electronic and thermal Enthalpies= -620.666867 Sum of electronic and thermal Free Energies= -620.716624 ----- TS 1a(NH) -> 1a'(NH) (rotation of azide group) 0,1 7 -1.850567 -1.337108 0.724174 7 -1.112357 -0.518828 -0.079880 6 -1.908481 0.268964 -0.870273 6 -3.212568 -0.040117 -0.557035 6 -3.112332 -1.040681 0.438137 6 0.300462 -0.645595 -0.077692 6 0.859631 -1.900268 0.196014 6 2.240241 -2.072097 0.211178 6 3.086501 -0.996106 -0.062406 6 2.538963 0.255949 -0.330883 6 1.155035 0.446137 -0.318464 7 0.641279 1.754904 -0.637498 7 0.407112 2.523966 0.307068 7 0.148292 3.339142 1.059552 1 2.653239 -3.053859 0.423474 1 -4.105302 0.392133 -0.985023 1 3.172914 1.110749 -0.544653 1 4.164405 -1.127353 -0.065849 1 -3.908738 -1.552837 0.962580 1 0.186617 -2.723860 0.401650 1 -1.484157 0.963385 -1.577549 SCF Done: E(RBLYP) = -620.832149036 Sum of electronic and zero-point Energies= -620.677191 Sum of electronic and thermal Energies= -620.667271 Sum of electronic and thermal Enthalpies= -620.666327 Sum of electronic and thermal Free Energies= -620.713560 ------------------------------------------------------- 2-(1-pyrazolyl)-phenylnitrene 2a and its photoproducts ------------------------------------------------------- 2a (NN) triplet 0,3 6 -1.903356 -1.122646 0.520253 6 -3.025878 0.567964 -0.350098 6 -3.186623 -0.675555 0.310505 6 0.346183 -0.196708 -0.027740 6 1.021509 -1.410165 -0.114625 6 2.418146 -1.456617 -0.107943 6 3.166508 -0.270774 -0.030965 6 2.523190 0.948489 0.046243 6 1.089010 1.040003 0.061749 7 0.527305 2.234997 0.189187 7 -1.061167 -0.171727 0.000289 7 -1.748637 0.872342 -0.538054 1 4.251875 -0.311126 -0.036691 1 2.920159 -2.416325 -0.182867 1 0.452279 -2.328857 -0.215130 1 -3.790200 1.250246 -0.698453 1 -4.104672 -1.164691 0.601828 1 -1.522890 -2.000954 1.019525 1 3.078794 1.878472 0.107568 SCF Done: E(UBLYP) = -511.306482676 S**2 before annihilation 2.0507, after 2.0012 Sum of electronic and zero-point Energies= -511.163716 Sum of electronic and thermal Energies= -511.154697 Sum of electronic and thermal Enthalpies= -511.153753 Sum of electronic and thermal Free Energies= -511.199652 ----- 2a (NH) triplet 0,3 7 -1.894480 -1.083358 0.000000 6 -2.089013 -2.392546 0.000000 6 -0.869616 -3.114924 0.000000 6 0.106668 -2.148411 0.000000 7 -0.533782 -0.931734 0.000000 6 0.005920 0.367977 0.000000 6 1.439566 0.587366 0.000000 6 1.906714 1.951100 0.000000 6 1.027462 3.009944 0.000000 6 -0.359041 2.767014 0.000000 6 -0.855565 1.465000 0.000000 7 2.336301 -0.382328 0.000000 1 -1.056596 3.599095 0.000000 1 -0.725442 -4.185355 0.000000 1 2.981023 2.101934 0.000000 1 1.404292 4.028514 0.000000 1 -3.100720 -2.777617 0.000000 1 -1.921157 1.274559 0.000000 1 1.183756 -2.214309 0.000000 SCF Done: E(UBLYP) = -511.313536605 S**2 before annihilation 2.0484, after 2.0011 Sum of electronic and zero-point Energies= -511.170462 Sum of electronic and thermal Energies= -511.161502 Sum of electronic and thermal Enthalpies= -511.160558 Sum of electronic and thermal Free Energies= -511.206625 ----- 2a TS: (NN) <--> (NH) triplet 0,3 7 1.753817 -0.023720 -1.148347 6 3.030488 -0.028666 -0.774001 6 3.179549 -0.179737 0.623666 6 1.888683 -0.269019 1.099363 7 1.063838 -0.175602 0.015192 6 -0.360135 -0.201601 0.006033 6 -1.086582 1.040167 0.064162 6 -2.519792 0.976984 0.041588 6 -3.170183 -0.241949 -0.028671 6 -2.438311 -1.438232 -0.080461 6 -1.036408 -1.407141 -0.064755 7 -0.470125 2.212788 0.150965 1 -2.954557 -2.391471 -0.138671 1 4.092528 -0.215010 1.200137 1 -3.070192 1.911116 0.082814 1 -4.256010 -0.271402 -0.044652 1 3.802192 0.076000 -1.525859 1 -0.460666 -2.326107 -0.117269 1 1.490151 -0.382225 2.097287 SCF Done: E(UBLYP) = -511.302534828 S**2 before annihilation 2.0521, after Sum of electronic and zero-point Energies= -511.160146 Sum of electronic and thermal Energies= -511.151823 Sum of electronic and thermal Enthalpies= -511.150878 Sum of electronic and thermal Free Energies= -511.195095 ----- TS: 2a (NN) <--> 13a (NN) 0,1 6 -2.460667 0.142007 1.099661 6 -3.012818 -0.606711 0.108565 6 -2.337542 -0.821497 -1.154130 6 -1.015062 -0.496579 -1.343752 6 -0.313649 0.106116 -0.256464 6 -1.179609 0.752410 0.748014 1 -3.994787 -1.051721 0.246117 1 -2.876863 -1.338076 -1.942802 1 -0.488930 -0.826200 -2.236099 7 1.064604 -0.024048 -0.097287 7 -0.712567 1.911959 0.575801 7 1.589760 -0.313227 1.129422 6 2.898329 -0.367283 0.922274 6 3.241288 -0.116033 -0.431464 1 3.557645 -0.591475 1.750949 1 4.224405 -0.093341 -0.878551 6 2.036877 0.105520 -1.055100 1 1.788662 0.365714 -2.073615 1 -2.945599 0.324613 2.052822 SCF Done: E(UBLYP) = -511.257647515 S**2 before annihilation 0.2997, after 0.0156 Sum of electronic and zero-point Energies= -511.116404 Sum of electronic and thermal Energies= -511.107540 Sum of electronic and thermal Enthalpies= -511.106596 Sum of electronic and thermal Free Energies= -511.151148 ----- 13a (NN) 0,1 6 -2.372404 0.482238 1.188379 6 -2.922005 -0.537973 0.457512 6 -2.309088 -1.064139 -0.742408 6 -1.041874 -0.736146 -1.150124 6 -0.307321 0.283304 -0.408791 6 -1.235689 1.015029 0.514501 1 -3.854070 -0.986384 0.792479 1 -2.853300 -1.835595 -1.280172 1 -0.539681 -1.317015 -1.920341 7 1.065859 0.048332 -0.093946 7 -0.769668 1.734177 -0.416168 7 2.052448 0.807635 -0.637879 6 3.175972 0.274695 -0.168568 6 2.932463 -0.837256 0.674008 1 4.126962 0.707769 -0.451574 1 3.651646 -1.455408 1.191829 6 1.560411 -0.953082 0.696296 1 0.899738 -1.643381 1.201340 1 -2.754565 0.838994 2.137558 SCF Done: E(RBLYP) = -511.278372894 Sum of electronic and zero-point Energies= -511.135419 Sum of electronic and thermal Energies= -511.126405 Sum of electronic and thermal Enthalpies= -511.125461 Sum of electronic and thermal Free Energies= -511.171529 ----- TS: 2a (NH) <--> 13a (NH) 0,1 6 2.498012 1.015518 -0.465118 6 3.016568 -0.236696 -0.552956 6 2.306900 -1.396784 -0.043257 6 0.991161 -1.352961 0.335325 6 0.317295 -0.090812 0.223271 6 1.201475 1.075657 0.212099 1 4.000931 -0.389462 -0.987805 1 2.831410 -2.348053 -0.030661 1 0.432057 -2.249210 0.579526 7 -1.060553 -0.039082 0.002864 7 0.715270 1.561014 1.276502 7 -1.824023 -1.136762 0.275434 6 -3.057051 -0.773933 -0.051923 6 -3.112000 0.559870 -0.529769 1 -3.867393 -1.481805 0.064575 1 -3.976786 1.115036 -0.862599 6 -1.810872 1.000304 -0.481216 1 -1.361772 1.952286 -0.716536 1 3.017765 1.904056 -0.808838 SCF Done: E(UBLYP) = -511.261166396 S**2 before annihilation 0.1910, after 0.0053 Sum of electronic and zero-point Energies= -511.119533 Sum of electronic and thermal Energies= -511.110716 Sum of electronic and thermal Enthalpies= -511.109771 Sum of electronic and thermal Free Energies= -511.154364 ----- 13a (NH) 0,1 6 -2.383137 0.617343 1.119932 6 -2.937382 -0.457593 0.475012 6 -2.314793 -1.103258 -0.658045 6 -1.035415 -0.837301 -1.071623 6 -0.303326 0.243159 -0.425313 6 -1.230028 1.064590 0.417111 1 -3.884046 -0.856019 0.831632 1 -2.859652 -1.918791 -1.124978 1 -0.522939 -1.508639 -1.755302 7 1.074997 0.043854 -0.108971 7 -0.740637 1.695398 -0.568941 7 1.480145 -1.125713 0.453841 6 2.798086 -0.990328 0.579934 6 3.252579 0.263314 0.108158 1 3.376210 -1.798390 1.009887 1 4.263130 0.645133 0.090636 6 2.112389 0.901058 -0.333676 1 1.945181 1.870583 -0.778302 1 -2.773259 1.065438 2.025991 SCF Done: E(RBLYP) = -511.282661535 Sum of electronic and zero-point Energies= -511.139524 Sum of electronic and thermal Energies= -511.130596 Sum of electronic and thermal Enthalpies= -511.129652 Sum of electronic and thermal Free Energies= -511.174526 ----- TS: 13a (NH) <--> 15a (NH) 0,1 6 -2.394858 0.695120 1.166684 6 -3.029772 -0.328369 0.451104 6 -2.406484 -1.017606 -0.607686 6 -1.051795 -0.887072 -0.926855 6 -0.259698 0.177758 -0.450233 6 -1.313625 1.170794 0.460141 1 -4.023821 -0.640593 0.763111 1 -2.961972 -1.823655 -1.078163 1 -0.539806 -1.720264 -1.400603 7 1.104218 -0.005252 -0.145688 7 -0.697615 1.594310 -0.547946 7 1.556734 -1.207327 0.311961 6 2.867034 -1.036517 0.443011 6 3.275850 0.272717 0.086013 1 3.476229 -1.857876 0.798238 1 4.272485 0.689362 0.103998 6 2.115326 0.907776 -0.291486 1 1.913887 1.907062 -0.646211 1 -2.692217 1.046239 2.147188 SCF Done: E(RBLYP) = -511.278845828 Sum of electronic and zero-point Energies= -511.136948 Sum of electronic and thermal Energies= -511.128323 Sum of electronic and thermal Enthalpies= -511.127378 Sum of electronic and thermal Free Energies= -511.171329 ----- 15a (NH) 0,1 6 -2.064498 1.069064 0.313661 6 -3.337605 0.566800 0.437150 6 -3.167431 -0.841591 0.446417 7 -1.894239 -1.195013 0.334596 7 -1.220917 -0.012146 0.256412 6 0.175951 0.021311 0.158441 7 0.732220 1.323076 0.053437 6 1.676001 1.261688 -0.773656 6 2.725088 0.702497 -1.355004 6 3.258301 -0.352691 -0.487694 6 2.408893 -1.148753 0.227247 6 0.962119 -1.088811 0.296478 1 -3.925625 -1.610127 0.525815 1 -1.676226 2.074003 0.263388 1 -4.257558 1.128471 0.506989 1 0.442316 -1.998634 0.578213 1 2.855437 -1.961710 0.797892 1 4.333552 -0.509936 -0.411032 1 3.087741 0.929424 -2.350620 SCF Done: E(RBLYP) = -511.296883005 Sum of electronic and zero-point Energies= -511.153349 Sum of electronic and thermal Energies= -511.144404 Sum of electronic and thermal Enthalpies= -511.143460 Sum of electronic and thermal Free Energies= -511.188014 ----- 15a (NH) (nitrile ilyde form) 0,1 6 0.718040 -1.386827 0.477225 6 -0.096198 -2.421829 0.801111 6 -1.533537 -2.387320 1.067130 6 -2.280366 -1.359412 1.569752 6 -1.623837 -0.134801 2.039685 7 -0.817308 0.311694 1.134969 6 0.144654 -0.051956 0.361236 7 0.638353 0.847038 -0.599804 1 1.771852 -1.539153 0.268671 1 0.354369 -3.412237 0.839487 1 -2.027099 -3.355442 0.990883 1 -3.327592 -1.531471 1.810721 6 0.303307 2.164174 -0.770257 7 1.546430 0.419501 -1.521337 6 1.020550 2.611078 -1.855868 1 -0.392829 2.649972 -0.103715 6 1.773929 1.486738 -2.277828 1 1.014312 3.605865 -2.277037 1 2.475406 1.415758 -3.098926 SCF Done: E(RBLYP) = -511.265602462 Sum of electronic and zero-point Energies= -511.122663 Sum of electronic and thermal Energies= -511.113556 Sum of electronic and thermal Enthalpies= -511.112612 Sum of electronic and thermal Free Energies= -511.157548 ----- TS: 13a (NN) <--> 15a (NN) 0,1 6 -2.374501 0.619524 1.204824 6 -3.010204 -0.388340 0.469811 6 -2.400335 -1.026593 -0.628748 6 -1.055174 -0.858409 -0.973190 6 -0.263237 0.194317 -0.463368 6 -1.316574 1.145041 0.494125 1 -3.989018 -0.732808 0.795597 1 -2.956678 -1.815836 -1.126165 1 -0.551139 -1.650476 -1.523637 7 1.095250 -0.009438 -0.149262 7 -0.725656 1.605139 -0.508699 7 2.037766 0.930118 -0.443271 6 3.180195 0.384355 -0.048442 6 2.999540 -0.911142 0.500792 1 4.101893 0.939359 -0.168877 1 3.748899 -1.577299 0.903199 6 1.644429 -1.128358 0.425338 1 1.023098 -1.955084 0.736928 1 -2.653406 0.929053 2.204732 SCF Done: E(RBLYP) = -511.275078629 Sum of electronic and zero-point Energies= -511.133310 Sum of electronic and thermal Energies= -511.124673 Sum of electronic and thermal Enthalpies= -511.123729 Sum of electronic and thermal Free Energies= -511.167759 ----- 15a (NN) 0,1 6 0.162688 -0.148102 0.100408 7 0.090060 1.849070 -1.213347 6 0.028996 3.147357 -0.954136 6 0.019593 3.416656 0.438209 1 -0.007206 3.850436 -1.776133 1 0.123507 1.885321 2.067244 1 -0.009728 4.375771 0.934715 7 0.120326 1.255343 0.013472 6 -0.158030 -0.842240 1.234224 7 0.703337 -0.808685 -1.027029 1 -0.423774 -0.261184 2.113015 6 -0.072402 -2.282105 1.441367 6 -0.258639 -3.274010 0.525580 1 0.128956 -2.582764 2.468719 6 -0.616932 -2.941832 -0.862693 1 -0.136633 -4.313632 0.828130 6 0.032994 -1.848024 -1.218462 1 -1.363980 -3.458889 -1.452455 6 0.077199 2.178108 1.029686 SCF Done: E(RBLYP) = -511.287979450 Sum of electronic and zero-point Energies= -511.144848 Sum of electronic and thermal Energies= -511.135772 Sum of electronic and thermal Enthalpies= -511.134827 Sum of electronic and thermal Free Energies= -511.180334 ----- 15a (NN) (nitrile ylide form) 0,1 6 3.156541 -0.783805 0.192957 7 1.921335 -1.149939 -0.127551 7 1.213973 0.012343 -0.125957 6 1.996499 1.094502 0.190997 6 3.267196 0.612725 0.405249 6 -0.167725 0.020068 -0.390794 7 -0.844184 -1.068561 -0.394608 6 -2.028491 -1.546384 -0.457748 6 -2.866440 -0.909890 0.569148 6 -2.910083 0.452887 0.647295 6 -2.128902 1.425526 -0.120738 6 -0.877280 1.279052 -0.621609 1 -0.412851 2.076994 -1.198079 1 -2.622558 2.381767 -0.289097 1 -3.724541 0.885300 1.226827 1 -3.587376 -1.504482 1.126149 1 1.583784 2.089544 0.259340 1 4.145507 1.182299 0.671794 1 3.932275 -1.536420 0.251346 SCF Done: E(RBLYP) = -511.259594889 Sum of electronic and zero-point Energies= -511.116818 Sum of electronic and thermal Energies= -511.107696 Sum of electronic and thermal Enthalpies= -511.106752 Sum of electronic and thermal Free Energies= -511.151816 ----- TS: 2a (NN) <--> 14a (NN) 0,1 6 -2.100624 1.139996 0.077284 7 -1.148707 0.150933 0.023378 7 -1.711626 -1.093401 -0.020075 6 -3.016591 -0.870892 -0.003839 6 -3.322864 0.514495 0.054703 6 0.237875 0.267909 -0.031528 6 0.930618 1.438873 -0.197180 6 2.363501 1.471570 -0.171258 6 3.126259 0.376317 0.188828 6 2.458502 -0.823381 0.530832 6 1.074881 -0.933027 0.073135 7 1.282979 -1.997457 -0.572628 1 4.199775 0.475210 0.327749 1 2.847052 2.422539 -0.374981 1 0.398023 2.368752 -0.371409 1 -3.699154 -1.710346 -0.023300 1 -4.296086 0.982023 0.090924 1 -1.832985 2.184031 0.133530 1 2.915516 -1.633890 1.076897 SCF Done: E(UBLYP) = -511.264869606 S**2 before annihilation 0.1819, after 0.0069 Sum of electronic and zero-point Energies= -511.123224 Sum of electronic and thermal Energies= -511.114402 Sum of electronic and thermal Enthalpies= -511.113458 Sum of electronic and thermal Free Energies= -511.158247 ----- 14a (NN) 0,1 6 -2.127363 1.124433 0.215807 7 -1.208218 0.129434 0.004280 7 -1.799040 -1.091581 -0.138542 6 -3.097243 -0.847869 -0.021713 6 -3.365808 0.527475 0.197760 6 0.179889 0.228491 -0.097080 6 0.906542 1.371338 -0.302556 6 2.350100 1.390587 -0.212618 6 3.100549 0.340777 0.245830 6 2.433142 -0.917054 0.553490 6 1.046948 -0.916308 0.026033 7 1.762417 -1.739867 -0.606485 1 4.150591 0.488153 0.488712 1 2.836743 2.335129 -0.440153 1 0.395077 2.301456 -0.533359 1 -3.800156 -1.667623 -0.092158 1 -4.323728 1.006687 0.338169 1 -1.824980 2.148469 0.375376 1 2.719803 -1.509397 1.418920 SCF Done: E(RBLYP) = -511.279387096 Sum of electronic and zero-point Energies= -511.135880 Sum of electronic and thermal Energies= -511.126929 Sum of electronic and thermal Enthalpies= -511.125985 Sum of electronic and thermal Free Energies= -511.170838 ----- TS: 2a (NH) <--> 14a (NH) 0,1 6 1.855634 1.082519 0.025064 6 3.188064 -0.680234 0.029317 6 3.184922 0.739321 0.011539 6 -0.237366 -0.235741 0.010010 6 -0.899395 -1.422931 -0.147467 6 -2.333461 -1.470301 -0.179130 6 -3.132265 -0.382421 0.114470 6 -2.494435 0.828970 0.487004 6 -1.097759 0.947545 0.092725 7 -1.297183 2.009736 -0.565633 7 1.145338 -0.095234 0.048140 7 1.963454 -1.187264 0.053401 1 -4.210853 -0.492935 0.188497 1 -2.794966 -2.431246 -0.388984 1 -0.323899 -2.331513 -0.282517 1 4.039030 -1.349221 0.031780 1 4.032746 1.408159 -0.002440 1 1.352803 2.038025 0.015265 1 -2.979752 1.627709 1.025835 SCF Done: E(UBLYP) = -511.269865059 S**2 before annihilation 0.0990, after 0.0020 Sum of electronic and zero-point Energies= -511.127798 Sum of electronic and thermal Energies= -511.119051 Sum of electronic and thermal Enthalpies= -511.118107 Sum of electronic and thermal Free Energies= -511.162445 --- 14a (NH) 0,1 6 -1.965772 -1.034214 0.004183 7 -1.204433 0.106163 0.033950 7 -1.966125 1.230574 0.127360 6 -3.214988 0.780939 0.151979 6 -3.278839 -0.633468 0.081036 6 0.186707 0.191564 -0.052734 6 0.911522 1.333736 -0.252550 6 2.359556 1.333343 -0.237061 6 3.123590 0.265463 0.148508 6 2.451266 -0.984736 0.493325 6 1.050753 -0.958731 0.037315 7 1.708873 -1.812593 -0.625406 1 4.190952 0.389749 0.316277 1 2.844796 2.276296 -0.474303 1 0.379279 2.262154 -0.429283 1 -4.031502 1.487515 0.226131 1 -4.155734 -1.263915 0.087759 1 -1.508061 -2.009973 -0.071844 1 2.769303 -1.574214 1.349918 SCF Done: E(RBLYP) = -511.281737863 Sum of electronic and zero-point Energies= -511.138075 Sum of electronic and thermal Energies= -511.129139 Sum of electronic and thermal Enthalpies= -511.128195 Sum of electronic and thermal Free Energies= -511.172892 ----- TS, 14a (NH) <--> 16a (NH) 0,1 6 -2.097844 -0.984636 -0.233400 7 -1.226509 0.053190 -0.047111 7 -1.849994 1.173029 0.408420 6 -3.129510 0.822978 0.502890 6 -3.345799 -0.522624 0.122185 6 0.159507 0.062003 -0.288479 6 0.898420 1.212868 -0.622828 6 2.270906 1.311528 -0.374405 6 3.001025 0.362543 0.368911 6 2.595904 -0.949132 0.603610 6 0.977254 -1.034381 -0.155948 7 1.941998 -1.765352 -0.461511 1 3.860093 0.718346 0.936459 1 2.751433 2.258150 -0.603755 1 0.354520 2.072484 -1.003540 1 -3.853901 1.550049 0.846516 1 -4.276001 -1.071534 0.103610 1 -1.757599 -1.939233 -0.608431 1 2.883806 -1.501214 1.495337 SCF Done: E(RBLYP) = -511.268965991 Sum of electronic and zero-point Energies= -511.127083 Sum of electronic and thermal Energies= -511.118313 Sum of electronic and thermal Enthalpies= -511.117369 Sum of electronic and thermal Free Energies= -511.161872 ----- 16a (NH) 0,1 6 0.855508 -0.802091 1.169846 6 0.105818 -1.694973 1.875744 6 -1.344176 -1.761234 1.972992 6 -2.243729 -0.738152 1.909647 7 -1.833741 0.609589 1.795808 6 -0.900147 0.703128 0.955305 6 0.175314 0.198492 0.355111 1 1.942080 -0.845196 1.192205 1 0.640791 -2.469080 2.423825 1 -1.752083 -2.731389 2.249829 1 -3.304500 -0.906447 2.079560 7 0.627835 0.547726 -0.932554 7 1.551318 -0.232732 -1.550776 6 1.730157 0.344023 -2.737379 6 0.926231 1.496419 -2.895350 6 0.232480 1.600376 -1.708190 1 2.436475 -0.086621 -3.434984 1 0.872641 2.164085 -3.742939 1 -0.478033 2.326653 -1.341185 SCF Done: E(RBLYP) = -511.285776809 Sum of electronic and zero-point Energies= -511.142332 Sum of electronic and thermal Energies= -511.133215 Sum of electronic and thermal Enthalpies= -511.132271 Sum of electronic and thermal Free Energies= -511.177544 ----- 16a (NH) (nitrile ylide form) 0,1 6 -3.270964 0.474445 0.950011 6 -3.226986 -0.772817 0.271319 7 -1.999768 -1.096221 -0.109817 7 -1.226615 -0.059237 0.325453 6 -1.968152 0.905426 0.965901 6 0.154323 -0.039181 0.125937 6 0.845676 -1.152270 -0.281756 6 2.271540 -1.287311 -0.509902 6 3.180066 -0.327869 -0.852415 6 2.731336 1.037280 -1.036798 7 1.758286 1.446213 -0.296111 6 0.898553 1.151028 0.600540 1 4.218121 -0.596807 -1.034392 1 3.123000 1.694749 -1.809713 1 2.635809 -2.311458 -0.449553 1 0.271380 -2.073858 -0.312993 1 -1.484573 1.782325 1.368427 1 -4.046805 -1.442106 0.043250 1 -4.132600 0.979489 1.361281 SCF Done: E(RBLYP) = -511.270408030 Sum of electronic and zero-point Energies= -511.127112 Sum of electronic and thermal Energies= -511.118128 Sum of electronic and thermal Enthalpies= -511.117184 Sum of electronic and thermal Free Energies= -511.161733 ----- TS: 14a (NN) <--> 16a (NN) 0,1 6 -2.015758 1.070988 0.433301 7 -1.221799 0.075508 -0.066111 7 -1.929967 -1.048262 -0.362056 6 -3.183557 -0.742598 -0.041982 6 -3.301950 0.577380 0.454616 6 0.164500 0.111592 -0.289073 6 0.906055 1.275075 -0.577367 6 2.268297 1.381686 -0.278239 6 2.978522 0.419074 0.467775 6 2.574832 -0.901123 0.644236 6 0.983827 -0.985638 -0.175735 7 1.969541 -1.686311 -0.473604 1 3.813392 0.764087 1.076608 1 2.751459 2.333649 -0.478579 1 0.381342 2.135275 -0.987562 1 -3.961524 -1.482265 -0.179941 1 -4.192898 1.088787 0.788775 1 -1.598622 2.018047 0.742090 1 2.833821 -1.482737 1.525810 SCF Done: E(RBLYP) = -511.268647285 Sum of electronic and zero-point Energies= -511.126749 Sum of electronic and thermal Energies= -511.117993 Sum of electronic and thermal Enthalpies= -511.117049 Sum of electronic and thermal Free Energies= -511.161499 ----- 16a (NN) 0,1 6 0.437976 -0.184464 0.029906 6 1.076820 0.908076 -0.369977 7 1.688653 1.977679 -0.134442 6 1.139640 2.588161 1.018617 6 0.836891 1.868473 2.135694 6 0.954200 0.429068 2.331401 6 0.809137 -0.551921 1.397274 7 -0.534087 -0.875680 -0.717386 1 0.985519 -1.593882 1.666885 1 1.189062 0.118427 3.348814 1 0.598068 2.448029 3.025075 1 1.093493 3.674558 1.014080 6 -1.390758 -1.843043 -0.274697 7 -0.734347 -0.566999 -2.024131 6 -2.188937 -2.184051 -1.347510 1 -1.374340 -2.185508 0.749237 6 -1.736141 -1.358511 -2.401247 1 -2.976248 -2.923443 -1.366122 1 -2.090053 -1.313910 -3.423032 SCF Done: E(RBLYP) = -511.284007472 Sum of electronic and zero-point Energies= -511.140569 Sum of electronic and thermal Energies= -511.131452 Sum of electronic and thermal Enthalpies= -511.130508 Sum of electronic and thermal Free Energies= -511.175815 ----- 16a (NN) (nitrile ylide form) 0,1 7 1.778935 -1.361380 0.222175 6 2.878663 -0.843458 0.651099 1 4.331092 0.679935 -0.025220 1 3.412112 -1.317874 1.470626 6 0.789132 -1.251712 -0.567636 6 3.278013 0.420332 0.056872 6 0.117922 0.031714 -0.230192 1 2.664939 2.252365 -0.755990 7 -1.266605 0.053526 -0.065187 6 0.874083 1.176390 -0.272000 1 0.336141 2.114172 -0.391176 6 2.322502 1.298855 -0.358082 7 -2.012805 -1.048164 -0.382147 1 -1.616707 2.003196 0.764196 6 -3.257231 -0.697761 -0.104013 6 -2.048572 1.073706 0.426483 1 -4.057549 -1.407639 -0.268823 6 -3.344604 0.626277 0.406597 1 -4.226156 1.161919 0.727721 SCF Done: E(RBLYP) = -511.261767319 Sum of electronic and zero-point Energies= -511.118884 Sum of electronic and thermal Energies= -511.109804 Sum of electronic and thermal Enthalpies= -511.108860 Sum of electronic and thermal Free Energies= -511.153900 ----- TS: 2a (NN) <--> 5a 0,1 6 -3.179709 -0.651738 0.110297 6 -1.955339 -1.297353 0.135383 6 -2.881865 0.707508 -0.121395 6 0.397704 -0.339924 -0.017585 6 0.916404 0.995770 0.028854 6 2.339060 1.134488 -0.015697 6 3.146539 0.009134 -0.005895 6 2.600451 -1.286078 -0.029566 6 1.214773 -1.459427 -0.057911 7 -1.003327 -0.345487 -0.077423 7 -1.566175 0.873008 -0.253387 7 0.104076 2.045055 0.146347 1 0.783978 -2.454875 -0.119950 1 3.251867 -2.153675 -0.054996 1 2.759594 2.134225 -0.010764 1 4.226121 0.133673 -0.003580 1 -3.547258 1.551859 -0.230454 1 -1.691689 -2.330071 0.306676 1 -4.154290 -1.103719 0.225551 SCF Done: E(UBLYP) = -511.282999223 S**2 before annihilation 0.6546, after 0.0572 Sum of electronic and zero-point Energies= -511.140486 Sum of electronic and thermal Energies= -511.132241 Sum of electronic and thermal Enthalpies= -511.131297 Sum of electronic and thermal Free Energies= -511.174104 ----- 5a (heteropentalene) 0,1 6 0.577743 2.372328 0.000000 6 -0.675361 0.057800 0.000000 6 -2.085789 -2.296742 0.000000 6 0.037165 -1.175974 0.000000 6 -2.066090 0.141847 0.000000 6 -2.767667 -1.059253 0.000000 6 -0.701365 -2.376521 0.000000 7 1.390011 -0.997639 0.000000 1 -2.579260 1.098780 0.000000 1 -3.853134 -1.044577 0.000000 1 -0.185186 -3.330906 0.000000 1 -2.666936 -3.214988 0.000000 1 3.557611 0.896920 0.000000 7 1.516993 0.340549 0.000000 7 0.318247 1.025683 0.000000 6 2.535020 1.234672 0.000000 1 -0.222900 3.093794 0.000000 6 1.958638 2.513858 0.000000 1 2.499288 3.448744 0.000000 SCF Done: E(RBLYP) = -511.351082356 Sum of electronic and zero-point Energies= -511.204898 Sum of electronic and thermal Energies= -511.196987 Sum of electronic and thermal Enthalpies= -511.196043 Sum of electronic and thermal Free Energies= -511.237664 ----- TS: 2a (NH) <--> 17 0,1 6 1.224865 -1.496548 0.227314 6 0.387140 -0.394969 0.187914 6 0.867014 0.944556 -0.064219 6 2.288673 1.120376 -0.183784 6 3.113530 0.014871 -0.149522 6 2.595584 -1.286021 0.052314 7 -0.017352 1.912021 -0.244856 6 -1.612881 0.865920 0.506309 7 -0.998800 -0.386013 0.319295 6 -2.926968 0.689888 0.026230 6 -2.979007 -0.633101 -0.429024 7 -1.812381 -1.284030 -0.286639 1 0.815758 -2.489063 0.383780 1 3.274697 -2.132352 0.088534 1 2.676654 2.121516 -0.339004 1 4.185940 0.143623 -0.268277 1 -3.730921 1.409470 0.070794 1 -3.818843 -1.158631 -0.865878 1 -1.351263 1.461757 1.374263 SCF Done: E(UBLYP) = -511.275881504 S**2 before annihilation 0.8586, after 0.2862 Sum of electronic and zero-point Energies= -511.133905 Sum of electronic and thermal Energies= -511.125748 Sum of electronic and thermal Enthalpies= -511.124804 Sum of electronic and thermal Free Energies= -511.167353 ----- 17 0,1 6 1.820300 2.468020 -0.246056 7 0.463589 2.294175 -0.021250 7 0.350977 1.002214 0.219503 6 1.635679 0.265827 0.293037 6 2.565682 1.322110 -0.218185 6 -0.639750 0.086823 0.123984 6 0.048475 -1.192330 0.018317 7 1.375755 -1.110822 0.007084 6 -0.764929 -2.365701 -0.090887 6 -2.127970 -2.219077 -0.146948 6 -2.769779 -0.939701 -0.076526 6 -2.039373 0.219622 0.059810 1 -2.506762 1.197316 0.114656 1 -3.853192 -0.891955 -0.128738 1 -0.287761 -3.338890 -0.141845 1 -2.753709 -3.102165 -0.246968 1 3.640067 1.230003 -0.276536 1 2.169607 3.475790 -0.433501 1 1.889486 0.257378 1.376284 SCF Done: E(RBLYP) = -511.318194939 Sum of electronic and zero-point Energies= -511.173212 Sum of electronic and thermal Energies= -511.165334 Sum of electronic and thermal Enthalpies= -511.164390 Sum of electronic and thermal Free Energies= -511.206019 ----- TS: 2a (NH) <--> 17 (triplet) 0,3 6 -1.944531 0.226176 0.296107 6 -0.575440 0.044854 0.276702 6 0.032346 -1.217232 -0.041182 6 -0.830975 -2.317825 -0.328454 6 -2.203306 -2.134103 -0.292450 6 -2.761524 -0.877076 0.011637 7 1.368610 -1.282107 -0.068762 6 1.709721 0.518770 0.682406 7 0.412532 1.036366 0.471004 6 2.572535 1.431686 0.030415 6 1.727376 2.349629 -0.615600 7 0.434511 2.103815 -0.406322 1 -2.365890 1.201789 0.514512 1 -3.840899 -0.759044 0.026774 1 -0.390035 -3.279643 -0.569439 1 -2.862369 -2.971484 -0.504213 1 3.652600 1.424380 0.052354 1 2.008625 3.190602 -1.237722 1 1.931183 0.037611 1.628811 SCF Done: E(UBLYP) = -511.281363217 S**2 before annihilation 2.0821, after 2.003 Sum of electronic and zero-point Energies= -511.139509 Sum of electronic and thermal Energies= -511.131410 Sum of electronic and thermal Enthalpies= -511.130466 Sum of electronic and thermal Free Energies= -511.173825 ----- 17 triplet 0,3 6 1.686165 2.289807 -0.589709 7 0.407291 2.209453 -0.158127 7 0.349742 1.056931 0.620816 6 1.653014 0.319341 0.625461 6 2.486095 1.224704 -0.231518 6 -0.628516 0.099973 0.299391 6 0.055361 -1.136894 0.055649 7 1.393212 -1.050026 0.182377 6 -0.699426 -2.284055 -0.300337 6 -2.075352 -2.159049 -0.410851 6 -2.719364 -0.923600 -0.185109 6 -1.999487 0.225877 0.170414 1 -2.492473 1.178877 0.330129 1 -3.798878 -0.861495 -0.288156 1 -0.189919 -3.224623 -0.483205 1 -2.673841 -3.024747 -0.680092 1 3.530799 1.071223 -0.462609 1 1.970472 3.149358 -1.186390 1 2.051196 0.260281 1.654509 SCF Done: E(UBLYP) = -511.308332297 S**2 = 2.0565 Sum of electronic and zero point Energies -511.164881 Sum of electronic and thermal Energies -511.156788 Sum of electronic and thermal Enthalpies -511.155843 Sum of electronic and thermal Free Energies -511.199085 ---- TS: 17 <--> 7 0,1 6 1.832930 2.509694 -0.111575 7 0.493596 2.327981 0.005482 7 0.380582 0.995320 0.119299 6 1.613840 0.313083 0.105198 6 2.585444 1.334323 -0.123262 6 -0.636241 0.076560 0.033725 6 0.008922 -1.197040 -0.002709 7 1.385039 -1.119687 -0.033044 6 -0.780834 -2.365356 -0.018466 6 -2.157039 -2.223549 -0.056048 6 -2.774821 -0.948398 -0.042665 6 -2.028045 0.218694 0.010448 1 -2.487819 1.200818 0.030094 1 -3.858757 -0.886102 -0.069906 1 -0.303984 -3.340198 -0.026936 1 -2.783808 -3.109910 -0.095000 1 3.656606 1.219648 -0.175292 1 2.207554 3.522768 -0.186730 1 1.770758 -0.340380 1.113715 SCF Done: E(RBLYP) = -511.298120125 Sum of electronic and zero-point Energies= -511.156200 Sum of electronic and thermal Energies= -511.148494 Sum of electronic and thermal Enthalpies= -511.147550 Sum of electronic and thermal Free Energies= -511.188868 ----- 7 0,1 7 -1.657923 .000000 .342551 6 -.878509 .000000 -.816996 6 1.153071 .000000 -2.710040 6 -1.228767 .000000 -2.164045 6 .483436 .000000 -.426683 6 1.512307 .000000 -1.359585 6 -.192922 .000000 -3.103145 1 -2.269147 .000000 -2.476216 7 .471883 .000000 .964178 1 2.548349 .000000 -1.039123 1 -.441064 .000000 -4.160501 1 1.931755 .000000 -3.466792 6 -.815132 .000000 1.437485 7 1.408460 .000000 1.949070 1 -2.664040 .000000 .377788 6 -.740718 .000000 2.820409 6 .661041 .000000 3.057551 1 -1.541101 .000000 3.543736 1 1.155473 .000000 4.020820 SCF Done: E(RBLYP) = -511.398944862 Sum of electronic and zero-point Energies= -511.252031 Sum of electronic and thermal Energies= -511.243644 Sum of electronic and thermal Enthalpies= -511.242700 Sum of electronic and thermal Free Energies= -511.285643 ------------------------------------------------------- 2-[1-(3,5-dimethylpyrazolyl]-phenylazides 1b ------------------------------------------------------- 1b(NMe) 0,1 7 1.906922 0.695528 -0.752513 7 0.966673 0.186196 0.102245 6 1.491245 -0.765726 0.944877 6 2.819127 -0.886557 0.590081 6 3.026102 0.036947 -0.465801 6 -0.327584 0.770033 0.105891 6 -0.444360 2.148425 0.304041 6 -1.691134 2.768174 0.290148 6 -2.840726 2.002880 0.081841 6 -2.739581 0.631449 -0.130762 6 -1.484640 0.005749 -0.138448 7 -1.304607 -1.375344 -0.403400 7 -2.302432 -2.053681 -0.676026 7 -3.129216 -2.794100 -0.941324 6 0.715877 -1.439086 2.031941 6 4.284865 0.317634 -1.229613 1 -1.765316 3.839878 0.447306 1 3.544903 -1.547618 1.044058 1 -3.634034 0.041426 -0.310597 1 -3.820083 2.472632 0.077343 1 0.465216 2.718033 0.459805 1 0.044568 -2.209317 1.637477 1 1.406874 -1.914708 2.733403 1 0.103028 -0.723723 2.592819 1 4.627039 -0.568460 -1.778287 1 4.111430 1.121218 -1.950289 1 5.099868 0.620919 -0.561106 SCF Done: E(RBLYP) = -699.477233917 Sum of electronic and zero-point Energies= -699.266759 Sum of electronic and thermal Energies= -699.252399 Sum of electronic and thermal Enthalpies= -699.251455 Sum of electronic and thermal Free Energies= -699.309070 ----- TS 1b(NMe) -> 1b'(NN) (rotation of azide group) 0,1 6 1.475290 0.502553 0.310104 6 0.729378 -0.586732 -0.175186 6 1.392871 -1.664093 -0.769754 6 2.782475 -1.667799 -0.879123 6 3.519913 -0.579991 -0.409904 6 2.867245 0.498841 0.185021 7 -0.686230 -0.572754 -0.093760 7 -1.373380 0.468749 -0.653546 6 -2.654253 0.204442 -0.415697 6 -2.799407 -1.007796 0.307426 6 -1.520679 -1.487078 0.503606 6 -1.040046 -2.703986 1.231013 6 -3.722162 1.139121 -0.897766 7 0.810094 1.541156 1.034366 7 0.715925 2.654803 0.505301 7 0.558246 3.727568 0.155108 1 3.284077 -2.510740 -1.345179 1 -3.715876 -1.467023 0.652186 1 3.430046 1.340025 0.578496 1 4.602308 -0.571081 -0.499646 1 0.805912 -2.483476 -1.172123 1 -0.187884 -2.477073 1.881139 1 -1.847114 -3.097819 1.854800 1 -0.727981 -3.505803 0.550426 1 -4.328364 1.516479 -0.065270 1 -3.267220 1.992749 -1.407078 1 -4.404245 0.642208 -1.598482 SCF Done: E(RBLYP) = -699.471273526 Sum of electronic and zero-point Energies= -699.260989 Sum of electronic and thermal Energies= -699.247423 Sum of electronic and thermal Enthalpies= -699.246478 Sum of electronic and thermal Free Energies= -699.302074 ----- 1b'(NN) 0,1 7 -1.286190 -0.043456 -1.109443 7 -0.482623 -0.496532 -0.096644 6 -1.200099 -1.081097 0.918712 6 -2.523693 -0.985475 0.542976 6 -2.523717 -0.334860 -0.719119 6 0.930936 -0.372978 -0.213975 6 1.692589 -1.494730 -0.550276 6 3.075869 -1.408314 -0.686930 6 3.705059 -0.175273 -0.498136 6 2.959147 0.950486 -0.168665 6 1.566110 0.870874 -0.014271 7 0.944700 2.081286 0.343286 7 -0.270212 2.162757 0.587826 7 -1.334771 2.462942 0.861314 6 -0.564187 -1.649893 2.147943 6 -3.694841 0.029080 -1.580519 1 3.653175 -2.289315 -0.949936 1 -3.378229 -1.332366 1.107758 1 3.434556 1.913767 -0.015874 1 4.782229 -0.088379 -0.608403 1 1.173781 -2.433782 -0.718273 1 0.064336 -0.911744 2.660470 1 -1.339866 -1.975094 2.846083 1 0.071482 -2.514540 1.922815 1 -4.361871 0.733038 -1.068455 1 -3.345431 0.496901 -2.504624 1 -4.289529 -0.854384 -1.842383 SCF Done: E(RBLYP) = -699.476075666 Sum of electronic and zero-point Energies= -699.265858 Sum of electronic and thermal Energies= -699.251399 Sum of electronic and thermal Enthalpies= -699.250455 Sum of electronic and thermal Free Energies= -699.308691 ------------------------------------------------------------------ 2-[1-(3,5-dimethylpyrazolyl]phenylnitrene 2b and its photoproducts ------------------------------------------------------------------ 2b (NN) triplet 0,3 7 -1.363337 -.882208 -.422198 7 -.585969 .187534 -.070235 6 -.783475 2.545119 .882666 6 .815726 .062904 -.145087 6 -2.613801 -.489923 -.215666 6 -3.755790 -1.414348 -.507539 6 -2.654674 .840023 .281657 6 -1.343887 1.254926 .370081 1 -3.527324 1.417203 .555644 1 -3.373739 -2.376530 -.857709 1 -4.418923 -1.002012 -1.277843 1 -4.364386 -1.588580 .387985 1 -.512537 3.238824 .076760 1 .110737 2.387085 1.494783 1 -1.535086 3.042891 1.501739 6 3.623581 -.203509 -.277122 6 1.441317 -1.151785 .330549 6 1.600030 1.086892 -.664676 6 2.992528 .967766 -.724980 6 2.871284 -1.243879 .232880 7 .767207 -2.154801 .876701 1 1.118011 1.977094 -1.053532 1 3.580174 1.780156 -1.141619 1 3.336428 -2.159352 .583638 1 4.704308 -.295576 -.336298 SCF Done: E(UBLYP) = -589.946577058 S**2 before annihilation 2.0507, after 2.0012 Sum of electronic and zero-point Energies= -589.748175 Sum of electronic and thermal Energies= -589.735714 Sum of electronic and thermal Enthalpies= -589.734770 Sum of electronic and thermal Free Energies= -589.788313 ----- 2b (NMe) triplet 0,3 6 2.658356 -0.617743 0.164807 6 2.663403 0.731891 -0.276289 6 1.341649 1.101068 -0.398773 6 -0.783731 -0.225317 -0.040792 6 -1.276637 -1.409916 -0.580870 6 -2.647294 -1.673844 -0.600115 6 -3.560355 -0.741644 -0.074413 6 -3.104341 0.430779 0.490298 6 -1.696540 0.721703 0.558801 6 3.826990 -1.504930 0.468038 6 0.756995 2.379253 -0.911139 7 1.418661 -1.069364 0.304510 7 0.610479 -0.008161 -0.022432 7 -1.291202 1.803218 1.205712 1 -4.626460 -0.947765 -0.105268 1 -3.006840 -2.600640 -1.036889 1 -0.565470 -2.121924 -0.983811 1 3.521170 1.353264 -0.494846 1 -3.785832 1.155962 0.922713 1 3.476391 -2.501727 0.748133 1 4.490771 -1.600453 -0.399862 1 4.427307 -1.105473 1.294474 1 0.305007 2.976151 -0.112682 1 1.547836 2.969948 -1.381822 1 -0.020415 2.195009 -1.661985 SCF Done: E(UBLYP) = -589.949971082 S**2 before annihilation 2.0491, after 2.0011 Sum of electronic and zero-point Energies= -589.751424 Sum of electronic and thermal Energies= -589.739029 Sum of electronic and thermal Enthalpies= -589.738085 Sum of electronic and thermal Free Energies= -589.791181 ----- TS: 2b (NN) <--> 2b (NMe) triplet 0,3 6 1.501637 0.026679 -1.385057 6 0.808016 -0.084704 -0.191490 6 1.515054 -0.354631 1.034888 6 2.939956 -0.511309 0.967322 6 3.604982 -0.393874 -0.239818 6 2.895539 -0.122502 -1.419990 7 -0.606440 0.057344 -0.161904 6 -1.335190 1.217388 -0.081102 6 -2.657504 0.824124 -0.053860 6 -2.641267 -0.593401 -0.114668 7 -1.396355 -1.058771 -0.176447 6 -0.705414 2.572522 -0.013910 6 -3.802153 -1.541907 -0.116079 7 0.888686 -0.438704 2.202007 1 -3.519162 1.474730 0.009167 1 -3.439504 -2.571953 -0.166694 1 -4.464685 -1.365926 -0.972469 1 -4.407373 -1.433710 0.792151 1 -1.483342 3.337941 0.047800 1 -0.089829 2.787487 -0.895760 1 -0.061164 2.675004 0.868008 1 0.942749 0.217925 -2.296157 1 3.422477 -0.036113 -2.365302 1 3.472512 -0.720459 1.889298 1 4.684160 -0.514324 -0.273040 Sum of electronic and zero-point Energies= -589.746700 Sum of electronic and thermal Energies= -589.734867 Sum of electronic and thermal Enthalpies= -589.733923 Sum of electronic and thermal Free Energies= -589.785860 SCF Done: E(UBLYP) = -589.944658139 S**2 before annihilation 2.0523, after 2.0013 ----- TS: 2b (NN) <--> 13b (NN) collapses to TS (NMe) ----- 13b (NN) 0,1 6 0.464951 -0.064843 -1.503796 7 -0.455436 -0.043631 -0.480867 7 -1.737450 -0.169103 -0.934101 6 -1.627899 -0.254760 -2.255652 6 -0.267821 -0.194650 -2.663677 6 -0.200441 -0.002503 0.919784 6 0.269863 -1.211194 1.592915 6 1.287838 -1.106035 2.504260 6 1.998670 0.127962 2.766411 6 1.590852 1.339771 2.277172 6 0.331049 1.208540 1.618156 7 -0.923326 1.085111 1.720173 1 2.898605 0.078155 3.374508 1 1.658240 -2.004504 2.990396 1 -0.089788 -2.186176 1.272238 6 -2.851943 -0.394526 -3.109469 1 0.123861 -0.235093 -3.671170 6 1.939558 0.053549 -1.281808 1 2.137793 2.268294 2.391885 1 2.463203 -0.025721 -2.238158 1 2.210561 1.015359 -0.829229 1 2.319074 -0.733487 -0.619509 1 -2.953000 0.446510 -3.806531 1 -2.820098 -1.312186 -3.709594 1 -3.743036 -0.425631 -2.477050 SCF Done: E(RBLYP) = -589.920151999 Sum of electronic and zero-point Energies= -589.721510 Sum of electronic and thermal Energies= -589.709059 Sum of electronic and thermal Enthalpies= -589.708115 Sum of electronic and thermal Free Energies= -589.760931 ----- TS: 2b (NMe) <--> 13b (NMe) 0,1 6 1.476335 1.182285 -0.246909 7 0.589508 0.136422 -0.099344 7 1.229306 -1.067434 0.067917 6 2.521489 -0.777578 0.001892 6 2.729333 0.617532 -0.195404 6 -0.800880 0.174585 -0.041762 6 -1.609375 0.674904 -1.102904 6 -2.886471 0.178590 -1.237237 6 -3.409498 -0.847611 -0.363008 6 -2.767611 -1.213790 0.778553 6 -1.565891 -0.436759 1.070852 7 -1.167574 0.363935 1.959985 1 -4.349147 -1.322166 -0.633618 1 -3.493834 0.493316 -2.080952 1 -1.182090 1.307916 -1.875902 6 3.549464 -1.859998 0.128231 1 3.673397 1.139430 -0.272776 6 1.042330 2.607791 -0.361373 1 -3.136441 -1.979602 1.452758 1 1.902057 3.267050 -0.215640 1 0.610440 2.840189 -1.343202 1 0.290424 2.849089 0.398540 1 4.165235 -1.935022 -0.776413 1 4.227348 -1.667775 0.968740 1 3.058577 -2.822599 0.292968 SCF Done: E(UBLYP) = -589.900127566 S**2 before annihilation 0.3212, after 0.0187 Sum of electronic and zero-point Energies= -589.703329 Sum of electronic and thermal Energies= -589.690986 Sum of electronic and thermal Enthalpies= -589.690041 Sum of electronic and thermal Free Energies= -589.742476 ----- 13b (NMe) 0,1 6 1.732454 -0.800987 -0.484068 7 0.577434 -0.104512 -0.224027 7 0.531088 1.094569 -0.882470 6 1.666620 1.150115 -1.570881 6 2.454029 -0.012662 -1.355839 6 -0.490931 -0.465349 0.643972 6 -0.624606 0.215143 1.930518 6 -1.863021 0.644280 2.325596 6 -3.039686 0.559841 1.486626 6 -3.062803 -0.131099 0.305986 6 -1.839126 -0.840629 0.127380 7 -1.127508 -1.846027 0.417157 1 -3.936443 1.080714 1.812969 1 -1.962693 1.176641 3.267517 1 0.262674 0.508144 2.487053 6 1.971431 2.335095 -2.437035 1 3.420316 -0.245826 -1.782334 6 2.045390 -2.132498 0.122324 1 -3.896044 -0.147338 -0.386207 1 3.022431 -2.475131 -0.228895 1 2.078993 -2.083096 1.217721 1 1.294905 -2.884685 -0.141110 1 2.897825 2.832690 -2.124721 1 2.097892 2.042908 -3.486792 1 1.154540 3.059267 -2.377295 SCF Done: E(RBLYP) = -589.923368296 Sum of electronic and zero-point Energies= -589.724673 Sum of electronic and thermal Energies= -589.712170 Sum of electronic and thermal Enthalpies= -589.711226 Sum of electronic and thermal Free Energies= -589.764392 ----- TS: 13b (NMe) <--> 15b (NMe) 1,0 6 1.688416 -0.843201 -0.581490 7 0.632105 -0.049744 -0.177119 7 0.676086 1.199102 -0.747595 6 1.758237 1.189666 -1.513718 6 2.423606 -0.065790 -1.447100 6 -0.397475 -0.344116 0.733763 6 -0.750353 0.574041 1.746530 6 -2.067351 0.773999 2.169440 6 -3.193445 0.352432 1.435083 6 -3.095567 -0.474368 0.309594 6 -1.870002 -1.101442 0.281207 7 -0.903861 -1.750301 0.742428 1 -4.172678 0.732016 1.717949 1 -2.235414 1.448474 3.004144 1 0.013558 1.277237 2.069137 6 2.135160 2.401213 -2.310985 1 3.328671 -0.361766 -1.960203 6 1.933114 -2.237127 -0.096218 1 -3.860513 -0.586689 -0.448827 1 2.894381 -2.587946 -0.481785 1 1.963786 -2.286500 0.997912 1 1.152273 -2.931343 -0.422622 1 3.130535 2.768814 -2.032936 1 2.158448 2.181197 -3.385267 1 1.410597 3.201253 -2.138118 SCF Done: E(RBLYP) = -589.919066310 Sum of electronic and zero-point Energies= -589.721602 Sum of electronic and thermal Energies= -589.709508 Sum of electronic and thermal Enthalpies= -589.708564 Sum of electronic and thermal Free Energies= -589.760271 ------ 15b (NMe) 0,1 7 -0.293770 0.118704 0.682556 6 -1.602450 0.104628 1.144246 6 -1.505571 0.102263 2.516265 6 -0.116775 0.117271 2.820396 7 0.611445 0.125748 1.715012 6 -2.839746 0.107421 0.301673 6 0.542939 0.117325 4.164868 6 0.196451 0.163151 -0.628449 6 1.485369 0.527767 -0.918267 6 2.112051 0.586618 -2.222358 6 1.840873 -0.163873 -3.332004 6 0.814235 -1.206959 -3.281398 6 -0.192959 -0.796621 -2.525713 7 -0.746589 -0.065042 -1.668547 1 -2.334178 0.090476 3.211065 1 2.067388 0.889394 -0.077792 1 2.929606 1.302266 -2.298151 1 2.392130 0.020872 -4.253364 1 0.901466 -2.187760 -3.733778 1 0.259583 -0.767783 4.747132 1 1.629662 0.121775 4.048120 1 0.252468 0.998246 4.750134 1 -2.912910 -0.785481 -0.326328 1 -3.709624 0.138726 0.964444 1 -2.879707 0.969452 -0.370194 SCF Done: E(RBLYP) = -589.935917180 Sum of electronic and zero-point Energies= -589.736685 Sum of electronic and thermal Energies= -589.724351 Sum of electronic and thermal Enthalpies= -589.723407 Sum of electronic and thermal Free Energies= -589.775704 ------ 15b (NN) 6 -1.670018 -0.188889 1.104444 6 -1.602332 -0.175436 2.480040 6 -0.224056 -0.070420 2.806645 7 0.523763 -0.026686 1.712143 7 -0.361793 -0.089998 0.669726 6 0.166172 -0.081785 -0.634846 7 1.332670 -0.866513 -0.819192 6 2.097118 -0.246214 -1.589782 6 2.407793 0.483449 -2.645621 6 1.265440 0.473713 -3.576683 6 -0.007813 0.503024 -3.095569 6 -0.437596 0.525908 -1.699584 6 0.412438 -0.012096 4.161740 6 -2.862828 -0.343805 0.214115 1 -2.439587 -0.254345 3.160275 1 -1.388599 1.013808 -1.512458 1 -0.816629 0.556004 -3.823615 1 1.433438 0.440523 -4.652957 1 3.302775 1.081187 -2.767519 1 0.168379 -0.901450 4.755375 1 1.499011 0.046945 4.059279 1 0.069318 0.862265 4.728132 1 -2.660396 -1.018807 -0.624173 1 -3.691255 -0.759555 0.794510 1 -3.204852 0.611120 -0.204993 SCF Done: E(RBLYP) = -589.927794531 Sum of electronic and zero-point Energies= -589.728746 Sum of electronic and thermal Energies= -589.716381 Sum of electronic and thermal Enthalpies= -589.715437 Sum of electronic and thermal Free Energies= -589.767687 ----- TS: 2b (NN) <--> 14b (NN) 0,1 6 1.410437 -1.126074 0.192610 6 0.741975 0.150006 -0.113778 6 1.599184 1.162548 -0.469234 6 3.021491 0.998770 -0.417941 6 3.624763 -0.110250 0.147651 6 2.796727 -1.129983 0.666009 7 -0.645823 0.219981 -0.039233 6 -1.498138 1.303657 0.111894 6 -2.768336 0.778305 0.096600 6 -2.615859 -0.629750 -0.051999 7 -1.337532 -0.963199 -0.124425 7 1.462523 -2.300695 -0.260838 1 4.701277 -0.136208 0.296819 1 3.632932 1.822062 -0.776117 1 1.207978 2.108539 -0.822781 6 -3.680779 -1.680531 -0.113572 1 -3.689679 1.333998 0.206376 6 -1.062890 2.722476 0.296427 1 3.135569 -1.899795 1.341810 1 -4.312109 -1.660015 0.782938 1 -4.337733 -1.530028 -0.978740 1 -3.222908 -2.669410 -0.194557 1 -1.904903 3.306705 0.677637 1 -0.237732 2.806693 1.012036 1 -0.738314 3.189805 -0.641951 SCF Done: E(UBLYP) = -589.905364240 S**2 before annihilation 0.1924, after 0.0073 Sum of electronic and zero-point Energies= -589.707752 Sum of electronic and thermal Energies= -589.695683 Sum of electronic and thermal Enthalpies= -589.694739 Sum of electronic and thermal Free Energies= -589.746466 ----- 14b (NN) 0,1 6 1.506241 -0.935146 0.156160 6 0.671154 0.203483 -0.148786 6 1.445953 1.285100 -0.484295 6 2.885546 1.278195 -0.339765 6 3.588209 0.285645 0.289787 6 2.872056 -0.901148 0.735345 7 -0.719259 0.123949 -0.087561 6 -1.671364 1.104907 0.122383 6 -2.882766 0.451783 0.106295 6 -2.589261 -0.923999 -0.103742 7 -1.283309 -1.120017 -0.214815 7 2.218908 -1.852837 -0.332225 1 4.632501 0.439538 0.553002 1 3.408098 2.168951 -0.678397 1 0.980369 2.184457 -0.870981 6 -3.541227 -2.076507 -0.196619 1 -3.854476 0.905701 0.245652 6 -1.370596 2.551742 0.351260 1 3.108631 -1.380454 1.682230 1 -4.150314 -2.164085 0.711146 1 -4.230191 -1.956303 -1.041356 1 -2.986034 -3.007838 -0.333512 1 -2.255010 3.040115 0.769396 1 -0.540206 2.689017 1.052594 1 -1.111418 3.078907 -0.575686 SCF Done: E(RBLYP) = -589.920273374 Sum of electronic and zero-point Energies= -589.720913 Sum of electronic and thermal Energies= -589.708649 Sum of electronic and thermal Enthalpies= -589.707705 Sum of electronic and thermal Free Energies= -589.759844 ----- TS: 2b (NMe) <--> 14b (NMe) 0,1 6 -1.723948 0.753100 0.067590 6 -0.686720 -0.284516 -0.053952 6 -1.182997 -1.553884 -0.226257 6 -2.587405 -1.825724 -0.212141 6 -3.531348 -0.883955 0.154465 6 -3.068001 0.399134 0.521317 7 0.681919 -0.015164 -0.000328 6 1.368945 1.191697 0.003082 6 2.700893 0.858321 0.050314 6 2.757333 -0.563722 0.070904 7 1.543330 -1.087049 0.043440 7 -2.108050 1.780894 -0.563896 1 -4.575736 -1.159584 0.273539 1 -2.901210 -2.840995 -0.438849 1 -0.481848 -2.362474 -0.392469 6 3.966110 -1.445991 0.117091 1 3.529749 1.552582 0.064095 6 0.754642 2.556125 -0.028553 1 -3.655320 1.120340 1.068486 1 4.609203 -1.283400 -0.756268 1 4.571166 -1.243473 1.008991 1 3.663076 -2.495894 0.133972 1 1.557298 3.297557 -0.067614 1 0.104705 2.701895 -0.896415 1 0.153489 2.759160 0.864855 SCF Done: E(UBLYP) = -589.908871665 S**2 before annihilation 0.1692, after 0.0060 Sum of electronic and zero-point Energies= -589.711174 Sum of electronic and thermal Energies= -589.699067 Sum of electronic and thermal Enthalpies= -589.698122 Sum of electronic and thermal Free Energies= -589.750457 ----- 14b (NMe) 0,1 6 0.992789 -0.344758 1.492506 6 -0.148530 0.001981 0.677262 6 -1.251451 0.200609 1.466470 6 -1.242142 -0.049247 2.890367 6 -0.218836 -0.670199 3.554722 6 0.980557 -1.024646 2.804344 7 -0.139938 0.096844 -0.715819 6 0.928003 0.312735 -1.566658 6 0.385878 0.382217 -2.829400 6 -1.016428 0.208290 -2.666493 7 -1.331525 0.035474 -1.389968 7 1.911160 0.108207 2.234429 1 -0.354456 -1.003215 4.581241 1 -2.149683 0.205907 3.431236 1 -2.163654 0.549001 0.994612 6 -2.081431 0.196459 -3.719576 1 0.929551 0.541112 -3.750538 6 2.349566 0.447634 -1.120370 1 1.481344 -1.976858 2.964264 1 -2.104454 1.143176 -4.272801 1 -1.910852 -0.603480 -4.450209 1 -3.060315 0.040765 -3.258882 1 2.970423 0.708085 -1.981684 1 2.474201 1.228557 -0.362417 1 2.742165 -0.483176 -0.694351 SCF Done: E(RBLYP) = -589.923052883 Sum of electronic and zero-point Energies= -589.723760 Sum of electronic and thermal Energies= -589.711410 Sum of electronic and thermal Enthalpies= -589.710466 Sum of electronic and thermal Free Energies= -589.762841 ----- TS: 14b (NMe) <--> 16b (NMe) 0,1 6 1.051074 -0.301908 1.429305 6 0.008264 0.198608 0.686019 6 -1.043170 0.621831 1.526031 6 -1.187547 0.156960 2.835694 6 -0.413463 -0.885559 3.386700 6 0.820231 -1.303667 2.897633 7 -0.064498 0.200705 -0.716979 6 0.943688 0.433581 -1.625449 6 0.346787 0.372013 -2.866483 6 -1.028131 0.110709 -2.625291 7 -1.274831 0.003898 -1.323734 7 1.833137 -0.324453 2.401621 1 -0.880067 -1.514708 4.143847 1 -2.063836 0.485626 3.387004 1 -1.807670 1.260667 1.093117 6 -2.136417 -0.047911 -3.621374 1 0.837674 0.503753 -3.821091 6 2.361630 0.704867 -1.235052 1 1.179531 -2.324553 3.005579 1 -2.261625 0.856967 -4.228613 1 -1.939128 -0.877612 -4.311007 1 -3.077469 -0.247858 -3.102309 1 2.932239 1.002137 -2.119151 1 2.432841 1.512936 -0.497474 1 2.853165 -0.175549 -0.802659 SCF Done: E(RBLYP) = -589.910757904 Sum of electronic and zero-point Energies= -589.713328 Sum of electronic and thermal Energies= -589.701065 Sum of electronic and thermal Enthalpies= -589.700121 Sum of electronic and thermal Free Energies= -589.752492 ------ 16b (NMe) 0,1 6 -0.062131 1.308165 -1.374315 7 0.432525 0.323129 -0.550991 7 1.453832 -0.374199 -1.130359 6 1.605762 0.171731 -2.334026 6 0.682595 1.229772 -2.533584 6 0.052885 -0.017029 0.757294 6 -0.854415 0.589073 1.523195 7 -1.716682 0.546144 2.442613 6 -2.308828 -0.731754 2.508229 6 -1.570826 -1.873461 2.401920 6 -0.139278 -1.990717 2.167204 6 0.662421 -1.151143 1.456446 1 1.732905 -1.324313 1.383862 1 0.331861 -2.864960 2.614865 1 -2.086175 -2.798634 2.652020 1 -3.359630 -0.763046 2.787237 6 2.650629 -0.347885 -3.273976 1 0.570352 1.854833 -3.408966 6 -1.175508 2.224861 -0.987290 1 -1.316057 2.979197 -1.766562 1 -2.126080 1.692344 -0.859006 1 -0.965623 2.742332 -0.042393 1 3.370868 0.433902 -3.544356 1 3.195987 -1.171732 -2.806036 1 2.204024 -0.715114 -4.206090 SCF Done: E(RBLYP) = -589.927625609 Sum of electronic and zero-point Energies= -589.728547 Sum of electronic and thermal Energies= -589.716021 Sum of electronic and thermal Enthalpies= -589.715077 Sum of electronic and thermal Free Energies= -589.768025 ------ 16b (NMe) (nitrile ylide form) 0,1 6 -2.885002 -0.026041 0.626722 6 -2.543609 1.279569 0.173597 7 -1.247289 1.374855 -0.068827 7 -0.726602 0.138750 0.232502 6 -1.713916 -0.743597 0.656638 6 0.643479 -0.070824 0.070249 6 1.501318 0.976736 -0.175115 6 2.936317 0.941221 -0.376419 6 3.711938 -0.075767 -0.853320 6 3.087028 -1.331405 -1.213962 7 2.052369 -1.692838 -0.533902 6 1.235350 -1.388412 0.399659 6 -3.446285 2.454922 -0.039811 6 -1.513217 -2.175361 1.042604 1 4.780467 0.068916 -0.995855 1 3.410175 -1.941811 -2.054160 1 3.436256 1.886503 -0.171161 1 1.063279 1.965518 -0.081414 1 -3.865066 -0.397018 0.893467 1 -2.869911 3.308084 -0.406415 1 -3.945449 2.746568 0.892212 1 -4.231093 2.224911 -0.770541 1 -0.850430 -2.283335 1.904547 1 -1.068503 -2.762191 0.231908 1 -2.489485 -2.607763 1.283938 SCF Done: E(RBLYP) = -589.909720819 Sum of electronic and zero-point Energies= -589.710832 Sum of electronic and thermal Energies= -589.698418 Sum of electronic and thermal Enthalpies= -589.697474 Sum of electronic and thermal Free Energies= -589.749866 ------ 16b NN 0,1 6 2.736182 -0.866270 0.005100 7 1.493732 -1.204034 -0.327934 7 0.769062 -0.048989 -0.216130 6 1.541262 1.012826 0.192566 6 2.819299 0.510613 0.333764 6 -0.624755 -0.092756 -0.440728 6 -1.397203 0.969427 -1.086773 6 -2.635232 1.285980 -0.610370 6 -3.348338 0.653659 0.493542 6 -3.293736 -0.648105 0.890938 7 -2.529125 -1.607126 0.173489 6 -1.413776 -1.100947 -0.088004 1 -0.991720 1.496407 -1.950806 1 -3.164306 2.105784 -1.094161 1 -4.099321 1.268887 0.985664 1 -3.924008 -1.029514 1.690667 6 1.014732 2.389609 0.454480 1 3.695528 1.068515 0.635427 6 3.828044 -1.892903 -0.012684 1 4.290094 -2.003702 0.975991 1 3.421202 -2.862013 -0.313248 1 4.624629 -1.619914 -0.715579 1 1.799533 2.991531 0.920912 1 0.701794 2.903733 -0.461906 1 0.152001 2.374525 1.130065 SCF Done: E(RBLYP) = -589.922893955 Sum of electronic and zero-point Energies= -589.723962 Sum of electronic and thermal Energies= -589.711341 Sum of electronic and thermal Enthalpies= -589.710397 Sum of electronic and thermal Free Energies= -589.764042 ------ 16b (NN) (nitrile ylide form) 0,1 7 2.401198 0.916406 0.647533 6 3.377578 0.144314 0.989505 1 4.676982 -1.360749 0.029214 1 3.884373 0.307427 1.936914 6 1.499344 1.171229 -0.209028 6 3.666047 -0.965974 0.103099 6 0.622381 -0.037653 -0.267693 1 2.909244 -2.393593 -1.233366 7 -0.756462 0.123857 -0.177996 6 1.232518 -1.227489 -0.583948 1 0.597166 -2.004129 -0.998617 6 2.653690 -1.540476 -0.607513 7 -1.284709 1.375281 -0.397319 6 -1.496812 -2.216166 0.570156 6 -2.585617 1.243608 -0.206194 6 -1.739296 -0.790972 0.184467 6 -3.499727 2.417987 -0.372334 6 -2.920587 -0.092019 0.161896 1 -3.899186 -0.485061 0.402223 1 -2.918590 3.307190 -0.628609 1 -4.059063 2.619470 0.549276 1 -4.234218 2.241043 -1.167414 1 -0.613232 -2.320683 1.208145 1 -1.354791 -2.871066 -0.298511 1 -2.365985 -2.586993 1.120749 SCF Done: E(RBLYP) = -589.901876441 Sum of electronic and zero-point Energies= -589.703208 Sum of electronic and thermal Energies= -589.690827 Sum of electronic and thermal Enthalpies= -589.689883 Sum of electronic and thermal Free Energies= -589.742128 ----- TS: 2b (NN) <--> 5b 0,1 7 1.685369 0.454387 -0.273160 6 2.522434 1.484748 -0.170046 6 1.774147 2.680169 -0.057835 6 0.436856 2.318766 -0.067160 7 0.417999 0.950899 -0.194693 6 -0.572828 -0.037546 -0.066063 6 -0.001270 -1.325208 0.228169 6 -0.896866 -2.438877 0.283584 6 -2.261061 -2.244243 0.147929 6 -2.788255 -0.972533 -0.129328 6 -1.937167 0.129465 -0.262325 7 1.298768 -1.461449 0.473640 1 -2.344733 1.097228 -0.529616 1 -3.856196 -0.843126 -0.274011 1 -0.480025 -3.421614 0.476361 1 -2.930446 -3.096510 0.229748 6 4.004013 1.279832 -0.216730 6 -0.782285 3.172464 0.066026 1 2.158396 3.689427 0.004422 1 4.483303 1.659558 0.693149 1 4.229929 0.214511 -0.305997 1 4.453850 1.803741 -1.068486 1 -0.479124 4.197128 0.296886 1 -1.374922 3.201695 -0.856843 1 -1.438177 2.824210 0.872635 SCF Done: E(UBLYP) = -589.924961909 S**2 before annihilation 0.6931, after 0.0731 Sum of electronic and zero-point Energies= -589.726681 Sum of electronic and thermal Energies= -589.714965 Sum of electronic and thermal Enthalpies= -589.714020 Sum of electronic and thermal Free Energies= -589.764697 ----- 5b (heteropentalene) 0,1 6 -0.464653 0.796495 -1.838633 6 0.898162 0.270759 0.356762 6 2.407059 -0.206833 2.602880 6 0.375810 -0.580947 1.375308 6 2.147322 0.882691 0.437329 6 2.901199 0.632095 1.580689 6 1.162958 -0.815380 2.521056 7 -0.864096 -1.062115 1.072445 1 2.518834 1.526196 -0.353726 1 3.880722 1.088361 1.685502 1 0.790577 -1.458924 3.311398 1 3.022130 -0.380821 3.481916 6 -3.364288 -1.337912 -0.764632 7 -1.112998 -0.510549 -0.132997 7 -0.098442 0.294835 -0.612222 6 -2.131777 -0.541662 -1.025069 6 0.421599 1.705973 -2.620893 6 -1.729594 0.277055 -2.097128 1 -2.314733 0.471756 -2.984914 1 -4.060785 -1.230605 -1.600467 1 -3.869437 -1.008038 0.151857 1 -3.135065 -2.403604 -0.639283 1 0.643363 2.635134 -2.078613 1 -0.070879 1.977368 -3.558641 1 1.381245 1.233969 -2.871644 SCF Done: E(RBLYP) = -589.994768866 Sum of electronic and zero-point Energies= -589.792659 Sum of electronic and thermal Energies= -589.781189 Sum of electronic and thermal Enthalpies= -589.780245 Sum of electronic and thermal Free Energies= -589.829775 ----- TS: 2b (NMe) <--> 18 0,1 7 -1.451892 -1.085133 -0.096631 7 -0.631041 -0.010042 0.138763 6 -1.356939 1.162456 0.267244 6 -2.679873 0.813005 0.078684 6 -2.683389 -0.590074 -0.129078 6 0.763427 -0.223225 0.135531 6 1.726653 0.792091 -0.292555 6 3.103967 0.359858 -0.411005 6 3.507600 -0.916177 -0.102423 6 2.557630 -1.858505 0.339123 6 1.213494 -1.507628 0.445320 7 1.510203 2.059098 -0.607026 6 -0.716430 2.439797 0.554106 6 -3.854412 -1.493004 -0.369009 1 4.553848 -1.194160 -0.191927 1 2.865745 -2.867830 0.594930 1 0.475106 -2.240675 0.746067 1 -3.528894 1.480966 0.119074 1 3.807623 1.116392 -0.741721 1 -3.510854 -2.521164 -0.508318 1 -4.553420 -1.471896 0.475917 1 -4.413536 -1.189401 -1.262075 1 0.376285 2.430888 -0.217604 1 -0.235731 2.522247 1.532949 1 -1.317428 3.315612 0.311338 SCF Done: E(UBLYP) = -589.912685485 S**2 before annihilation 1.0402, after 0.3244 Sum of electronic and zero-point Energies= -589.719633 Sum of electronic and thermal Energies= -589.708137 Sum of electronic and thermal Enthalpies= -589.707193 Sum of electronic and thermal Free Energies= -589.757105 ----- TS: 2b (NMe) <--> 18 (closed-shell singlet, RDFT) 0,1 7 -1.504223 -1.104407 -0.178345 7 -0.629960 -0.062761 -0.012194 6 -1.290097 1.121842 0.210760 6 -2.636459 0.825897 0.171663 6 -2.714167 -0.575598 -0.069787 6 0.762436 -0.310662 -0.012789 6 1.681195 0.777169 -0.250161 6 3.073255 0.494616 -0.084530 6 3.533080 -0.806364 0.083370 6 2.616552 -1.841885 0.275092 6 1.238244 -1.579982 0.276976 7 1.402014 1.987720 -0.746965 6 -0.581021 2.389814 0.462981 6 -3.937285 -1.425396 -0.228809 1 4.600591 -1.004583 0.121815 1 2.963193 -2.854871 0.457222 1 0.521055 -2.370714 0.464702 1 -3.452462 1.523876 0.298086 1 3.753744 1.332958 -0.187963 1 -3.647766 -2.464744 -0.403002 1 -4.569367 -1.385532 0.666515 1 -4.548819 -1.090581 -1.075283 1 0.254285 2.416216 -0.471428 1 -0.041449 2.456157 1.408357 1 -1.182219 3.281245 0.274899 SCF Done: E(RBLYP) = -589.897730551 Sum of electronic and zero-point Energies= -589.702710 Sum of electronic and thermal Energies= -589.691463 Sum of electronic and thermal Enthalpies= -589.690519 Sum of electronic and thermal Free Energies= -589.739983 ----- TS: 2b (NMe) <--> 18 (triplet) 0,3 7 -1.453987 -1.085988 -0.103258 7 -0.630245 -0.015686 0.147335 6 -1.349561 1.156651 0.288726 6 -2.675521 0.814206 0.091643 6 -2.683588 -0.586445 -0.132389 6 0.765504 -0.226813 0.131692 6 1.714591 0.778850 -0.320671 6 3.090503 0.366513 -0.426500 6 3.510365 -0.900636 -0.089418 6 2.570792 -1.842977 0.365102 6 1.223590 -1.503341 0.464738 7 1.474371 2.044914 -0.674938 6 -0.704831 2.422857 0.591773 6 -3.857676 -1.482152 -0.385299 1 4.559628 -1.168472 -0.173098 1 2.888196 -2.845128 0.637758 1 0.491095 -2.236005 0.780996 1 -3.522339 1.484474 0.139992 1 3.786503 1.122155 -0.775655 1 -3.516733 -2.508330 -0.544370 1 -4.554121 -1.475360 0.461990 1 -4.418654 -1.161171 -1.271030 1 0.397685 2.418039 -0.248518 1 -0.163293 2.476981 1.539337 1 -1.303949 3.309865 0.392251 SCF Done: E(UBLYP) = -589.919591889 S**2 before annihilation 2.0490, after 2.0013 Sum of electronic and zero-point Energies= -589.726356 Sum of electronic and thermal Energies= -589.714951 Sum of electronic and thermal Enthalpies= -589.714007 Sum of electronic and thermal Free Energies= -589.764698 ----- 18 (closed shell singlet state) 0,1 6 -3.105813 -0.409607 -0.094534 6 -3.400808 -0.107537 1.263466 6 -2.387518 0.182584 2.125534 6 -0.982157 0.202799 1.741511 6 -0.717046 -0.060626 0.323640 6 -1.806850 -0.370758 -0.535656 1 -3.900938 -0.687122 -0.779602 1 -4.429756 -0.123868 1.613721 1 -2.597494 0.398594 3.170861 7 -0.039926 0.452560 2.622800 1 -1.577736 -0.589468 -1.569638 6 1.895192 -0.147029 0.152752 6 2.675829 -0.133770 -1.049003 6 1.808905 0.092580 -2.081902 7 0.522512 0.204181 -1.636615 7 0.529664 0.052982 -0.306224 1 3.753229 -0.212032 -1.078241 6 2.082803 0.250466 -3.544780 1 3.150640 0.144483 -3.754164 1 1.538162 -0.501786 -4.126782 1 1.754847 1.234371 -3.898765 6 2.363155 -0.275630 1.419562 1 1.719182 -0.143212 2.280904 1 3.424005 -0.483271 1.530743 1 -0.474041 0.654417 3.527696 SCF Done: E(RBLYP) = -589.935593904 Sum of electronic and zero-point Energies= -589.736209 Sum of electronic and thermal Energies= -589.724268 Sum of electronic and thermal Enthalpies= -589.723324 Sum of electronic and thermal Free Energies= -589.774975 ----- 18 (triplet state) 0,3 6 -3.096062 -0.657431 0.150533 6 -3.319540 -0.151579 1.444678 6 -2.276857 0.414137 2.146376 6 -0.953148 0.519598 1.593955 6 -0.746555 -0.065850 0.285378 6 -1.819682 -0.613113 -0.413353 1 -3.914166 -1.099424 -0.410496 1 -4.311524 -0.201442 1.884826 1 -2.438808 0.824468 3.140798 7 0.053309 1.158084 2.193709 1 -1.639262 -1.003130 -1.408455 6 1.769103 -0.433557 0.118799 6 2.621843 -0.280663 -0.994032 6 1.822394 0.180124 -2.051231 7 0.547395 0.317582 -1.671103 7 0.513478 -0.023311 -0.346442 1 3.680599 -0.499958 -1.007151 6 2.224999 0.518223 -3.454749 1 2.908388 1.375750 -3.477725 1 2.739535 -0.322449 -3.934972 1 1.340938 0.769014 -4.046660 6 2.059655 -0.964132 1.372202 1 1.321612 -1.049665 2.155577 1 3.075168 -1.276420 1.584548 1 -0.278650 1.522224 3.095228 SCF Done: E(UBLYP) = -589.943546461 S**2 before annihilation 2.0591, after 2.0021 Sum of electronic and zero-point Energies= -589.746334 Sum of electronic and thermal Energies= -589.734070 Sum of electronic and thermal Enthalpies= -589.733126 Sum of electronic and thermal Free Energies= -589.785927 ----- TS: 18 <--> 8 0,1 7 -0.606870 0.010437 0.272424 6 -1.338995 1.236622 0.239199 6 -2.664685 0.861172 -0.121328 6 -2.673077 -0.515958 -0.154355 7 -1.431881 -1.028815 0.056304 6 -0.899081 2.465913 0.646983 6 -3.820006 -1.451317 -0.383500 6 0.773141 -0.225563 0.244036 6 1.760102 0.796491 -0.089357 6 3.028284 0.283692 -0.574446 6 3.381802 -1.032939 -0.475635 6 2.453480 -1.980197 0.028266 6 1.175732 -1.579964 0.342474 7 1.575295 2.092459 0.093957 1 2.737191 -3.022591 0.135483 1 4.375773 -1.353197 -0.777372 1 3.743742 1.021298 -0.931134 1 0.430417 -2.303886 0.645979 1 -3.498718 1.540437 -0.224193 1 -4.706102 -0.905191 -0.718818 1 -3.563582 -2.200712 -1.139804 1 -4.077761 -1.990746 0.535796 1 -0.005051 2.622640 1.218984 1 -1.562165 3.310554 0.475873 1 2.310276 2.615113 -0.393605 SCF Done: E(RBLYP) = -589.933746435 Sum of electronic and zero-point Energies= -589.734844 Sum of electronic and thermal Energies= -589.723492 Sum of electronic and thermal Enthalpies= -589.722547 Sum of electronic and thermal Free Energies= -589.772649 ----- TS: 18 <--> 8 triplet 0,3 7 -0.623383 -0.122942 0.189967 6 0.712330 -0.359429 0.092926 6 3.509827 -0.799035 -0.041628 6 1.638569 0.757507 -0.207178 6 1.234447 -1.678244 0.187555 6 2.587701 -1.890854 0.122307 6 3.036579 0.481467 -0.184857 7 1.112785 1.951411 -0.502364 1 0.531743 -2.491212 0.323304 1 2.975008 -2.902152 0.207565 1 3.720209 1.314394 -0.335623 1 4.576902 -0.995736 -0.066231 6 -0.397826 2.287795 0.480961 7 -1.558417 -1.135022 0.037779 6 -2.720698 -0.485914 -0.094037 6 -3.985941 -1.269515 -0.265186 6 -2.577215 0.920389 -0.025806 6 -1.225978 1.151382 0.224142 1 -3.364012 1.660931 -0.054796 1 0.124103 2.331044 1.437273 1 -0.806584 3.250406 0.181819 1 1.802508 2.702826 -0.577402 1 -3.760831 -2.338188 -0.308218 1 -4.506947 -0.985005 -1.187290 1 -4.679774 -1.094739 0.566734 SCF Done: E(UBLYP) = -589.905893197 S**2 before annihilation 2.0105, after 2.0001 Sum of electronic and zero-point Energies= -589.708024 Sum of electronic and thermal Energies= -589.696724 Sum of electronic and thermal Enthalpies= -589.695779 Sum of electronic and thermal Free Energies= -589.746453 ----- 8 0,1 7 0.146826 -0.041067 -0.635474 6 0.410014 -0.048758 0.749536 6 0.804921 -0.004361 3.498330 6 -0.698249 0.158319 1.598714 6 1.690640 -0.232260 1.263423 6 1.890386 -0.207738 2.644063 6 -0.478682 0.172578 2.981162 7 -1.953126 0.412190 1.032042 1 2.510090 -0.381831 0.569747 1 2.888763 -0.348629 3.046726 1 -1.321977 0.332758 3.649624 1 0.951743 0.011985 4.574666 6 -2.276899 -0.225456 -0.246355 7 1.116408 0.027747 -1.583333 6 0.457744 0.033156 -2.742795 6 1.207386 0.106542 -4.038110 6 -0.948089 -0.027705 -2.539785 6 -1.107905 -0.071912 -1.171562 1 -1.725697 -0.037094 -3.290858 1 -2.522959 -1.298099 -0.127626 1 -3.159610 0.263435 -0.670634 1 -2.711586 0.373372 1.702565 1 2.282766 0.132345 -3.843816 1 0.938206 1.004800 -4.607109 1 0.991907 -0.759553 -4.675669 SCF Done: E(RBLYP) = -590.038838429 Sum of electronic and zero-point Energies= -589.834293 Sum of electronic and thermal Energies= -589.823386 Sum of electronic and thermal Enthalpies= -589.822442 Sum of electronic and thermal Free Energies= -589.871046 ------ 8 triplet 0,3 6 0.711207 -0.409257 0.009186 6 3.523609 -0.758858 -0.044030 6 1.630841 0.760870 -0.061265 6 1.268853 -1.742777 -0.004822 6 2.618468 -1.897604 -0.026645 6 3.000440 0.543070 -0.067878 6 -0.301257 2.289031 0.271249 6 -2.739706 -0.490005 -0.004941 6 -4.026846 -1.248901 -0.089553 6 -2.558205 0.910801 0.055445 6 -1.188007 1.108036 0.084051 7 -0.616487 -0.167180 0.038722 7 1.061575 2.004485 -0.192180 7 -1.568396 -1.155313 -0.016015 1 0.581546 -2.579204 0.004374 1 3.041282 -2.898803 -0.033914 1 3.668837 1.401119 -0.106641 1 4.595304 -0.919741 -0.043886 1 -3.327770 1.669921 0.079605 1 -0.263360 2.586540 1.334202 1 -0.686579 3.150826 -0.285990 1 1.706078 2.784597 -0.141288 1 -3.945214 -2.201485 0.443607 1 -4.290501 -1.479428 -1.130809 1 -4.852847 -0.674720 0.342271 SCF Done: E(UBLYP) = -589.924834852 S**2 before annihilation 2.0177, after 2.0001 Sum of electronic and zero-point Energies= -589.725691 Sum of electronic and thermal Energies= -589.713757 Sum of electronic and thermal Enthalpies= -589.712813 Sum of electronic and thermal Free Energies= -589.765144 ------