Electronic Structure of the Naphtalene Radical Cation and Some Simple Alkylated Derivatives. by Thomas Bally,* Claudio Carra, Markus F¸lscher, and Zhendong Zhu SUPPORTING INFORMATION ********************** B3LYP/6-31G* optimized geometries of all isomers discussed in the paper. Total energies in hartree Naphtalene radical cation opt geometry (N+.), G.S. 2-Au, E(UB3LYP) = -385.613630366 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.716279 0.000000 0.000000 2 6 -0.716279 0.000000 0.000000 3 6 1.402314 1.236160 0.000000 4 6 1.402314 -1.236160 0.000000 5 6 -1.402314 1.236160 0.000000 6 6 -1.402314 -1.236160 0.000000 7 6 0.696179 2.452503 0.000000 8 6 0.696179 -2.452503 0.000000 9 6 -0.696179 2.452503 0.000000 10 6 -0.696179 -2.452503 0.000000 11 1 2.488952 1.243593 0.000000 12 1 2.488952 -1.243593 0.000000 13 1 -2.488952 1.243593 0.000000 14 1 -2.488952 -1.243593 0.000000 15 1 1.242928 3.389936 0.000000 16 1 1.242928 -3.389936 0.000000 17 1 -1.242928 3.389936 0.000000 18 1 -1.242928 -3.389936 0.000000 ---------------------------------------------------------- Naphtalene neutral opt geometry (N), G.S. 1-Ag. E(B3LYP) = -385.613630366 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 0.716278 2 6 0.000000 1.236158 1.402314 3 6 0.000000 2.452504 0.696180 4 1 0.000000 1.243593 2.488953 5 1 0.000000 3.389936 1.242926 6 6 0.000000 -1.236158 1.402314 7 6 0.000000 -2.452504 0.696180 8 1 0.000000 -1.243593 2.488953 9 1 0.000000 -3.389936 1.242926 10 6 0.000000 0.000000 -0.716278 11 6 0.000000 1.236158 -1.402314 12 6 0.000000 2.452504 -0.696180 13 1 0.000000 1.243593 -2.488953 14 1 0.000000 3.389936 -1.242926 15 6 0.000000 -1.236158 -1.402314 16 6 0.000000 -2.452504 -0.696180 17 1 0.000000 -1.243593 -2.488953 18 1 0.000000 -3.389936 -1.242926 ---------------------------------------------------------- Dihydroacenaphthene radical cation geometry (A+.), G.S. 2-A2, E(UB3LYP) = -463.051452414 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 -0.090884 2 6 0.000000 0.000000 1.321961 3 6 0.000000 1.164424 -0.877445 4 6 0.000000 -1.164424 -0.877445 5 6 0.000000 1.268528 1.949558 6 6 0.000000 -1.268528 1.949558 7 6 0.000000 2.414748 -0.227964 8 6 0.000000 -2.414748 -0.227964 9 6 0.000000 2.445182 1.169379 10 6 0.000000 -2.445182 1.169379 11 6 0.000000 0.780772 -2.331897 12 6 0.000000 -0.780772 -2.331897 13 1 0.000000 1.344849 3.033302 14 1 0.000000 -1.344849 3.033302 15 1 0.000000 3.341720 -0.793396 16 1 0.000000 -3.341720 -0.793396 17 1 0.000000 3.404728 1.677119 18 1 0.000000 -3.404728 1.677119 19 1 0.875811 1.192897 -2.850022 20 1 0.875811 -1.192897 -2.850022 21 1 -0.875811 1.192897 -2.850022 22 1 -0.875811 -1.192897 -2.850022 ---------------------------------------------------------- Dihydroacenaphthene neutral geometry (A), G.S. 1-A1, E(B3LYP) = -463.314943385 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 0.000000 0.000000 -0.091244 2 6 0.000000 0.000000 1.323258 3 6 0.000000 1.175134 -0.874016 4 6 0.000000 -1.175134 -0.874016 5 6 0.000000 1.275512 1.951967 6 6 0.000000 -1.275512 1.951967 7 6 0.000000 2.396201 -0.236889 8 6 0.000000 -2.396201 -0.236889 9 6 0.000000 2.427211 1.186101 10 6 0.000000 -2.427211 1.186101 11 6 0.000000 -0.784747 -2.342972 12 6 0.000000 0.784747 -2.342972 13 1 0.000000 1.341715 3.037393 14 1 0.000000 -1.341715 3.037393 15 1 0.000000 3.330382 -0.793345 16 1 0.000000 -3.330382 -0.793345 17 1 0.000000 3.393504 1.684480 18 1 0.000000 -3.393504 1.684480 19 1 -0.877971 -1.184388 -2.864859 20 1 0.877971 -1.184388 -2.864859 21 1 -0.877971 1.184388 -2.864859 22 1 0.877971 1.184388 -2.864859 ---------------------------------------------------------- Tetrahydropyracene radical cation geometry (P+.), G.S. 2-Au, E(UB3LYP) = -540.475075891 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -.690628 .000000 .000000 2 6 .690628 .000000 .000000 3 6 -1.434032 1.181938 .000000 4 6 1.434032 1.181938 .000000 5 6 -1.434032 -1.181938 .000000 6 6 1.434032 -1.181938 .000000 7 6 -.705229 2.397285 .000000 8 6 .705229 2.397285 .000000 9 6 -.705229 -2.397285 .000000 10 6 .705229 -2.397285 .000000 11 6 -2.895129 .789515 .000000 12 6 2.895129 .789515 .000000 13 6 -2.895129 -.789515 .000000 14 6 2.895129 -.789515 .000000 15 1 -1.224110 3.351403 .000000 16 1 1.224110 3.351403 .000000 17 1 -1.224110 -3.351403 .000000 18 1 1.224110 -3.351403 .000000 19 1 -3.418507 1.192363 .876295 20 1 3.418507 1.192363 .876295 21 1 -3.418507 -1.192363 .876295 22 1 3.418507 -1.192363 .876295 23 1 -3.418507 1.192363 -.876295 24 1 3.418507 1.192363 -.876295 25 1 -3.418507 -1.192363 -.876295 26 1 3.418507 -1.192363 -.876295 ---------------------------------------------------------- Tetrahydropyracene neutral geometry (P), G.S. 1-Ag, E(B3LYP) = -540.725356275 ---------------------------------------------------------- Center Atomic Coordinates (Angstroms) Number Number X Y Z ---------------------------------------------------------- 1 6 -.691535 .000000 .000000 2 6 .691535 .000000 .000000 3 6 -1.431707 1.191817 .000000 4 6 1.431707 1.191817 .000000 5 6 -1.431707 -1.191817 .000000 6 6 1.431707 -1.191817 .000000 7 6 -.719386 2.380335 .000000 8 6 .719386 2.380335 .000000 9 6 -.719386 -2.380335 .000000 10 6 .719386 -2.380335 .000000 11 6 -2.905221 -.793224 .000000 12 6 2.905221 -.793224 .000000 13 6 -2.905221 .793224 .000000 14 6 2.905221 .793224 .000000 15 1 -1.229870 3.340974 .000000 16 1 1.229870 3.340974 .000000 17 1 -1.229870 -3.340974 .000000 18 1 1.229870 -3.340974 .000000 19 1 -3.433270 -1.184493 .878130 20 1 3.433270 -1.184493 .878130 21 1 -3.433270 1.184493 .878130 22 1 3.433270 1.184493 .878130 23 1 -3.433270 -1.184493 -.878130 24 1 3.433270 -1.184493 -.878130 25 1 -3.433270 1.184493 -.878130 26 1 3.433270 1.184493 -.878130 ---------------------------------------------------------- *********************************************************** CASSCF(9,10) and CASPT2 Energies: Naphtalene ********** Radical cation geometry: ------------------------------------------------------- E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- Au -383.261989 0.00 -384.305085 0.00 B3u -383.231624 0.83 -384.268771 0.99 -383.105468 4.26 -384.157111 4.03 B2g -383.184704 2.10 -384.235449 1.89 -383.096476 4.50 -384.158691 3.98 -383.071944 5.17 -384.142002 4.44 -383.007750 6.92 -384.067724 6.46 B1g -383.153823 2.94 -384.205977 2.70 -383.132060 3.53 -384.185983 3.24 -383.055778 5.61 -384.117841 5.09 -383.019641 6.59 -384.095928 5.69 Neutral geometry: ------------------------------------------------------- E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- Au -383.257562 0.00 -384.355798 0.00 B3u -383.240388 0.47 -384.328991 0.73 -383.102893 4.21 -384.207643 4.03 B2g -383.184911 1.98 -384.290264 1.78 -383.089378 4.58 -384.208106 4.02 -383.069265 5.12 -384.191589 4.47 -383.010778 6.71 -384.141964 5.82 B1g -383.150814 2.90 -384.258293 2.65 -383.120669 3.72 -384.228353 3.47 -383.056588 5.47 -384.175724 4.90 -383.018638 6.50 -384.154127 5.49 ------------------------------------------------------- Dihydroacenaphtene ****************** Radical cation geomtry ------------------------------------------------------- E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- A2 -460.157345 0.00 -461.511763 0.00 -460.049326 2.94 -461.411704 2.72 -460.031998 3.41 -461.394565 3.19 -459.948182 5.69 -461.320080 5.22 -459.946355 5.74 -461.321022 5.19 -459.928607 6.22 -461.314149 5.38 B1 -460.118948 1.04 -461.467458 1.21 -460.080393 2.09 -461.438336 2.00 -460.001768 4.23 -461.364150 4.02 -459.994689 4.43 -461.366846 3.94 -459.965845 5.21 -461.344262 4.56 -459.961322 5.33 -461.337882 4.73 Neutral geometry ------------------------------------------------------- E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- A2 -460.153283 0.00 -461.506924 0.00 -460.046461 2.91 -461.406840 2.72 -460.019828 3.63 -461.380650 3.44 -459.948109 5.58 -461.322127 5.03 B1 -460.127179 0.71 -461.472987 0.92 -460.080616 1.98 -461.438013 1.87 -459.997114 4.25 -461.357737 4.06 -459.987512 4.51 -461.360064 4.00 -459.962065 5.20 -461.340082 4.54 -459.954803 5.40 -461.327086 4.89 ------------------------------------------------------- Tetrahydropyracene ****************** Radical cation geomtry ------------------------------------------------------- E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- Au -537.072604 0.00 -538.681059 0.00 dB3u -537.026739 1.25 -538.631690 1.34 -536.911585 4.38 -538.531436 4.07 -536.875140 5.37 -538.504475 4.80 B2g -536.987600 2.31 -538.605805 2.05 -536.910538 4.41 -538.540940 3.81 -536.871593 5.47 -538.514993 4.52 -536.811801 7.10 -538.441623 6.52 -536.804272 7.30 -538.450662 6.30 B3g -536.960797 3.04 -538.582054 2.69 -536.946299 3.44 -538.569466 3.03 -536.854202 5.94 -538.487905 5.26 Neutral geometry ------------------------------------------------------- i E(tot)/h DE/eV E(tot)/h DE/eV CASSCF CASSCF CASPT2 CASPT2 ------------------------------------------------------- Au -537.067243 0.00 -538.676533 0.00 B3u -537.035544 0.86 -538.637750 1.06 -536.905450 4.40 -538.524339 4.14 -536.867300 5.44 -538.497682 4.87 B2g -536.987562 2.17 -538.605782 1.93 -536.902979 4.47 -538.533183 3.90 -536.869538 5.38 -538.507445 4.60 -536.813821 6.90 -538.457613 5.96 B1g -536.957041 3.00 -538.577289 2.70 -536.932758 3.66 -538.554603 3.32 -536.856418 5.74 -538.489774 5.08 -536.821619 6.68 -538.577144 2.70 **********************************************************