# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 2000 Radical Cations of Perinaphthocyclopropanes and Their Photo- rearrangement Products. Conditions for the Observation of 1,3-Perinaphthadiyl Radical Cations. Thomas Bally,* Zhendong Zhu, Jakob Wirz, Markus Fülscher, and Jun-Ya Hasegawa SUPPLEMENTARY DATA ****************** B3LYP/6-31G* optimized geometries and total energies of all species discussed in the paper. 1.6b,7a-dihydro-7H-cycloprop[a]acenaphthylene, neutral (1) HF=-501.3858736 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.998393 1.145551 0.000000 2 6 0.000000 0.150039 0.000000 3 6 1.431251 1.600527 1.277682 4 6 1.431251 1.600527 -1.277682 5 6 -0.562015 -0.403404 1.177522 6 6 -0.562015 -0.403404 -1.177522 7 6 0.877004 1.070280 2.428381 8 6 0.877004 1.070280 -2.428381 9 6 -0.126984 0.060360 2.398954 10 6 -0.126984 0.060360 -2.398954 11 6 -1.556378 -1.447237 0.767810 12 6 -1.556378 -1.447237 -0.767810 13 6 -1.004102 -2.633484 0.000000 14 1 2.192076 2.374551 1.345465 15 1 2.192076 2.374551 -1.345465 16 1 1.215727 1.435375 3.394858 17 1 1.215727 1.435375 -3.394858 18 1 -0.528493 -0.325743 3.332399 19 1 -0.528493 -0.325743 -3.332399 20 1 -2.473236 -1.583493 -1.334237 21 1 -2.473236 -1.583493 1.334237 22 1 -1.602438 -3.541331 0.000000 23 1 0.070009 -2.798998 0.000000 ---------------------------------------------------------- 2.6b,7a-dihydro-7H-cycloprop[a]acenaphthylene, radical cation (1.+) State=2-A"\HF=-501.1230669 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 1.140735 0.996137 0.000000 2 6 0.000000 0.169944 0.000000 3 6 1.642233 1.371483 1.271331 4 6 1.642233 1.371483 -1.271331 5 6 -0.630459 -0.308955 1.167370 6 6 -0.630459 -0.308955 -1.167370 7 6 1.014968 0.907575 2.445402 8 6 1.014968 0.907575 -2.445402 9 6 -0.103417 0.065855 2.416989 10 6 -0.103417 0.065855 -2.416989 11 6 -1.757119 -1.182262 0.758450 12 6 -1.757119 -1.182262 -0.758450 13 6 -1.325244 -2.446163 0.000000 14 1 2.511019 2.019023 1.348719 15 1 2.511019 2.019023 -1.348719 16 1 1.417810 1.214251 3.405615 17 1 1.417810 1.214251 -3.405615 18 1 -0.551356 -0.278006 3.344030 19 1 -0.551356 -0.278006 -3.344030 20 1 -2.672578 -1.237495 -1.338938 21 1 -2.672578 -1.237495 1.338938 22 1 -2.022329 -3.278913 0.000000 23 1 -0.274890 -2.720500 0.000000 ---------------------------------------------------------- 3. 2,3-dihydro-1H-1,3-perinaphthadiyl radical cation (obtained by breaking the central cyclopropane bond in 1.+), 2A2 state State=2-A2\HF=-501.1317615\S2=0.792\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 -0.030523 2 6 0.000000 0.000000 -1.449033 3 6 0.000000 -1.264833 0.678663 4 6 0.000000 1.264833 0.678663 5 6 0.000000 -1.247909 -2.136765 6 6 0.000000 1.247909 -2.136765 7 6 0.000000 -2.485774 -0.063929 8 6 0.000000 2.485774 -0.063929 9 6 0.000000 -2.462315 -1.450062 10 6 0.000000 2.462315 -1.450062 11 1 0.000000 1.242109 -3.223010 12 1 0.000000 -1.242109 -3.223010 13 1 0.000000 -3.393513 -2.007562 14 1 0.000000 3.393513 -2.007562 15 1 0.000000 -3.427326 0.476446 16 1 0.000000 3.427326 0.476446 17 6 0.000000 -1.254324 2.063928 18 6 0.000000 1.254324 2.063928 19 6 0.000000 0.000000 2.830021 20 1 0.000000 -2.189407 2.617912 21 1 0.000000 2.189407 2.617912 22 1 -0.856154 0.000000 3.533821 23 1 0.856154 0.000000 3.533821 ---------------------------------------------------------- 4. 2,3-dihydro-1H-1,3-perinaphthadiyl radical cation (obtained by breaking the central cyclopropane bond in 1.+), 2B1 state State=2-B1\HF=-501.1278254\S2=0.807\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 -0.038343 2 6 0.000000 0.000000 -1.457608 3 6 0.000000 -1.241338 0.680631 4 6 0.000000 1.241338 0.680631 5 6 0.000000 -1.234508 -2.152751 6 6 0.000000 1.234508 -2.152751 7 6 0.000000 -2.455280 -0.072192 8 6 0.000000 2.455280 -0.072192 9 6 0.000000 -2.448721 -1.460577 10 6 0.000000 2.448721 -1.460577 11 1 0.000000 1.230625 -3.239415 12 1 0.000000 -1.230625 -3.239415 13 1 0.000000 -3.385057 -2.008411 14 1 0.000000 3.385057 -2.008411 15 1 0.000000 -3.401160 0.463023 16 1 0.000000 3.401160 0.463023 17 6 0.000000 -1.250139 2.070734 18 6 0.000000 1.250139 2.070734 19 6 0.000000 0.000000 2.897110 20 1 0.000000 -2.201281 2.597148 21 1 0.000000 2.201281 2.597148 22 1 -0.864360 0.000000 3.589115 23 1 0.864360 0.000000 3.589115 ---------------------------------------------------------- 5. Diyl radical cation (D.+) obtained by breaking a lateral cyclopropane bond in 1.+. Geometry composed of the opti- mized naphthyl cation and the optimized CH2-radical) HF=-501.085555\S2=0.757\S2-1=0.\S2A=0.75 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 1.128232 0.491500 -0.198037 2 6 2.052996 -0.717772 -0.331902 3 6 3.141163 -0.780870 0.686105 4 1 2.937468 -0.518118 1.720050 5 1 4.097474 -1.240265 0.456829 6 1 2.512260 -0.697333 -1.330815 7 6 1.089029 -1.872302 -0.270329 8 6 1.317026 1.865695 -0.177665 9 6 -0.174242 0.011704 -0.079625 10 6 -0.213080 -1.429752 -0.120755 11 6 -1.474677 -2.081103 -0.016714 12 6 -2.607858 -1.289666 0.119735 13 6 -2.538375 0.124322 0.157507 14 6 -1.318124 0.823047 0.056531 15 6 -1.102065 2.232238 0.076327 16 6 0.188202 2.721461 -0.038921 17 1 2.306073 2.306725 -0.266563 18 1 0.351865 3.794216 -0.024581 19 1 -1.941559 2.913283 0.179155 20 1 -3.464033 0.684584 0.269320 21 1 -3.581691 -1.761218 0.201371 22 1 -1.554965 -3.163760 -0.043119 23 1 1.407744 -2.909125 -0.335194 ---------------------------------------------------------- 6.1H-phenalene, neutral State=1-A'\HF=-501.4146058 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.250009 1.446802 0.000000 2 6 0.000000 0.037418 0.000000 3 6 1.590565 1.907885 0.000000 4 6 -0.855569 2.344313 0.000000 5 6 1.094701 -0.874918 0.000000 6 6 -1.355270 -0.434773 0.000000 7 6 2.636826 1.011355 0.000000 8 6 -2.145982 1.868975 0.000000 9 6 2.386047 -0.376894 0.000000 10 6 -2.395897 0.477378 0.000000 11 6 0.850103 -2.374056 0.000000 12 6 -1.597262 -1.875114 0.000000 13 6 -0.599589 -2.769859 0.000000 14 1 1.778377 2.978918 0.000000 15 1 -0.659893 3.413900 0.000000 16 1 3.662992 1.369466 0.000000 17 1 -2.983041 2.562091 0.000000 18 1 3.225908 -1.068975 0.000000 19 1 -3.421576 0.115780 0.000000 20 1 -0.819183 -3.835309 0.000000 21 1 -2.633519 -2.207169 0.000000 22 1 1.348924 -2.829893 0.870579 23 1 1.348924 -2.829893 -0.870579 ---------------------------------------------------------- 7. 1H-phenalene radical cation, (3.+) State=2-A"\HF=-501.1623803 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -0.059656 1.460248 0.000000 2 6 0.000000 0.031977 0.000000 3 6 1.144983 2.201115 0.000000 4 6 -1.325633 2.094024 0.000000 5 6 1.251894 -0.619033 0.000000 6 6 -1.220873 -0.726133 0.000000 7 6 2.375305 1.546136 0.000000 8 6 -2.510289 1.345910 0.000000 9 6 2.428209 0.152095 0.000000 10 6 -2.461472 -0.041571 0.000000 11 6 1.320952 -2.118174 0.000000 12 6 -1.174822 -2.158008 0.000000 13 6 0.012687 -2.822726 0.000000 14 1 1.103137 3.286612 0.000000 15 1 -1.373551 3.179556 0.000000 16 1 3.295163 2.122126 0.000000 17 1 -3.468623 1.855428 0.000000 18 1 3.392061 -0.350113 0.000000 19 1 -3.380835 -0.619892 0.000000 20 1 0.030739 -3.909164 0.000000 21 1 -2.111751 -2.707854 0.000000 22 1 1.912978 -2.465934 0.865035 23 1 1.912978 -2.465934 -0.865035 ---------------------------------------------------------- 8. 6b,7a-dihydro-7,7-dimethyl-cycloprop[a]acenaphthylene, neutral (2) State=1-A'\HF=-580.0175267 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -0.809159 1.876580 0.000000 2 6 0.000000 0.721761 0.000000 3 6 -1.159612 2.397713 1.277589 4 6 -1.159612 2.397713 -1.277589 5 6 0.448591 0.071709 1.176294 6 6 0.448591 0.071709 -1.176294 7 6 -0.715785 1.771940 2.428460 8 6 -0.715785 1.771940 -2.428460 9 6 0.091663 0.599347 2.398291 10 6 0.091663 0.599347 -2.398291 11 6 1.253830 -1.123696 0.770384 12 6 1.253830 -1.123696 -0.770384 13 6 0.566122 -2.251942 0.000000 14 6 1.322414 -3.571383 0.000000 15 6 -0.941170 -2.423426 0.000000 16 1 -1.771642 3.293995 1.345349 17 1 -1.771642 3.293995 -1.345349 18 1 -0.990231 2.187044 3.395096 19 1 -0.990231 2.187044 -3.395096 20 1 0.412092 0.143504 3.331669 21 1 0.412092 0.143504 -3.331669 22 1 2.147246 -1.382189 -1.334163 23 1 2.147246 -1.382189 1.334163 24 1 2.406653 -3.413640 0.000000 25 1 1.069929 -4.168013 -0.886050 26 1 1.069929 -4.168013 0.886050 27 1 -1.478387 -1.472339 0.000000 28 1 -1.258281 -2.988202 -0.885821 29 1 -1.258281 -2.988202 0.885821 ---------------------------------------------------------- 9. 6b,7a-dihydro-7,7-dimethyl-cycloprop[a]acenaphthylene, radical cation (2.+) State=2-A"\HF=-579.7606113\S2=0.763\ ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -0.869296 1.839089 0.000000 2 6 0.000000 0.730602 0.000000 3 6 -1.249503 2.334891 1.272712 4 6 -1.249503 2.334891 -1.272712 5 6 0.472604 0.092873 1.166039 6 6 0.472604 0.092873 -1.166039 7 6 -0.781189 1.711176 2.444093 8 6 -0.781189 1.711176 -2.444093 9 6 0.060479 0.591128 2.414813 10 6 0.060479 0.591128 -2.414813 11 6 1.325618 -1.039327 0.756507 12 6 1.325618 -1.039327 -0.756507 13 6 0.625608 -2.222370 0.000000 14 6 1.418394 -3.511759 0.000000 15 6 -0.873212 -2.418544 0.000000 16 1 -1.904016 3.198381 1.350902 17 1 -1.904016 3.198381 -1.350902 18 1 -1.086868 2.113314 3.404938 19 1 -1.086868 2.113314 -3.404938 20 1 0.391398 0.133870 3.342116 21 1 0.391398 0.133870 -3.342116 22 1 2.199046 -1.320766 -1.337776 23 1 2.199046 -1.320766 1.337776 24 1 2.498108 -3.335088 0.000000 25 1 1.169271 -4.112178 -0.883310 26 1 1.169271 -4.112178 0.883310 27 1 -1.443345 -1.487091 0.000000 28 1 -1.168747 -2.997033 -0.882702 29 1 -1.168747 -2.997033 0.882702 ---------------------------------------------------------- 10. 2,3-dihydro-1,1-dimethyl-1,3-perinaphthadiyl radical cation (obtained by breaking the central cyclopropane bond in 2.+), 2A2 state State=2-A2\HF=-579.7616879\S2=0.793\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 2.057587 0.000000 2 6 0.000000 0.639066 0.000000 3 6 -1.249256 2.742456 0.000000 4 6 1.249256 2.742456 0.000000 5 6 -1.259541 -0.074335 0.000000 6 6 1.259541 -0.074335 0.000000 7 6 -2.461800 2.051547 0.000000 8 6 2.461800 2.051547 0.000000 9 6 -2.482954 0.665275 0.000000 10 6 2.482954 0.665275 0.000000 11 6 -1.239693 -1.459072 0.000000 12 6 1.239693 -1.459072 0.000000 13 6 0.000000 -2.261264 0.000000 14 6 0.000000 -3.191990 1.272926 15 6 0.000000 -3.191990 -1.272926 16 1 -1.246744 3.828587 0.000000 17 1 1.246744 3.828587 0.000000 18 1 -3.394116 2.607051 0.000000 19 1 3.394116 2.607051 0.000000 20 1 -3.423361 0.123072 0.000000 21 1 3.423361 0.123072 0.000000 22 1 2.179915 -2.007108 0.000000 23 1 -2.179915 -2.007108 0.000000 24 1 0.000000 -2.603200 2.193341 25 1 0.000000 -2.603200 -2.193341 26 1 0.888484 -3.828928 1.256800 27 1 -0.888484 -3.828928 1.256800 28 1 0.888484 -3.828928 -1.256800 29 1 -0.888484 -3.828928 -1.256800 ---------------------------------------------------------- 11. 2,3-dihydro-1,1-dimethyl-1,3-perinaphthadiyl radical cation (obtained by breaking the central cyclopropane bond in 2.+), 2B1 state State=2-B1\HF=-579.759907\S2=0.801\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 2.070982 0.000000 2 6 0.000000 0.652157 0.000000 3 6 -1.236013 2.764106 0.000000 4 6 1.236013 2.764106 0.000000 5 6 -1.238641 -0.069530 0.000000 6 6 1.238641 -0.069530 0.000000 7 6 -2.447731 2.069570 0.000000 8 6 2.447731 2.069570 0.000000 9 6 -2.452342 0.679752 0.000000 10 6 2.452342 0.679752 0.000000 11 6 -1.239748 -1.461283 0.000000 12 6 1.239748 -1.461283 0.000000 13 6 0.000000 -2.316249 0.000000 14 6 0.000000 -3.227261 1.265862 15 6 0.000000 -3.227261 -1.265862 16 1 -1.234283 3.850770 0.000000 17 1 1.234283 3.850770 0.000000 18 1 -3.385302 2.615356 0.000000 19 1 3.385302 2.615356 0.000000 20 1 -3.397830 0.143771 0.000000 21 1 3.397830 0.143771 0.000000 22 1 2.192859 -1.986925 0.000000 23 1 -2.192859 -1.986925 0.000000 24 1 0.000000 -2.633761 2.184603 25 1 0.000000 -2.633761 -2.184603 26 1 0.886471 -3.871002 1.266989 27 1 -0.886471 -3.871002 1.266989 28 1 0.886471 -3.871002 -1.266989 29 1 -0.886471 -3.871002 -1.266989 ---------------------------------------------------------- 12. Diyl radical cation (D.+) obtained by breaking a lateral cyclopropane bond in 2.+. HF=-579.7320954\S2=0.794\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.960814 1.838536 -0.484794 2 6 0.653834 0.475087 -0.523511 3 6 1.434374 -0.822391 -0.922676 4 6 -0.654799 0.041102 -0.202759 5 6 -1.684555 0.923741 0.161106 6 6 -1.342984 2.302036 0.208036 7 6 2.254819 -0.551035 0.261423 8 6 0.385241 -1.905505 -0.830066 9 6 -0.835340 -1.366388 -0.397596 10 6 -2.964363 0.341841 0.408634 11 6 -2.117942 -1.901948 -0.141311 12 6 -3.147031 -1.033837 0.261962 13 1 -2.314879 -2.962144 -0.264452 14 1 -2.097520 3.031561 0.490055 15 1 -4.131305 -1.450944 0.452215 16 1 -3.798651 0.974642 0.695351 17 6 3.557084 0.154923 0.090040 18 1 0.162953 3.797939 -0.090764 19 6 -0.060914 2.736453 -0.119135 20 1 1.948157 2.220059 -0.720825 21 6 1.931956 -1.078398 1.614439 22 1 1.975442 -0.747406 -1.869731 23 1 0.606460 -2.943625 -1.045258 24 1 2.146428 -0.342424 2.395156 25 1 0.911243 -1.449461 1.702955 26 1 2.609743 -1.929960 1.791332 27 1 3.769166 0.852508 0.905468 28 1 4.333566 -0.626812 0.133547 29 1 3.658033 0.650770 -0.877800 ---------------------------------------------------------- 13. 2,2-dimethyl-1H-phenalene, radical cation (7.+) State=2-A"\HF=-579.7897797 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.557117 0.000000 2 6 0.816834 1.732702 0.000000 3 6 -1.429122 0.706023 0.000000 4 6 0.597497 -0.724475 0.000000 5 6 0.196904 3.005634 0.000000 6 6 2.223665 1.599985 0.000000 7 6 -1.999982 2.003725 0.000000 8 6 2.003340 -0.806409 0.000000 9 6 -1.197905 3.135811 0.000000 10 6 2.805484 0.335553 0.000000 11 1 2.844178 2.491421 0.000000 12 1 0.821324 3.894994 0.000000 13 1 -1.647687 4.123320 0.000000 14 1 3.886006 0.234586 0.000000 15 1 -3.081738 2.100238 0.000000 16 1 2.481977 -1.780195 0.000000 17 6 -2.259631 -0.456334 0.000000 18 6 -1.713378 -1.702414 0.000000 19 6 -0.247129 -1.985420 0.000000 20 1 -3.338439 -0.328152 0.000000 21 1 -2.366325 -2.572161 0.000000 22 6 0.064775 -2.848122 1.270303 23 6 0.064775 -2.848122 -1.270303 24 1 -0.140150 -2.291441 2.188881 25 1 -0.140150 -2.291441 -2.188881 26 1 -0.551969 -3.751634 1.262031 27 1 -0.551969 -3.751634 -1.262031 28 1 1.114092 -3.154709 1.272330 29 1 1.114092 -3.154709 -1.272330 ---------------------------------------------------------- 14. 2,3-dimethyl-1H-phenalene, radical cation (8.+) HF=-579.8003232 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.608565 -0.031518 -0.050173 2 6 2.014040 0.227747 -0.006157 3 6 0.138705 -1.387660 0.010077 4 6 -0.305709 1.032166 -0.179552 5 6 2.907748 -0.862740 0.132314 6 6 2.473238 1.560577 -0.111223 7 6 1.077265 -2.442653 0.145156 8 6 0.191616 2.340768 -0.294361 9 6 -1.253693 -1.661878 -0.112899 10 6 -1.794820 0.778887 -0.160215 11 6 2.438855 -2.180118 0.212104 12 6 1.564032 2.602623 -0.264102 13 1 3.540020 1.761606 -0.079315 14 1 3.975757 -0.667776 0.172659 15 1 0.715081 -3.465567 0.190760 16 1 -0.503334 3.167085 -0.413582 17 6 -2.192432 -0.669201 -0.241942 18 1 -1.571447 -2.701277 -0.127565 19 1 -2.248305 1.300535 -1.017734 20 6 -2.424314 1.429768 1.123339 21 1 3.144812 -2.997473 0.316549 22 1 1.919454 3.623506 -0.358631 23 6 -3.638390 -0.999423 -0.447099 24 1 -2.173761 2.491967 1.165764 25 1 -3.512640 1.339289 1.103898 26 1 -2.041502 0.945228 2.025875 27 1 -4.018193 -0.516352 -1.357261 28 1 -3.798309 -2.076451 -0.533872 29 1 -4.255864 -0.628392 0.380851 ---------------------------------------------------------- 15. 2,2,7,7-tetramethyldicyclopropa(a,g)pyracene radical cation (anti, C2h) \State=2-AU\HF=-773.879781\S2=0.757\S2A=0.750 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.686465 0.000000 2 6 0.000000 -0.686465 0.000000 3 6 -0.035119 1.436285 1.184391 4 6 -0.035116 1.436285 -1.184391 5 6 0.035119 -1.436285 1.184391 6 6 0.035116 -1.436285 -1.184391 7 6 -0.031091 0.707016 2.396308 8 6 -0.031091 0.707016 -2.396308 9 6 0.031091 -0.707016 2.396308 10 6 0.031091 -0.707016 -2.396308 11 6 0.117194 -2.860597 0.766815 12 6 0.117194 -2.860597 -0.766815 13 6 -0.117194 2.860597 0.766815 14 6 -0.117194 2.860597 -0.766815 15 6 1.402157 -3.293730 0.000000 16 6 -1.402157 3.293730 0.000000 17 6 2.675244 -2.443845 0.000000 18 6 -2.675244 2.443845 0.000000 19 6 1.654482 -4.789022 0.000000 20 6 -1.654482 4.789022 0.000000 21 1 -0.061719 1.222487 3.351700 22 1 -0.061719 1.222487 -3.351700 23 1 0.061719 -1.222487 3.351700 24 1 0.061719 -1.222487 -3.351700 25 1 2.751435 -1.805626 -0.884863 26 1 2.751435 -1.805626 0.884863 27 1 -2.751435 1.805626 -0.884863 28 1 -2.751435 1.805626 0.884863 29 1 -0.380721 -3.640660 -1.335275 30 1 -0.380721 -3.640660 1.335275 31 1 0.380721 3.640660 -1.335275 32 1 0.380721 3.640660 1.335275 33 1 2.236978 -5.074383 -0.884224 34 1 2.236978 -5.074383 0.884224 35 1 -2.236978 5.074383 -0.884224 36 1 -2.236978 5.074383 0.884224 37 1 3.549516 -3.100476 0.000000 38 1 -3.549516 3.100476 0.000000 39 1 0.726577 -5.369464 0.000000 40 1 -0.726577 5.369464 0.000000 ---------------------------------------------------------- 16. 2,2,7,7-tetramethyldicyclopropa(a,g)pyracene radical cation (syn, C2v, 4.+) State=2-A2\HF=-773.8794612\S2=0.757\S2A=0.750 --------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z --------------------------------------------------------- 1 6 0.000000 0.686323 -0.677669 2 6 0.000000 -0.686323 -0.677669 3 6 1.184353 1.437006 -0.657890 4 6 -1.184353 1.437006 -0.657890 5 6 1.184353 -1.437006 -0.657890 6 6 -1.184353 -1.437006 -0.657890 7 6 2.395785 0.707762 -0.628406 8 6 -2.395785 0.707762 -0.628406 9 6 2.395785 -0.707762 -0.628406 10 6 -2.395785 -0.707762 -0.628406 11 6 0.766857 -2.863192 -0.618363 12 6 -0.766857 -2.863192 -0.618363 13 6 0.766857 2.863192 -0.618363 14 6 -0.766857 2.863192 -0.618363 15 6 0.000000 -3.336379 0.652009 16 6 0.000000 3.336379 0.652009 17 6 0.000000 -4.839147 0.856887 18 6 0.000000 -2.526962 1.950702 19 6 0.000000 4.839147 0.856887 20 6 0.000000 2.526962 1.950702 21 1 3.351302 1.223666 -0.611780 22 1 -3.351302 1.223666 -0.611780 23 1 3.351302 -1.223666 -0.611780 24 1 -3.351302 -1.223666 -0.611780 25 1 -1.335109 -3.627616 -1.140194 26 1 1.335109 -3.627616 -1.140194 27 1 -1.335109 3.627616 -1.140194 28 1 1.335109 3.627616 -1.140194 29 1 0.000000 -5.389389 -0.089189 30 1 -0.884181 -5.143352 1.429840 31 1 0.884181 -5.143352 1.429840 32 1 0.000000 -3.209514 2.804818 33 1 -0.885024 -1.891408 2.046485 34 1 0.885024 -1.891408 2.046485 35 1 0.000000 5.389389 -0.089189 36 1 0.884181 5.143352 1.429840 37 1 -0.884181 5.143352 1.429840 38 1 0.000000 3.209514 2.804818 39 1 0.885024 1.891408 2.046485 40 1 -0.885024 1.891408 2.046485 --------------------------------------------------------- 17. Diyl radical cation obtained by breaking one of the central cyclopropane bonds in 2,2,7,7-tetramethyldi cyclopropa a,g)pyracene radical cation (4.+), 2A' state State=2-A'\HF=-773.8908411\S2=0.808\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.708280 0.000000 2 6 0.644636 -0.522621 0.000000 3 6 -0.310204 1.317293 1.255065 4 6 -0.310204 1.317293 -1.255065 5 6 0.988713 -1.233867 1.170455 6 6 0.988713 -1.233867 -1.170455 7 6 0.046906 0.587568 2.442517 8 6 0.046906 0.587568 -2.442517 9 6 0.668367 -0.658323 2.414234 10 6 0.668367 -0.658323 -2.414234 11 6 1.602984 -2.517832 0.761897 12 6 1.602984 -2.517832 -0.761897 13 6 -0.933696 2.556951 1.255361 14 6 -0.933696 2.556951 -1.255361 15 6 0.693145 -3.517688 0.000000 16 6 -1.305968 3.317360 0.000000 17 6 1.197970 -4.949107 0.000000 18 6 -0.833822 -3.392257 0.000000 19 6 -0.550148 4.682339 0.000000 20 6 -2.858626 3.592593 0.000000 21 1 -0.182071 1.036487 3.405810 22 1 -0.182071 1.036487 -3.405810 23 1 0.907748 -1.162506 3.345164 24 1 0.907748 -1.162506 -3.345164 25 1 2.420088 -2.944586 -1.335725 26 1 2.420088 -2.944586 1.335725 27 1 -1.178998 3.038286 -2.200090 28 1 -1.178998 3.038286 2.200090 29 1 2.291169 -5.005971 0.000000 30 1 0.827659 -5.480805 -0.884344 31 1 0.827659 -5.480805 0.884344 32 1 -1.279451 -4.390635 0.000000 33 1 -1.210532 -2.871868 -0.885060 34 1 -1.210532 -2.871868 0.885060 35 1 0.534452 4.538725 0.000000 36 1 -0.824542 5.264704 -0.886641 37 1 -0.824542 5.264704 0.886641 38 1 -3.070936 4.665315 0.000000 39 1 -3.336950 3.149139 -0.879392 40 1 -3.336950 3.149139 0.879392 ---------------------------------------------------------- 18. Diyl radical cation obtained by breaking one of the central cyclopropane bonds in 2,2,7,7-tetramethyldi cyclopropa a,g)pyracene radical cation (4.+), 2A" state State=2-A"\HF=-773.8888336\S2=0.787\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.697268 0.000000 2 6 0.515674 -0.585152 0.000000 3 6 -0.231909 1.335875 1.274184 4 6 -0.231909 1.335875 -1.274184 5 6 0.846417 -1.299255 1.183895 6 6 0.846417 -1.299255 -1.183895 7 6 0.104265 0.606844 2.469694 8 6 0.104265 0.606844 -2.469694 9 6 0.641179 -0.677150 2.424391 10 6 0.641179 -0.677150 -2.424391 11 6 1.381525 -2.617931 0.782377 12 6 1.381525 -2.617931 -0.782377 13 6 -0.756180 2.611706 1.253900 14 6 -0.756180 2.611706 -1.253900 15 6 0.452524 -3.556181 0.000000 16 6 -1.055357 3.356529 0.000000 17 6 0.896991 -5.011718 0.000000 18 6 -1.066119 -3.362295 0.000000 19 6 -0.146718 4.648015 0.000000 20 6 -2.576545 3.818550 0.000000 21 1 -0.064840 1.086888 3.428887 22 1 -0.064840 1.086888 -3.428887 23 1 0.892829 -1.186026 3.350008 24 1 0.892829 -1.186026 -3.350008 25 1 2.183098 -3.076964 -1.353997 26 1 2.183098 -3.076964 1.353997 27 1 -0.958391 3.133262 -2.187489 28 1 -0.958391 3.133262 2.187489 29 1 1.987309 -5.112075 0.000000 30 1 0.508667 -5.527638 -0.885688 31 1 0.508667 -5.527638 0.885688 32 1 -1.561694 -4.337201 0.000000 33 1 -1.415163 -2.821786 -0.885515 34 1 -1.415163 -2.821786 0.885515 35 1 0.915533 4.390158 0.000000 36 1 -0.368554 5.246798 -0.887887 37 1 -0.368554 5.246798 0.887887 38 1 -2.636408 4.909257 0.000000 39 1 -3.103147 3.444814 -0.880674 40 1 -3.103147 3.444814 0.880674 ---------------------------------------------------------- 19. Diyl radical cation obtained by breaking one of the lateral cyclopropane bonds in 2,2,7,7-tetramethyldi- cyclopropa a,g)pyracene radical cation (4.+), HF=-773.6623969\S2=0.786\S2A=0.751 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 1 -5.145188 -0.892548 -1.150749 2 1 -5.590079 0.044914 0.286531 3 1 -3.428148 0.794768 -1.737666 4 1 -5.208180 -1.677696 0.438650 5 1 -2.894102 -1.835802 -1.478067 6 1 4.588838 0.648155 -1.606201 7 1 -2.111432 0.049020 1.831500 8 1 -3.772241 0.613401 2.045265 9 1 -3.398395 -1.108081 2.206982 10 1 5.333215 -1.396803 0.044849 11 6 -2.472716 -1.098385 -0.805168 12 6 -2.797083 0.428446 -0.935396 13 6 -3.477663 -0.401039 0.171564 14 6 -4.936939 -0.753547 -0.084758 15 6 -3.157797 -0.200139 1.641999 16 6 1.155839 -1.929019 0.397946 17 6 1.615706 -0.590085 0.457658 18 6 2.868363 0.227603 1.010747 19 6 0.708863 0.434868 0.095132 20 6 -0.562021 0.141118 -0.326133 21 6 -1.044053 -1.185293 -0.398790 22 6 3.480809 -0.417013 -0.164750 23 6 2.428770 1.683203 0.909092 24 6 1.130029 1.771140 0.356681 25 6 -1.525793 1.145934 -0.593455 26 6 0.179340 2.794959 0.066992 27 6 -1.126199 2.477158 -0.398922 28 1 0.433937 3.836967 0.226265 29 1 4.060877 -2.166433 0.992044 30 1 -1.817545 3.293074 -0.579567 31 1 4.135280 -2.390815 -0.781701 32 6 4.268333 -1.678053 0.037172 33 1 -0.480568 -3.256724 -0.059546 34 6 -0.163371 -2.220642 -0.032132 35 1 1.804634 -2.757493 0.658159 36 6 3.570446 0.239315 -1.506226 37 1 3.252988 -0.099918 1.977613 38 1 3.068167 2.492611 1.234643 39 1 3.436955 -0.482060 -2.317395 40 1 2.873805 1.068300 -1.627130 ---------------------------------------------------------- 20. 2,7-dihydro-2,2,7,7-tetramethylpyrene radical cation (6.+) \State=2-B1U\HF=-773.9255272\S2=0.767\S2A=0.750 --------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z --------------------------------------------------------- 1 6 -0.699719 0.000000 0.000000 2 6 0.699719 0.000000 0.000000 3 6 -1.427946 1.255048 0.000000 4 6 -1.427946 -1.255048 0.000000 5 6 1.427946 1.255048 0.000000 6 6 1.427946 -1.255048 0.000000 7 6 -0.676208 2.494918 0.000000 8 6 -0.676208 -2.494918 0.000000 9 6 0.676208 2.494918 0.000000 10 6 0.676208 -2.494918 0.000000 11 6 -2.798222 1.240440 0.000000 12 6 -2.798222 -1.240440 0.000000 13 6 2.798222 1.240440 0.000000 14 6 2.798222 -1.240440 0.000000 15 6 -3.624249 0.000000 0.000000 16 6 3.624249 0.000000 0.000000 17 6 -4.545928 0.000000 1.267423 18 6 -4.545928 0.000000 -1.267423 19 6 4.545928 0.000000 1.267423 20 6 4.545928 0.000000 -1.267423 21 1 -1.230491 3.428827 0.000000 22 1 -1.230491 -3.428827 0.000000 23 1 1.230491 3.428827 0.000000 24 1 1.230491 -3.428827 0.000000 25 1 -3.338355 2.185334 0.000000 26 1 -3.338355 -2.185334 0.000000 27 1 3.338355 2.185334 0.000000 28 1 3.338355 -2.185334 0.000000 29 1 -3.955381 0.000000 2.187413 30 1 -3.955381 0.000000 -2.187413 31 1 3.955381 0.000000 2.187413 32 1 3.955381 0.000000 -2.187413 33 1 -5.186813 -0.887066 1.260064 34 1 -5.186813 0.887066 1.260064 35 1 -5.186813 -0.887066 -1.260064 36 1 -5.186813 0.887066 -1.260064 37 1 5.186813 -0.887066 1.260064 38 1 5.186813 0.887066 1.260064 39 1 5.186813 0.887066 -1.260064 40 1 5.186813 -0.887066 -1.260064 ---------------------------------------------------------