Generation and Identification of 1,4-Perinaphthadiyl Radical Cation - First Observation of the Electronic Absorption Spectrum of an Ionized Diradical. by Zhendong Zhu, Thomas Bally, Jakob Wirz, and Markus F¸lscher SUPPORTING INFORMATION ********************** B3LYP/6-31G* optimized geometries of all isomers discussed in the paper. Total energies in hartree 6b,7,8,8a-tetrahydrocyclobut[a]acenaphthylene (CAN) neutral State=1-A'\HF=-540.7047084 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.436209 0.000000 2 6 -0.798715 1.603696 0.000000 3 6 0.438613 -0.210671 1.179724 4 6 0.438613 -0.210671 -1.179724 5 6 -1.154080 2.124297 1.274865 6 6 -1.154080 2.124297 -1.274865 7 6 0.078511 0.319539 2.399902 8 6 0.078511 0.319539 -2.399902 9 6 -0.723227 1.494715 2.428579 10 6 -0.723227 1.494715 -2.428579 11 6 1.235950 -1.435327 -0.789639 12 6 1.235950 -1.435327 0.789639 13 1 -1.764950 3.021760 1.339091 14 1 -1.764950 3.021760 -1.339091 15 1 0.392506 -0.139139 3.334456 16 1 0.392506 -0.139139 -3.334456 17 1 -1.003586 1.910029 3.393541 18 1 -1.003586 1.910029 -3.393541 19 6 0.466117 -2.800022 -0.776992 20 6 0.466117 -2.800022 0.776992 21 1 2.215364 -1.482464 -1.276738 22 1 2.215364 -1.482464 1.276738 23 1 1.026996 -3.625901 -1.225383 24 1 1.026996 -3.625901 1.225383 25 1 -0.521483 -2.759186 -1.245091 26 1 -0.521483 -2.759186 1.245091 ---------------------------------------------------------- 6b,7,8,8a-tetrahydrocyclobut[a]acenaphthylene (CAN) radical cation State=2-A"\HF=-540.4443231\S2=0.762 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.437467 0.000000 2 6 -0.819432 1.588438 0.000000 3 6 0.450990 -0.206873 1.168491 4 6 0.450990 -0.206873 -1.168491 5 6 -1.183068 2.101801 1.268354 6 6 -1.183068 2.101801 -1.268354 7 6 0.063782 0.319759 2.417223 8 6 0.063782 0.319759 -2.417223 9 6 -0.738265 1.464618 2.445344 10 6 -0.738265 1.464618 -2.445344 11 6 1.265179 -1.398228 -0.783820 12 6 1.265179 -1.398228 0.783820 13 1 -1.807051 2.988054 1.342106 14 1 -1.807051 2.988054 -1.342106 15 1 0.382417 -0.144791 3.345446 16 1 0.382417 -0.144791 -3.345446 17 1 -1.030731 1.881147 3.404253 18 1 -1.030731 1.881147 -3.404253 19 6 0.490018 -2.783691 -0.771623 20 6 0.490018 -2.783691 0.771623 21 1 2.235746 -1.447862 -1.285353 22 1 2.235746 -1.447862 1.285353 23 1 1.078605 -3.584072 -1.224008 24 1 1.078605 -3.584072 1.224008 25 1 -0.492502 -2.754512 -1.246647 26 1 -0.492502 -2.754512 1.246647 ---------------------------------------------------------- 1,8-divinylnaphthalene (DVN), neutral State=1-A\HF=-540.6789514 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.241391 2 6 0.000000 0.000000 1.681785 3 6 0.015273 1.278299 -0.428367 4 6 -0.015273 -1.278299 -0.428367 5 6 -0.063631 1.224174 2.398443 6 6 0.063631 -1.224174 2.398443 7 6 -0.047384 2.442076 0.327694 8 6 0.047384 -2.442076 0.327694 9 6 -0.107763 2.425139 1.734519 10 6 0.107763 -2.425139 1.734519 11 1 0.000000 3.394965 -0.190351 12 1 0.000000 -3.394965 -0.190351 13 1 -0.152217 3.361458 2.284071 14 1 0.152217 -3.361458 2.284071 15 1 -0.069140 1.188247 3.485173 16 1 0.069140 -1.188247 3.485173 17 6 0.176712 1.430112 -1.892704 18 6 -0.176712 -1.430112 -1.892704 19 6 -0.478555 2.322424 -2.645996 20 6 0.478555 -2.322424 -2.645996 21 1 -1.251605 2.966318 -2.233668 22 1 1.251605 -2.966318 -2.233668 23 1 0.911167 0.785230 -2.369686 24 1 -0.911167 -0.785230 -2.369686 25 1 -0.268233 2.427650 -3.706601 26 1 0.268233 -2.427650 -3.706601 ---------------------------------------------------------- 1,8-divinylnaphthalene (DVN), radical cation State=2-A\HF=-540.4210193\S2=0.767 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.229203 2 6 0.000000 0.000000 1.669540 3 6 0.056725 1.272755 -0.439386 4 6 -0.056725 -1.272755 -0.439386 5 6 -0.076276 1.214927 2.387746 6 6 0.076276 -1.214927 2.387746 7 6 -0.049735 2.457018 0.335417 8 6 0.049735 -2.457018 0.335417 9 6 -0.133337 2.436903 1.719626 10 6 0.133337 -2.436903 1.719626 11 1 0.000000 3.412055 -0.175925 12 1 0.000000 -3.412055 -0.175925 13 1 -0.197856 3.365581 2.277081 14 1 0.197856 -3.365581 2.277081 15 1 -0.089209 1.183707 3.473531 16 1 0.089209 -1.183707 3.473531 17 6 0.345069 1.419012 -1.863820 18 6 -0.345069 -1.419012 -1.863820 19 6 -0.045479 2.453088 -2.637420 20 6 0.045479 -2.453088 -2.637420 21 1 -0.687856 3.252512 -2.279367 22 1 0.687856 -3.252512 -2.279367 23 1 0.936485 0.631987 -2.323337 24 1 -0.936485 -0.631987 -2.323337 25 1 0.247815 2.502402 -3.681200 26 1 -0.247815 -2.502402 -3.681200 ---------------------------------------------------------- 1,4-Perinaphthadiyl radical cation (PND), "twist", C2 State=2-B\HF=-540.4355656\S2=0.797 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.249830 2 6 0.000000 0.000000 1.687402 3 6 -0.059993 1.292512 -0.409973 4 6 0.059993 -1.292512 -0.409973 5 6 0.035944 1.208425 2.424129 6 6 -0.035944 -1.208425 2.424129 7 6 0.012649 2.468656 0.402650 8 6 -0.012649 -2.468656 0.402650 9 6 0.067614 2.440983 1.785888 10 6 -0.067614 -2.440983 1.785888 11 6 0.249878 -1.557388 -1.773657 12 6 -0.249878 1.557388 -1.773657 13 1 0.042163 1.154703 3.509266 14 1 -0.042163 -1.154703 3.509266 15 1 0.000000 3.430222 -0.102884 16 1 0.000000 -3.430222 -0.102884 17 1 0.112187 3.362841 2.355657 18 1 -0.112187 -3.362841 2.355657 19 6 0.470805 -0.615259 -2.897397 20 6 -0.470805 0.615259 -2.897397 21 1 0.257665 -2.611385 -2.041587 22 1 -0.257665 2.611385 -2.041587 23 1 1.511555 -0.257648 -2.879761 24 1 -1.511555 0.257648 -2.879761 25 1 0.354266 -1.155095 -3.842225 26 1 -0.354266 1.155095 -3.842225 ---------------------------------------------------------- 1,4-Perinaphthadiyl radical cation (PND), "twist", C2 State=2-A\HF=-540.4199023\S2=0.79 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.249156 2 6 0.000000 0.000000 1.676786 3 6 -0.064627 1.306347 -0.414687 4 6 0.064627 -1.306347 -0.414687 5 6 0.068600 1.226691 2.403499 6 6 -0.068600 -1.226691 2.403499 7 6 0.026235 2.500393 0.384306 8 6 -0.026235 -2.500393 0.384306 9 6 0.111341 2.456907 1.762749 10 6 -0.111341 -2.456907 1.762749 11 6 0.360217 -1.524418 -1.753917 12 6 -0.360217 1.524418 -1.753917 13 1 0.088668 1.175860 3.488071 14 1 -0.088668 -1.175860 3.488071 15 1 0.000000 3.455818 -0.129909 16 1 0.000000 -3.455818 -0.129909 17 1 0.180013 3.374021 2.338531 18 1 -0.180013 -3.374021 2.338531 19 6 0.531575 -0.545367 -2.857612 20 6 -0.531575 0.545367 -2.857612 21 1 0.537587 -2.564530 -2.021084 22 1 -0.537587 2.564530 -2.021084 23 1 1.540654 -0.096990 -2.785140 24 1 -1.540654 0.096990 -2.785140 25 1 0.512983 -1.076563 -3.814327 26 1 -0.512983 1.076563 -3.814327 ---------------------------------------------------------- 1,4-Perinaphthadiyl radical cation (PND) planar, C2v State=2-A2\HF=-540.4086153\S2=0.79 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.279722 2 6 0.000000 0.000000 1.707475 3 6 0.000000 -1.306636 -0.384176 4 6 0.000000 1.306636 -0.384176 5 6 0.000000 -1.225574 2.440527 6 6 0.000000 1.225574 2.440527 7 6 0.000000 -2.502120 0.427465 8 6 0.000000 2.502120 0.427465 9 6 0.000000 -2.458800 1.806421 10 6 0.000000 2.458800 1.806421 11 6 0.000000 1.567444 -1.743464 12 6 0.000000 -1.567444 -1.743464 13 1 0.000000 -1.169182 3.524932 14 1 0.000000 1.169182 3.524932 15 1 0.000000 -3.459126 -0.083738 16 1 0.000000 3.459126 -0.083738 17 1 0.000000 -3.375891 2.386318 18 1 0.000000 3.375891 2.386318 19 6 0.000000 0.769409 -2.991105 20 6 0.000000 -0.769409 -2.991105 21 1 0.000000 2.631118 -1.979845 22 1 0.000000 -2.631118 -1.979845 23 1 -0.859664 1.140468 -3.571634 24 1 0.859664 1.140468 -3.571634 25 1 -0.859664 -1.140468 -3.571634 26 1 0.859664 -1.140468 -3.571634 ---------------------------------------------------------- 1,4-Perinaphthadiyl radical cation (PND) planar, C2v State=2-B1\HF=-540.429428 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.276842 2 6 0.000000 0.000000 1.714631 3 6 0.000000 -1.288895 -0.385560 4 6 0.000000 1.288895 -0.385560 5 6 0.000000 -1.207792 2.452798 6 6 0.000000 1.207792 2.452798 7 6 0.000000 -2.464591 0.430457 8 6 0.000000 2.464591 0.430457 9 6 0.000000 -2.439344 1.815013 10 6 0.000000 2.439344 1.815013 11 6 0.000000 1.571618 -1.758421 12 6 0.000000 -1.571618 -1.758421 13 1 0.000000 -1.153193 3.537846 14 1 0.000000 1.153193 3.537846 15 1 0.000000 -3.426956 -0.073320 16 1 0.000000 3.426956 -0.073320 17 1 0.000000 -3.362744 2.384039 18 1 0.000000 3.362744 2.384039 19 6 0.000000 0.765932 -2.997300 20 6 0.000000 -0.765932 -2.997300 21 1 0.000000 2.635879 -1.987729 22 1 0.000000 -2.635879 -1.987729 23 1 -0.859647 1.122560 -3.588587 24 1 0.859647 1.122560 -3.588587 25 1 -0.859647 -1.122560 -3.588587 26 1 0.859647 -1.122560 -3.588587 ---------------------------------------------------------- 1,4-ethanonaphto[1,8-de][1,2]diazepine (END) radical cation B3LYP optimized State=2-A"\HF=-649.931038\S2=0.763 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.570779 0.000000 2 6 -0.027433 2.005570 0.000000 3 6 0.042959 -0.106796 1.258052 4 6 0.042959 -0.106796 -1.258052 5 6 -0.036593 2.708782 1.229968 6 6 -0.036593 2.708782 -1.229968 7 6 0.087336 0.635586 2.445962 8 6 0.087336 0.635586 -2.445962 9 6 0.021177 2.032123 2.438597 10 6 0.021177 2.032123 -2.438597 11 6 0.054105 -1.591436 -1.366756 12 6 0.054105 -1.591436 1.366756 13 1 -0.075931 3.794227 1.212555 14 1 -0.075931 3.794227 -1.212555 15 1 0.154306 0.109788 3.394149 16 1 0.154306 0.109788 -3.394149 17 1 0.024300 2.580025 3.375020 18 1 0.024300 2.580025 -3.375020 19 6 -1.165921 -2.340849 -0.769386 20 6 -1.165921 -2.340849 0.769386 21 7 1.278803 -2.159283 -0.596908 22 7 1.278803 -2.159283 0.596908 23 1 -2.063827 -1.864608 -1.172947 24 1 -2.063827 -1.864608 1.172947 25 1 -1.141068 -3.365303 -1.150388 26 1 -1.141068 -3.365303 1.150388 27 1 0.214511 -1.892652 -2.400901 28 1 0.214511 -1.892652 2.400901 ----------------------------------------------------------