Towards the Rational Design of Novel Charge-Transfer Materials: Biaryls with A Dihedral Angle-Independent Hole Delocalization Mechanism Lena V. Ivanova*, Tushar S. Navale, Denan Wang, Sergey Lindeman, Maxim V. Ivanov* and Rajendra Rathore Department of Chemistry, Marquette University, P.O. Box 1881, Milwaukee, WI 53201-1881 Neutral HE1 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -959.000276 Hartree Sum of electronic and zero-point Energies= -958.672789 Sum of electronic and thermal Energies= -958.653871 Sum of electronic and thermal Enthalpies= -958.652927 Sum of electronic and thermal Free Energies= -958.719446 Coordinates in ang: O -0.28828 4.56069 -1.87849 O 1.93096 0.21018 0.65550 C 0.61078 2.34420 -2.05295 C 0.34815 3.48394 -1.29598 C 0.61231 3.51058 0.06708 C 1.14166 2.40768 0.72079 C 1.40738 1.25555 -0.03867 C 1.14696 1.22736 -1.40260 C 0.46316 5.33300 -2.77605 C 1.43024 2.42448 2.19535 C 2.22177 -0.98681 -0.03628 H 0.38197 4.40915 0.62172 H 1.37280 0.34907 -1.98537 H -0.26671 5.95123 -3.29723 H 2.48712 2.24131 2.39363 H 1.16161 3.38496 2.63070 H 0.87439 1.64357 2.71590 H 1.32407 -1.41600 -0.48378 H 2.97022 -0.82583 -0.81356 H 2.61685 -1.67385 0.70531 O 1.21459 4.56069 -3.67362 O -1.00464 0.21018 -6.20761 C 0.31553 2.34420 -3.49916 C 0.57816 3.48394 -4.25612 C 0.31400 3.51058 -5.61918 C -0.21535 2.40768 -6.27290 C -0.48107 1.25555 -5.51344 C -0.22065 1.22736 -4.14951 C -0.50392 2.42448 -7.74746 C -1.29546 -0.98681 -5.51583 H 0.54434 4.40915 -6.17382 H -0.44648 0.34907 -3.56673 H 1.19303 5.95123 -2.25487 H -1.56081 2.24131 -7.94574 H -0.23530 3.38496 -8.18280 H 0.05192 1.64357 -8.26800 H -0.39776 -1.41600 -5.06832 H -2.04390 -0.82583 -4.73854 H -1.69053 -1.67385 -6.25742 HE1 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -958.803185 Hartree Sum of electronic and zero-point Energies= -958.475540 Sum of electronic and thermal Energies= -958.456391 Sum of electronic and thermal Enthalpies= -958.455447 Sum of electronic and thermal Free Energies= -958.523315 Coordinates in ang: O 0.37723 4.95541 -1.52903 O 1.68787 0.13364 0.49884 C 0.64147 2.55135 -2.05102 C 0.66521 3.71560 -1.19221 C 1.00037 3.59913 0.17844 C 1.32495 2.41036 0.75436 C 1.33032 1.25172 -0.09855 C 0.99657 1.34800 -1.44829 C 0.00606 5.37094 -2.84436 C 1.68050 2.27501 2.19923 C 1.75764 -1.10048 -0.22244 H 0.98744 4.50974 0.75644 H 1.05729 0.46483 -2.05687 H -1.02396 5.06764 -3.02016 H 2.68791 1.87354 2.30966 H 1.62732 3.23726 2.70041 H 1.00562 1.57872 2.69710 H 0.78285 -1.35440 -0.63206 H 2.50078 -1.03259 -1.01335 H 2.05864 -1.84093 0.50780 O 0.86277 4.87336 -3.80430 O -0.79971 0.17503 -6.08778 C 0.28879 2.54966 -3.47326 C 0.48746 3.65400 -4.30965 C 0.32978 3.56019 -5.68465 C -0.07944 2.38290 -6.28349 C -0.35408 1.27492 -5.44716 C -0.16932 1.36070 -4.08213 C -0.27210 2.27075 -7.76438 C -1.09636 -0.98902 -5.33639 H 0.52062 4.43987 -6.28055 H -0.40825 0.51588 -3.46127 H 0.10763 6.44736 -2.81671 H -1.30441 2.01210 -8.00206 H -0.02221 3.20458 -8.26158 H 0.35177 1.47669 -8.17571 H -0.21232 -1.35470 -4.81320 H -1.89622 -0.80142 -4.61971 H -1.42335 -1.73139 -6.05605 Neutral HE2 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -998.271858 Hartree Sum of electronic and zero-point Energies= -997.914789 Sum of electronic and thermal Energies= -997.894721 Sum of electronic and thermal Enthalpies= -997.893777 Sum of electronic and thermal Free Energies= -997.962993 Coordinates in ang: O 12.44384 5.87638 -2.65820 O 7.50601 5.77328 -5.08556 O 12.22292 3.54603 -0.97328 O 8.19717 5.86385 1.98585 C 13.17272 4.67563 -2.88793 H 14.11525 4.79976 -2.36061 H 13.37856 4.55097 -3.95475 C 10.10464 5.37986 -2.47800 C 11.18670 5.85082 -3.21682 C 11.02107 6.29291 -4.52541 H 11.88914 6.66270 -5.05343 C 9.78538 6.28019 -5.15218 C 8.69285 5.78662 -4.42162 C 8.85354 5.35078 -3.11363 H 8.00952 4.96683 -2.56492 C 9.60146 6.76269 -6.56303 H 8.88308 7.58220 -6.61015 H 9.21397 5.97027 -7.20475 H 10.54518 7.10997 -6.97910 C 6.35675 5.29923 -4.41459 H 5.53900 5.38365 -5.12331 H 6.13368 5.90189 -3.53284 H 6.47034 4.25554 -4.11780 C 12.44633 3.45354 -2.36500 H 11.51519 3.27099 -2.89777 H 13.08498 2.58251 -2.50201 C 10.19857 5.01247 -1.03587 C 11.16547 4.21119 -0.41648 C 11.09499 3.99471 0.96636 H 11.85634 3.36218 1.39998 C 10.11519 4.53547 1.77237 C 9.14369 5.33990 1.15668 C 9.19875 5.56302 -0.20506 H 8.47198 6.20819 -0.66938 C 10.07376 4.28498 3.25288 H 10.89308 3.63794 3.55986 H 9.13457 3.81500 3.54760 H 10.14506 5.21873 3.81227 C 7.19324 6.68436 1.42851 H 6.55202 6.97942 2.25334 H 6.60149 6.14357 0.68772 H 7.61786 7.57675 0.96555 HE2 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -998.081524 Hartree Sum of electronic and zero-point Energies= -997.723980 Sum of electronic and thermal Energies= -997.703846 Sum of electronic and thermal Enthalpies= -997.702901 Sum of electronic and thermal Free Energies= -997.772643 Coordinates in ang: O 12.38900 5.82973 -2.59128 O 7.52001 5.81272 -5.14110 O 12.11354 3.52204 -0.99445 O 8.24373 5.80919 1.97702 C 13.15911 4.66199 -2.84484 H 14.07933 4.78331 -2.28151 H 13.39716 4.56702 -3.90583 C 10.04903 5.36802 -2.49278 C 11.16175 5.81328 -3.20550 C 11.03428 6.25343 -4.51706 H 11.91641 6.60764 -5.03063 C 9.80843 6.26011 -5.16136 C 8.68117 5.79955 -4.44963 C 8.80017 5.37223 -3.13732 H 7.93731 5.00882 -2.60461 C 9.65920 6.73376 -6.57658 H 8.95769 7.56630 -6.63676 H 9.26067 5.94213 -7.21186 H 10.61578 7.05549 -6.98158 C 6.33214 5.39149 -4.49609 H 5.54051 5.49944 -5.22965 H 6.11207 6.01622 -3.62984 H 6.39936 4.34816 -4.18650 C 12.41274 3.42554 -2.39293 H 11.49741 3.26143 -2.95234 H 13.04465 2.54771 -2.47484 C 10.13367 5.02516 -1.05990 C 11.15340 4.21739 -0.42825 C 11.15220 4.04252 0.98349 H 11.95194 3.44391 1.39083 C 10.19189 4.56314 1.79176 C 9.15067 5.32285 1.15901 C 9.15259 5.53352 -0.22699 H 8.39279 6.15866 -0.66250 C 10.17986 4.37046 3.27474 H 11.03206 3.77597 3.59157 H 9.26433 3.87098 3.59123 H 10.21110 5.33216 3.78675 C 7.13916 6.58021 1.48903 H 6.55350 6.82416 2.36620 H 6.54672 5.98924 0.79516 H 7.49681 7.48988 1.01324 Neutral HE3 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1037.561208 Hartree Sum of electronic and zero-point Energies= -1037.174945 Sum of electronic and thermal Energies= -1037.153636 Sum of electronic and thermal Enthalpies= -1037.152692 Sum of electronic and thermal Free Energies= -1037.224453 Coordinates in ang: O 0.93127 3.90348 3.18349 O 1.05829 -1.24753 1.22690 C -1.16136 4.93880 2.39810 C 0.36054 4.97956 2.44880 C 0.44813 1.60620 3.49797 C 0.88299 2.63501 2.66346 C 1.35502 2.34391 1.38602 C 1.40427 1.04302 0.90458 C 0.98053 0.00793 1.75053 C 0.51651 0.29074 3.02865 C 1.91047 0.73174 -0.47616 C 0.64393 -2.33749 2.02291 H -1.50697 5.90541 2.02447 H 0.69092 5.86834 2.98340 H 0.77546 5.02863 1.44090 H 1.71215 3.14613 0.75614 H 0.17625 -0.50068 3.67709 H 1.14626 0.23361 -1.07446 H 2.21003 1.64131 -0.99339 H 2.76796 0.05843 -0.44142 H 1.24233 -2.41829 2.93192 H -0.41004 -2.25637 2.29356 H 0.79106 -3.22619 1.41703 O -1.80450 3.24045 3.98406 O 0.64433 1.03312 8.39338 C -1.81286 4.64860 3.74397 C -0.05342 1.89261 4.86535 C -1.13314 2.74940 5.07071 C -1.57619 3.01876 6.36305 C -0.97318 2.45100 7.47642 C 0.09831 1.57006 7.26677 C 0.54497 1.29600 5.98011 C -1.45023 2.74497 8.87120 C 1.72919 0.13946 8.25899 H -1.50446 4.18404 1.68965 H -2.85408 4.97040 3.73198 H -1.30563 5.17154 4.55513 H -2.42560 3.67490 6.49549 H 1.38241 0.63623 5.81913 H -0.65553 3.18255 9.47704 H -2.28903 3.43834 8.85532 H -1.76720 1.83480 9.38211 H 1.45040 -0.74262 7.68015 H 2.58734 0.62117 7.78763 H 1.99674 -0.16302 9.26668 HE3 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1037.369610 Hartree Sum of electronic and zero-point Energies= -1036.983084 Sum of electronic and thermal Energies= -1036.961719 Sum of electronic and thermal Enthalpies= -1036.960775 Sum of electronic and thermal Free Energies= -1037.033118 Coordinates in ang: O 0.81144 3.82547 3.14264 O 1.21237 -1.21899 1.28512 C -1.12207 5.09535 2.42611 C 0.39832 5.01681 2.43967 C 0.46976 1.55075 3.52868 C 0.77512 2.62137 2.61142 C 1.10545 2.34827 1.27244 C 1.25204 1.05721 0.83820 C 1.04192 -0.01088 1.78277 C 0.65577 0.25100 3.10076 C 1.64649 0.72555 -0.56501 C 1.06214 -2.37880 2.11021 H -1.40091 6.11600 2.16051 H 0.83337 5.81898 3.02658 H 0.82371 5.04647 1.44067 H 1.30510 3.16024 0.59246 H 0.42775 -0.56042 3.77098 H 0.88624 0.10424 -1.03913 H 1.77865 1.62946 -1.15279 H 2.57487 0.15463 -0.58005 H 1.75987 -2.34160 2.94339 H 0.03925 -2.45490 2.47113 H 1.29278 -3.21870 1.46713 O -1.65975 3.30633 3.93458 O 0.51001 0.96309 8.40345 C -1.75800 4.72772 3.76105 C -0.02382 1.86604 4.86959 C -1.04954 2.80814 5.04267 C -1.49541 3.11664 6.32487 C -0.96069 2.50218 7.44533 C 0.04212 1.52404 7.26498 C 0.49049 1.20475 5.99569 C -1.43664 2.83530 8.82812 C 1.50009 -0.04431 8.31178 H -1.53094 4.43874 1.65792 H -2.81330 4.99171 3.75932 H -1.27324 5.24030 4.59096 H -2.29697 3.83122 6.44327 H 1.28013 0.48461 5.85773 H -0.61376 3.19904 9.44443 H -2.21206 3.59719 8.79995 H -1.83413 1.95139 9.32773 H 1.13985 -0.89978 7.73925 H 2.41402 0.33969 7.85736 H 1.70676 -0.35309 9.33089 Neutral HE4 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1076.848807 Hartree Sum of electronic and zero-point Energies= -1076.432501 Sum of electronic and thermal Energies= -1076.410135 Sum of electronic and thermal Enthalpies= -1076.409190 Sum of electronic and thermal Free Energies= -1076.483107 Coordinates in ang: O 4.05956 1.08983 8.02378 O 6.03722 1.89708 13.10611 O 2.70669 3.59175 8.24045 O -1.05247 1.12354 11.44451 C 3.79365 1.87905 5.77186 H 3.65418 0.88021 5.35451 H 4.31482 2.46436 5.01001 C 3.66494 1.81214 10.26327 C 4.53551 1.33565 9.28451 C 5.86514 1.06427 9.60506 H 6.51804 0.67925 8.83443 C 6.36979 1.25369 10.88219 C 5.49228 1.72602 11.86930 C 4.16593 1.99134 11.56042 H 3.49519 2.36655 12.31628 C 4.71589 1.79693 6.97431 H 5.63967 1.28390 6.69640 H 4.97939 2.79310 7.32812 C 7.80484 0.96081 11.21942 H 8.34091 0.59415 10.34607 H 7.88141 0.21161 12.00860 H 8.31543 1.85286 11.58507 C 5.21222 2.37352 14.14808 H 4.81767 3.36570 13.92312 H 5.84299 2.43005 15.02982 H 4.38158 1.69298 14.34247 C 2.41940 2.49710 6.05152 H 1.92821 2.69712 5.09711 H 1.78955 1.77996 6.57695 C 2.22567 2.07590 10.00364 C 1.77466 2.93004 8.99419 C 0.40484 3.14890 8.84008 H 0.05500 3.82143 8.07178 C -0.53896 2.54332 9.65646 C -0.08409 1.69407 10.67337 C 1.27528 1.47585 10.84023 H 1.62964 0.81195 11.61206 C 2.44364 3.79451 6.85179 H 3.24678 4.44861 6.51632 H 1.51051 4.34170 6.71951 C -2.01090 2.78651 9.47370 H -2.19154 3.47504 8.65036 H -2.45768 3.20594 10.37608 H -2.54205 1.85667 9.26549 C -0.66011 0.25066 12.48219 H -0.12234 -0.61574 12.09362 H -1.57675 -0.08120 12.95995 H -0.03495 0.75994 13.21757 HE4 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1076.658307 Hartree Sum of electronic and zero-point Energies= -1076.241534 Sum of electronic and thermal Energies= -1076.219074 Sum of electronic and thermal Enthalpies= -1076.218130 Sum of electronic and thermal Free Energies= -1076.292652 Coordinates in ang: O 4.00385 1.16145 8.04152 O 6.07538 1.81443 13.10137 O 2.68975 3.46243 8.27134 O -1.03906 1.21763 11.46723 C 3.78526 1.92911 5.75669 H 3.59140 0.94254 5.33514 H 4.35269 2.48092 5.00456 C 3.65632 1.80421 10.31029 C 4.51410 1.38482 9.28460 C 5.85478 1.13286 9.57166 H 6.50462 0.79375 8.77894 C 6.37248 1.28014 10.84730 C 5.50265 1.68320 11.88163 C 4.16771 1.92290 11.61516 H 3.50676 2.25454 12.39869 C 4.69967 1.79552 6.96169 H 5.57466 1.20562 6.68764 H 5.04583 2.77308 7.29674 C 7.81756 1.01278 11.14785 H 8.35165 0.70496 10.25199 H 7.92117 0.23100 11.90088 H 8.30123 1.90249 11.55250 C 5.27111 2.22142 14.19194 H 4.84854 3.21266 14.02307 H 5.92943 2.25247 15.05358 H 4.46598 1.50926 14.37679 C 2.43691 2.62403 5.99684 H 2.02760 2.93380 5.03463 H 1.72180 1.91567 6.41528 C 2.22880 2.04828 10.07938 C 1.76443 2.84164 8.96544 C 0.38268 2.97246 8.71000 H 0.04598 3.54260 7.86097 C -0.54939 2.43521 9.55433 C -0.08340 1.70745 10.70570 C 1.28321 1.53005 10.94300 H 1.61106 0.92666 11.77211 C 2.47498 3.85409 6.89320 H 3.31730 4.50296 6.67630 H 1.56594 4.44354 6.81790 C -2.01898 2.59105 9.32916 H -2.21281 3.17312 8.43264 H -2.48889 3.08463 10.17976 H -2.49582 1.61589 9.22700 C -0.72652 0.48015 12.65405 H -0.18501 -0.42793 12.40038 H -1.68318 0.23207 13.09601 H -0.14586 1.09502 13.33728 Neutral HE5 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1116.131270 Hartree Sum of electronic and zero-point Energies= -1115.685558 Sum of electronic and thermal Energies= -1115.661898 Sum of electronic and thermal Enthalpies= -1115.660954 Sum of electronic and thermal Free Energies= -1115.738117 Coordinates in ang: O 1.93678 9.48860 4.01098 O 1.65473 13.08115 -0.16940 O 1.31561 11.91560 5.59996 O -3.86408 10.53524 4.28482 C 3.17081 8.94800 4.46528 H 3.76189 8.59456 3.62117 H 2.88734 8.06859 5.04143 C 3.97362 9.92139 5.32812 H 3.86034 10.92696 4.92086 H 5.03142 9.66755 5.22898 C 3.62772 9.89195 6.82060 H 3.81519 8.88160 7.19430 H 4.33289 10.54082 7.34720 C 2.20766 10.29700 7.22989 H 1.46741 9.63766 6.77482 H 2.12211 10.15561 8.30965 C 1.83721 11.74555 6.91171 H 1.14048 12.14190 7.64944 H 2.72009 12.38232 6.93838 C 0.82286 11.26387 2.94486 C 1.93236 10.41636 3.00816 C 2.92006 10.50758 2.02834 H 3.78661 9.86638 2.06774 C 2.82462 11.40477 0.97083 C 1.69596 12.22799 0.89458 C 0.71287 12.15235 1.87304 H -0.14872 12.79975 1.83731 C 3.89922 11.49659 -0.07668 H 4.69835 10.78510 0.12302 H 4.33283 12.49715 -0.11142 H 3.50101 11.29451 -1.07191 C 0.54869 13.94888 -0.29242 H 0.71794 14.52778 -1.19521 H 0.47442 14.62588 0.56039 H -0.38610 13.39413 -0.39100 C -0.23958 11.21585 3.98066 C 0.04353 11.50415 5.31861 C -0.97765 11.43147 6.26510 H -0.77376 11.64340 7.30297 C -2.28193 11.10235 5.91449 C -2.56603 10.84537 4.56879 C -1.55223 10.90332 3.62092 H -1.75539 10.68357 2.58498 C -3.37354 11.02755 6.94576 H -2.98752 11.25679 7.93730 H -3.82324 10.03408 6.97495 H -4.17902 11.72824 6.72163 C -4.21144 10.25959 2.94513 H -5.27620 10.04727 2.94674 H -3.67216 9.39141 2.56233 H -4.01645 11.11596 2.29712 HE5 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1115.944843 Hartree Sum of electronic and zero-point Energies= -1115.498908 Sum of electronic and thermal Energies= -1115.475147 Sum of electronic and thermal Enthalpies= -1115.474202 Sum of electronic and thermal Free Energies= -1115.552098 Coordinates in ang: O 1.94389 9.55135 4.06092 O 1.63664 12.98185 -0.22883 O 1.27429 11.73489 5.59423 O -3.85525 10.70786 4.26777 C 3.17170 8.98532 4.52696 H 3.73793 8.59650 3.68331 H 2.86144 8.13147 5.12478 C 4.00535 9.96507 5.35292 H 3.89710 10.96519 4.93020 H 5.05637 9.69968 5.22716 C 3.71429 9.97125 6.85827 H 3.95070 8.98302 7.25875 H 4.41347 10.66290 7.33361 C 2.29826 10.33074 7.32026 H 1.57146 9.59635 6.96912 H 2.27927 10.27752 8.40992 C 1.82104 11.72589 6.93040 H 1.08296 12.11906 7.62260 H 2.64283 12.43329 6.87773 C 0.80593 11.26002 2.92611 C 1.95236 10.45683 3.05352 C 2.96531 10.56584 2.10006 H 3.85983 9.97084 2.18579 C 2.85011 11.41639 1.01160 C 1.67393 12.17876 0.86151 C 0.66639 12.08993 1.80406 H -0.22017 12.69711 1.72119 C 3.94474 11.52946 -0.00820 H 4.78165 10.88273 0.24471 H 4.30660 12.55582 -0.07747 H 3.58265 11.25830 -1.00035 C 0.48239 13.76821 -0.45372 H 0.66408 14.30948 -1.37616 H 0.32379 14.47960 0.35777 H -0.40469 13.14385 -0.56840 C -0.25887 11.19665 3.92676 C 0.04958 11.34669 5.32920 C -0.95456 11.15578 6.30033 H -0.71374 11.20799 7.34817 C -2.25692 10.94379 5.93410 C -2.57783 10.90443 4.53232 C -1.58031 11.02692 3.56168 H -1.82137 10.92119 2.51749 C -3.34913 10.76947 6.94046 H -2.95496 10.82296 7.95134 H -3.84544 9.80836 6.80484 H -4.11197 11.53840 6.81785 C -4.31952 10.65990 2.91577 H -5.39208 10.52883 2.98537 H -3.87369 9.81668 2.39345 H -4.08828 11.59112 2.40407 Neutral HE6 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1155.417167 Hartree Sum of electronic and zero-point Energies= -1154.942330 Sum of electronic and thermal Energies= -1154.917420 Sum of electronic and thermal Enthalpies= -1154.916476 Sum of electronic and thermal Free Energies= -1154.996453 Coordinates in ang: O -0.08376 6.56594 1.28971 O -5.53919 6.44025 2.08847 O -1.42037 7.27555 5.12904 O 1.16110 2.47410 4.25948 C 0.57728 7.81878 1.09986 H -0.02442 8.47112 0.46356 H 1.48295 7.56530 0.55251 C 0.93940 8.51531 2.40835 H 1.77161 9.19575 2.20423 H 1.32080 7.75405 3.09032 C -0.19963 9.31095 3.05140 H -1.07963 8.68347 3.16692 H -0.47932 10.11829 2.36868 C 0.16578 9.92783 4.40650 H 1.08521 10.50951 4.29420 H -0.61127 10.64414 4.68747 C 0.35664 8.94743 5.57113 H 0.74024 9.50503 6.42926 H 1.11793 8.20301 5.33290 C -0.91219 8.24296 6.04225 H -0.75857 7.79064 7.02283 H -1.72327 8.96198 6.14524 C -1.91917 5.99355 2.70193 C -1.43539 6.55908 1.52462 C -2.32704 7.04747 0.56895 H -1.93458 7.45875 -0.35070 C -3.69907 7.01135 0.76121 C -4.18322 6.45129 1.95392 C -3.30325 5.94605 2.90044 H -3.67184 5.51063 3.81515 C -4.65657 7.54060 -0.26971 H -5.34455 6.76447 -0.60758 H -4.12012 7.92356 -1.13583 H -5.26980 8.34613 0.13668 C -6.09496 5.89783 3.26760 H -7.17137 5.99648 3.16651 H -5.76416 6.44387 4.15252 H -5.83911 4.84309 3.38110 C -0.99503 5.43330 3.72787 C -0.74894 6.10161 4.92901 C 0.12614 5.54124 5.86093 H 0.32767 6.05145 6.78997 C 0.76154 4.32787 5.63149 C 0.50789 3.65975 4.42737 C -0.36000 4.21163 3.49515 H -0.55667 3.70820 2.56241 C 1.70280 3.73303 6.64175 H 2.69735 3.58760 6.21786 H 1.35876 2.75241 6.97357 H 1.79353 4.37672 7.51474 C 0.96267 1.76222 3.05691 H 1.57327 0.86758 3.13159 H 1.28102 2.34449 2.19058 H -0.08251 1.47467 2.93014 HE6 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1155.230870 Hartree Sum of electronic and zero-point Energies= -1154.755286 Sum of electronic and thermal Energies= -1154.730315 Sum of electronic and thermal Enthalpies= -1154.729371 Sum of electronic and thermal Free Energies= -1154.809844 O -0.37454 7.51880 2.02404 O -5.42866 5.41626 1.48586 O -0.79468 7.51886 4.83011 O 0.33581 2.23761 4.69423 C 0.11170 8.65871 1.31052 H -0.71139 9.29960 1.00151 H 0.63350 8.30842 0.41995 C 1.02678 9.40903 2.26074 H 1.64717 10.09927 1.68728 H 1.70552 8.68381 2.71200 C 0.22861 10.17202 3.32861 H -0.72639 9.66975 3.48880 H -0.01565 11.16326 2.94273 C 0.93906 10.32567 4.67407 H 1.94441 10.72362 4.51897 H 0.40656 11.06913 5.27162 C 1.04832 9.04020 5.50204 H 1.55434 9.27340 6.44039 H 1.67270 8.30099 4.99854 C -0.29443 8.40576 5.86237 H -0.25329 7.85192 6.79561 H -1.07615 9.15400 5.94930 C -2.01787 6.03031 2.76396 C -1.63301 7.05849 1.88567 C -2.52534 7.47836 0.89764 H -2.23053 8.23584 0.18976 C -3.79071 6.92596 0.77551 C -4.17263 5.89789 1.65861 C -3.28567 5.44679 2.61866 H -3.56821 4.66164 3.30052 C -4.74742 7.39454 -0.28126 H -5.04007 6.57261 -0.93522 H -4.30412 8.18051 -0.88823 H -5.66425 7.77816 0.16767 C -5.88146 4.38176 2.33698 H -6.89673 4.16011 2.02524 H -5.88465 4.70038 3.38038 H -5.26784 3.48578 2.23323 C -1.07998 5.46562 3.74278 C -0.41410 6.26829 4.74429 C 0.53048 5.67741 5.61388 H 1.06283 6.28795 6.32284 C 0.77810 4.33233 5.59127 C 0.04968 3.52394 4.65250 C -0.85591 4.10217 3.75810 H -1.35459 3.49092 3.02563 C 1.76576 3.68444 6.50816 H 2.53654 3.16670 5.93707 H 1.27765 2.93500 7.13145 H 2.23926 4.42177 7.15025 C -0.31516 1.31518 3.81498 H 0.08110 0.34221 4.07702 H -0.07735 1.54918 2.77997 H -1.39057 1.33698 3.97389 Neutral pHE1 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1111.358569 Hartree Sum of electronic and zero-point Energies= -1111.001059 Sum of electronic and thermal Energies= -1110.982293 Sum of electronic and thermal Enthalpies= -1110.981349 Sum of electronic and thermal Free Energies= -1111.048009 Coordinates in ang: C -0.12665 0.27202 1.00058 C 0.00110 -0.35402 3.67683 C -0.04575 -1.06397 1.37170 C -0.14835 1.29416 1.95380 C -0.07619 0.98505 3.29510 C 0.02201 -1.37175 2.75226 C -0.00550 -2.32859 0.62382 C 0.11276 -4.99889 -0.24468 C -0.03303 -2.64923 -0.72724 C 0.08593 -3.38659 1.56060 C 0.13820 -4.68630 1.11420 C 0.01871 -3.97606 -1.16376 C 0.10526 -2.85846 2.96959 H 1.01303 -3.14687 3.50596 H -0.73163 -3.23591 3.56285 O -0.10010 -1.76204 -1.76107 O -0.18274 0.74822 -0.27650 O 0.04356 -0.52190 5.03234 O 0.21037 -5.79101 1.91538 C -0.11468 1.82250 4.54585 H 0.58681 2.65548 4.53617 H -1.11137 2.23614 4.71417 C -0.19883 2.61089 1.22494 H 0.76325 3.12560 1.27414 H -0.95522 3.29366 1.60899 C 0.01029 -3.97264 -2.66956 H 0.99603 -4.21995 -3.06965 H -0.70362 -4.67108 -3.10353 C 0.14731 -6.49840 -0.37650 H 0.88533 -6.85770 -1.09221 H -0.82455 -6.89072 -0.68380 C -0.52542 2.14424 -0.20465 H 0.03650 2.66176 -0.97642 H -1.59102 2.24252 -0.41632 C 0.25916 0.77819 5.61738 H 1.31197 0.85487 5.89071 H -0.34437 0.83924 6.51805 C 0.50298 -6.91757 1.06434 H 1.56569 -7.14358 1.15701 H -0.07082 -7.76447 1.42858 C -0.37433 -2.51093 -2.95915 H 0.19174 -2.05817 -3.76774 H -1.43907 -2.42066 -3.17852 pHE1 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1111.180559 Hartree Sum of electronic and zero-point Energies= -1110.823718 Sum of electronic and thermal Energies= -1110.804316 Sum of electronic and thermal Enthalpies= -1110.803372 Sum of electronic and thermal Free Energies= -1110.873445 Coordinates in ang: C -0.20948 0.24335 1.02151 C 0.07733 -0.36210 3.68425 C -0.06929 -1.11699 1.41202 C -0.20874 1.29644 1.96383 C -0.06668 1.00017 3.28392 C 0.07568 -1.40224 2.78333 C -0.03824 -2.34569 0.67126 C 0.09613 -4.98894 -0.24126 C -0.12735 -2.64829 -0.69672 C 0.12913 -3.41208 1.60102 C 0.19499 -4.69546 1.13497 C -0.06299 -3.97189 -1.14876 C 0.21206 -2.88273 3.00662 H 1.15672 -3.14021 3.49040 H -0.58191 -3.27577 3.64530 O -0.28264 -1.75873 -1.68224 O -0.35294 0.65624 -0.21841 O 0.20752 -0.49512 5.00072 O 0.34420 -5.80223 1.89782 C -0.04088 1.84871 4.51844 H 0.73941 2.60743 4.47602 H -0.99033 2.36503 4.66074 C -0.38690 2.58861 1.21811 H 0.44457 3.27215 1.38238 H -1.30045 3.10250 1.51381 C -0.22952 -3.96514 -2.64401 H 0.57534 -4.48634 -3.15975 H -1.16790 -4.43352 -2.94164 C 0.15629 -6.48080 -0.39648 H 0.87506 -6.80232 -1.14826 H -0.81868 -6.87735 -0.68520 C -0.45144 2.11310 -0.24555 H 0.37692 2.46302 -0.85266 H -1.38793 2.34668 -0.74031 C 0.22113 0.81446 5.63117 H 1.19579 0.93159 6.09540 H -0.54450 0.80356 6.39970 C 0.56110 -6.93189 1.02091 H 1.61606 -7.19477 1.07376 H -0.03148 -7.75761 1.40057 C -0.22104 -2.45528 -2.95553 H 0.69447 -2.13678 -3.44758 H -1.07386 -2.12569 -3.53960 Neutral pHE2 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1150.646270 Hartree Sum of electronic and zero-point Energies= -1150.258556 Sum of electronic and thermal Energies= -1150.238894 Sum of electronic and thermal Enthalpies= -1150.237950 Sum of electronic and thermal Free Energies= -1150.306301 Coordinates in ang: C -0.35595 0.01598 1.20488 C 0.51448 -0.03806 3.78157 C 0.08080 -1.20527 1.72038 C -0.32723 1.20390 1.93944 C 0.13300 1.18440 3.23481 C 0.48553 -1.22717 3.08038 C 0.07387 -2.48808 0.98509 C -0.01115 -4.99540 -0.32308 C 0.32425 -2.63010 -0.37881 C -0.13759 -3.67730 1.73073 C -0.19755 -4.87843 1.05274 C 0.25789 -3.85666 -1.04458 C -0.21445 -3.59836 3.23205 H -0.00104 -4.57569 3.66142 H -1.22174 -3.31999 3.55706 C 0.78258 -2.55071 3.73440 H 1.79857 -2.88111 3.49698 H 0.72588 -2.44894 4.81647 O 0.72802 -1.62379 -1.20633 O -0.90513 0.19444 -0.03252 O 0.88251 0.06667 5.09753 O -0.43131 -6.08743 1.65454 C 0.23522 2.23517 4.30713 H 0.76855 3.13109 3.99270 H -0.75387 2.54668 4.64998 C -0.85343 2.31226 1.06842 H -0.04317 2.94507 0.69937 H -1.57212 2.95812 1.57040 C 0.62348 -3.63287 -2.48775 H 1.61317 -4.03808 -2.71014 H -0.07839 -4.07772 -3.19152 C -0.16114 -6.44521 -0.69723 H 0.63160 -6.81507 -1.34574 H -1.11140 -6.62525 -1.20478 C -1.50412 1.50135 -0.06342 H -1.34112 1.91564 -1.05398 H -2.57687 1.38818 0.10144 C 1.00614 1.46881 5.40017 H 2.06583 1.72639 5.38643 H 0.61858 1.62678 6.40234 C -0.12087 -7.11181 0.69155 H 0.87589 -7.49622 0.91222 H -0.84362 -7.91267 0.81599 C 0.60488 -2.09579 -2.55693 H 1.42133 -1.66876 -3.13168 H -0.34159 -1.73220 -2.95985 pHE2 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1150.468586 Hartree Sum of electronic and zero-point Energies= -1150.080599 Sum of electronic and thermal Energies= -1150.060591 Sum of electronic and thermal Enthalpies= -1150.059647 Sum of electronic and thermal Free Energies= -1150.130078 Coordinates in ang: C -0.38648 0.00609 1.23404 C 0.52010 -0.03506 3.77175 C 0.07167 -1.24839 1.75263 C -0.30763 1.23697 1.94014 C 0.15581 1.22105 3.21158 C 0.46668 -1.25595 3.09244 C 0.05322 -2.50517 1.01127 C -0.00980 -4.99255 -0.31700 C 0.24614 -2.62120 -0.37171 C -0.09265 -3.70870 1.76151 C -0.15022 -4.89765 1.07448 C 0.19677 -3.84811 -1.04208 C -0.14871 -3.64536 3.26313 H 0.12425 -4.61206 3.68019 H -1.16545 -3.42792 3.60256 C 0.79923 -2.55664 3.76786 H 1.83250 -2.83599 3.54405 H 0.72459 -2.44425 4.84688 O 0.57306 -1.60166 -1.19290 O -0.99422 0.13454 0.08074 O 0.91928 0.07141 5.02694 O -0.33040 -6.11234 1.66274 C 0.35620 2.27780 4.25417 H 1.08600 3.02110 3.93560 H -0.57073 2.80381 4.47933 C -0.84551 2.32130 1.05443 H -0.05504 3.00064 0.73638 H -1.61392 2.91400 1.54645 C 0.49828 -3.60854 -2.49628 H 1.46959 -4.02389 -2.76907 H -0.24327 -4.03979 -3.16627 C -0.12734 -6.43992 -0.70098 H 0.66379 -6.77467 -1.36958 H -1.08053 -6.63138 -1.19736 C -1.41042 1.51740 -0.12748 H -1.01756 1.81236 -1.09382 H -2.49524 1.50548 -0.16216 C 0.86035 1.46133 5.45950 H 1.86240 1.73063 5.77600 H 0.19052 1.49192 6.31244 C -0.05083 -7.12756 0.67594 H 0.94735 -7.51934 0.86891 H -0.77700 -7.92291 0.80894 C 0.49429 -2.07054 -2.55785 H 1.33824 -1.64819 -3.09318 H -0.43017 -1.68531 -2.98501 Neutral pHE3 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1189.930917 Hartree Sum of electronic and zero-point Energies= -1189.513183 Sum of electronic and thermal Energies= -1189.492443 Sum of electronic and thermal Enthalpies= -1189.491499 Sum of electronic and thermal Free Energies= -1189.562130 Coordinates in ang: C 0.06778 0.14372 1.11992 C -0.76935 0.08533 3.70019 C -0.22978 -1.09444 1.68109 C -0.05315 1.34709 1.81393 C -0.48891 1.31975 3.11867 C -0.65970 -1.12197 3.03152 C -0.06945 -2.36262 0.92942 C 0.21122 -4.77818 -0.50160 C -0.64985 -2.56348 -0.31826 C 0.66435 -3.43480 1.49660 C 0.78028 -4.60005 0.75765 C -0.51009 -3.74239 -1.04934 O 1.48164 -5.70236 1.17446 O -1.15900 0.20178 5.01008 C -1.42396 1.59465 5.25663 H -1.08661 1.82260 6.26341 H -2.50201 1.75183 5.20004 C 1.15817 -6.78253 0.28024 H 0.41533 -7.41601 0.76692 H 2.06290 -7.36114 0.11853 O 0.53384 0.32229 -0.15145 O -1.45262 -1.65547 -0.94726 C -1.62635 -2.10071 -2.30348 H -0.93139 -1.54514 -2.93446 H -2.64292 -1.86258 -2.60216 C 0.99165 1.68216 -0.26089 H 2.07825 1.68376 -0.16379 H 0.72573 2.04191 -1.25045 C 1.29568 -3.29270 2.85770 H 1.85729 -2.35743 2.88456 H 2.01201 -4.09629 3.01652 C -0.97453 -2.43272 3.70443 H -1.63244 -3.00903 3.05190 H -1.52335 -2.24844 4.62597 C 0.27373 -3.28083 4.00957 H 0.77026 -2.90386 4.90584 H -0.04852 -4.30007 4.23157 C -0.69156 2.38900 4.15839 H 0.26444 2.78210 4.51142 H -1.28345 3.23352 3.80889 C 0.33171 2.46811 0.88639 H 1.01801 3.18741 1.33062 H -0.54758 3.01957 0.54624 C -1.30610 -3.60696 -2.31999 H -0.75501 -3.89217 -3.21488 H -2.21237 -4.21566 -2.28473 C 0.58770 -6.14664 -1.00200 H 1.33849 -6.08417 -1.79275 H -0.25350 -6.71617 -1.39439 pHE3 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1189.751632 Hartree Sum of electronic and zero-point Energies= -1189.333293 Sum of electronic and thermal Energies= -1189.312253 Sum of electronic and thermal Enthalpies= -1189.311309 Sum of electronic and thermal Free Energies= -1189.383833 Coordinates in ang: C 0.07145 0.13688 1.13845 C -0.79590 0.09644 3.68230 C -0.24288 -1.13389 1.70602 C -0.07756 1.37885 1.81251 C -0.51267 1.35948 3.09437 C -0.67477 -1.14800 3.02616 C -0.05859 -2.38239 0.94985 C 0.23543 -4.77411 -0.49594 C -0.59186 -2.54926 -0.32606 C 0.63513 -3.47244 1.54191 C 0.76249 -4.62452 0.79053 C -0.44751 -3.72500 -1.06153 O 1.42973 -5.73775 1.21245 O -1.20587 0.20349 4.92866 C -1.24266 1.60551 5.33280 H -0.58751 1.69321 6.19277 H -2.26482 1.81189 5.63119 C 1.14160 -6.80249 0.28382 H 0.39171 -7.45080 0.73671 H 2.05648 -7.36777 0.13682 O 0.58043 0.27554 -0.06031 O -1.34693 -1.62035 -0.96476 C -1.51771 -2.05668 -2.33174 H -0.82594 -1.48698 -2.95102 H -2.53583 -1.82062 -2.62382 C 0.81623 1.68618 -0.35517 H 1.87723 1.78020 -0.56004 H 0.25007 1.90758 -1.25313 C 1.23802 -3.35042 2.91776 H 1.83577 -2.43783 2.95805 H 1.92238 -4.17797 3.08818 C -1.02607 -2.43530 3.71871 H -1.68263 -2.99682 3.05312 H -1.58845 -2.22698 4.62538 C 0.19878 -3.30727 4.05180 H 0.68633 -2.93825 4.95498 H -0.15938 -4.31317 4.27218 C -0.77712 2.42455 4.11475 H 0.11940 3.00278 4.33441 H -1.54389 3.12117 3.77876 C 0.35219 2.47359 0.88277 H 1.15657 3.07207 1.30737 H -0.47137 3.14634 0.64719 C -1.19171 -3.56208 -2.35952 H -0.60157 -3.82962 -3.23419 H -2.09587 -4.17312 -2.37307 C 0.60666 -6.14069 -1.00058 H 1.37416 -6.07366 -1.77397 H -0.23429 -6.68996 -1.42045 Neutral pHE4 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1229.214229 Hartree Sum of electronic and zero-point Energies= -1228.767145 Sum of electronic and thermal Energies= -1228.745148 Sum of electronic and thermal Enthalpies= -1228.744203 Sum of electronic and thermal Free Energies= -1228.817757 Coordinates in ang: C 0.18520 0.08517 1.17049 C -0.75000 0.07198 3.70557 C -0.18106 -1.13959 1.72208 C 0.09635 1.29560 1.85142 C -0.38915 1.29012 3.14007 C -0.67352 -1.14855 3.04685 C -0.04060 -2.39070 0.93724 C 0.14281 -4.73978 -0.61368 C -0.75990 -2.57092 -0.24062 C 0.80792 -3.43820 1.36125 C 0.86272 -4.57476 0.56450 C -0.67870 -3.71501 -1.02847 O 1.65732 -5.65597 0.84921 O -1.19229 0.20536 4.99725 C -1.39967 1.60930 5.23751 H -1.09052 1.81999 6.25703 H -2.46610 1.81716 5.14060 C 1.27535 -6.71964 -0.04218 H 0.63860 -7.41206 0.50990 H 2.17963 -7.23898 -0.34568 O 0.68468 0.23291 -0.09325 O -1.64795 -1.65792 -0.73726 C -1.98075 -2.06581 -2.07599 H -1.38572 -1.47014 -2.76931 H -3.03272 -1.84876 -2.23633 C 1.19798 1.57287 -0.20358 H 2.28215 1.53149 -0.09018 H 0.96171 1.93686 -1.19914 C -1.10938 -2.40318 3.76414 H -1.50706 -3.12505 3.05067 C -0.58886 2.36916 4.17030 H 0.36749 2.72225 4.56240 H -1.12928 3.23728 3.79602 C 0.55306 2.39354 0.92901 H 1.26436 3.08090 1.38458 H -0.29170 2.98568 0.57027 C -1.62733 -3.56093 -2.18698 H -1.18287 -3.79904 -3.15226 H -2.50700 -4.19692 -2.06516 C 0.50739 -6.07225 -1.21087 H 1.13871 -5.94916 -2.09349 H -0.35395 -6.66949 -1.50662 C 1.64844 -3.37236 2.61368 H 2.56710 -3.92746 2.42683 H 1.93823 -2.34140 2.81708 H -1.92692 -2.13295 4.43189 C 0.96857 -3.97757 3.85845 H 1.74636 -4.28529 4.56098 H 0.45131 -4.89192 3.55892 C -0.00108 -3.06263 4.60989 H -0.47390 -3.65470 5.39672 H 0.55954 -2.27498 5.11853 pHE4 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1229.035091 Hartree Sum of electronic and zero-point Energies= -1228.587227 Sum of electronic and thermal Energies= -1228.564950 Sum of electronic and thermal Enthalpies= -1228.564006 Sum of electronic and thermal Free Energies= -1228.639857 Coordinates in ang: C 0.17125 0.07805 1.18091 C -0.76371 0.08268 3.68967 C -0.19615 -1.17983 1.74336 C 0.06142 1.32868 1.84472 C -0.40526 1.33024 3.11611 C -0.68440 -1.17715 3.03859 C -0.02563 -2.41461 0.95552 C 0.17805 -4.73696 -0.61171 C -0.69890 -2.55892 -0.25429 C 0.79006 -3.47888 1.40999 C 0.85569 -4.60226 0.59958 C -0.60775 -3.69639 -1.05001 O 1.61902 -5.69517 0.89688 O -1.20621 0.20380 4.92206 C -1.19112 1.60597 5.33175 H -0.55954 1.65934 6.21172 H -2.21176 1.85672 5.59940 C 1.27008 -6.74101 -0.03247 H 0.61775 -7.44507 0.48372 H 2.18618 -7.24983 -0.31580 O 0.68764 0.19034 -0.01796 O -1.54513 -1.62340 -0.76361 C -1.85803 -2.01338 -2.11914 H -1.25186 -1.40465 -2.78922 H -2.90710 -1.79315 -2.28846 C 0.97062 1.59045 -0.32254 H 2.03183 1.64566 -0.53965 H 0.40245 1.82819 -1.21510 C -1.15010 -2.40481 3.77320 H -1.53852 -3.12671 3.05660 C -0.65078 2.40503 4.13154 H 0.26491 2.93949 4.38058 H -1.37327 3.13770 3.77493 C 0.54768 2.39985 0.91621 H 1.38225 2.95476 1.34191 H -0.23912 3.11550 0.68181 C -1.50465 -3.50809 -2.24394 H -1.01708 -3.72742 -3.19225 H -2.39049 -4.14207 -2.17491 C 0.54370 -6.06648 -1.21219 H 1.20038 -5.93677 -2.07447 H -0.31788 -6.64496 -1.54137 C 1.60360 -3.43360 2.68138 H 2.50725 -4.01615 2.51052 H 1.92736 -2.41290 2.88859 H -1.97818 -2.11095 4.41577 C 0.88805 -4.01365 3.91751 H 1.64632 -4.33603 4.63315 H 0.34817 -4.91392 3.61769 C -0.06178 -3.06446 4.64763 H -0.56389 -3.62658 5.43594 H 0.51157 -2.28267 5.15046 Neutral pHE5 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1268.494547 Hartree Sum of electronic and zero-point Energies= -1268.017993 Sum of electronic and thermal Energies= -1267.994748 Sum of electronic and thermal Enthalpies= -1267.993804 Sum of electronic and thermal Free Energies= -1268.070135 Coordinates in ang: C 1.52509 0.33274 -0.57941 C 0.39538 1.16651 -0.73570 C -0.95334 0.77505 -0.24154 C -1.71769 -0.21546 -0.89980 C -1.20745 -0.94114 -2.12005 C -0.08909 -2.83969 -0.70994 C 1.50385 -0.96137 0.19575 C 0.56288 2.37382 -1.40501 C -1.51479 1.41046 0.85978 C 2.72211 0.77734 -1.12690 C -2.98516 -0.47792 -0.39648 C -2.78332 1.12174 1.35326 C 1.77443 2.79960 -1.94163 C -0.93873 -2.44149 -1.91953 H -0.46281 -2.81755 -2.82945 H -1.89607 -2.95799 -1.83695 H -1.94171 -0.84131 -2.92298 H -0.30052 -0.45281 -2.46830 C 1.33903 -2.27155 -0.61665 H 2.45306 -1.02183 0.72817 H 0.72421 -0.91542 0.95578 H 1.95574 -3.02543 -0.12475 H 1.76516 -2.14598 -1.61470 H -0.01897 -3.92994 -0.72599 H -0.62818 -2.59371 0.20820 C -3.53282 0.16064 0.71132 C 2.87470 1.98307 -1.80299 O -0.87587 2.37488 1.58927 O -0.45209 3.26120 -1.63746 O -3.83921 -1.40076 -0.94466 O 3.89256 0.06638 -1.05313 C -5.12991 -1.20823 -0.33652 C 4.95519 0.94134 -1.47488 C 4.30092 2.08542 -2.27277 C 1.54800 4.11408 -2.63870 C 0.14215 4.47800 -2.12525 C -1.84946 2.96389 2.47110 C -3.01835 1.96605 2.57684 C -4.89554 -0.42434 0.96860 H -5.66853 0.32458 1.13455 H -4.88433 -1.08252 1.84011 H -5.57523 -2.18735 -0.18694 H -5.75041 -0.63907 -1.02999 H -2.95919 1.36734 3.48843 H -3.98230 2.47289 2.58073 H -2.17726 3.90686 2.03179 H -1.35808 3.16747 3.41795 H 0.19819 5.18400 -1.29572 H -0.51403 4.88329 -2.88985 H 1.56501 3.99418 -3.72419 H 2.28117 4.87772 -2.38287 H 5.66101 0.35114 -2.05181 H 5.45646 1.32135 -0.58369 H 4.76515 3.04636 -2.05598 H 4.37441 1.92144 -3.35010 pHE5 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1268.314595 Hartree Sum of electronic and zero-point Energies= -1267.837212 Sum of electronic and thermal Energies= -1267.813707 Sum of electronic and thermal Enthalpies= -1267.812763 Sum of electronic and thermal Free Energies= -1267.890878 Coordinates in ang: C 1.50409 0.31664 -0.55669 C 0.39710 1.13314 -0.69379 C -0.95802 0.75644 -0.22650 C -1.71010 -0.25050 -0.87633 C -1.20497 -0.98378 -2.09455 C -0.05707 -2.87935 -0.71018 C 1.51028 -0.98771 0.19119 C 0.58556 2.38673 -1.34138 C -1.52541 1.42965 0.84787 C 2.72391 0.79676 -1.11067 C -2.98050 -0.49613 -0.37636 C -2.79771 1.15246 1.33729 C 1.81733 2.85365 -1.87312 C -0.93862 -2.48405 -1.89656 H -0.48935 -2.86242 -2.81828 H -1.89521 -2.99552 -1.78695 H -1.94567 -0.88196 -2.89045 H -0.30105 -0.49997 -2.45933 C 1.36153 -2.28467 -0.64958 H 2.45886 -1.03695 0.72398 H 0.72709 -0.95650 0.94597 H 2.01213 -3.02531 -0.18573 H 1.75745 -2.13206 -1.65577 H 0.03568 -3.96676 -0.73714 H -0.57720 -2.65193 0.22312 C -3.53621 0.17329 0.71313 C 2.89787 2.04416 -1.76402 O -0.88863 2.41084 1.54489 O -0.39534 3.23675 -1.52380 O -3.83067 -1.42226 -0.91165 O 3.83750 0.10310 -1.04294 C -5.12765 -1.22291 -0.31341 C 4.93532 0.84410 -1.66078 C 4.33192 2.16015 -2.18465 C 1.58717 4.20587 -2.47673 C 0.09245 4.44028 -2.19312 C -1.86204 3.01982 2.42246 C -3.04155 2.03383 2.53274 C -4.90328 -0.40003 0.96923 H -5.67289 0.35780 1.10516 H -4.90151 -1.03036 1.86055 H -5.56280 -2.20140 -0.13613 H -5.74842 -0.68141 -1.02731 H -3.00375 1.45933 3.46008 H -4.00025 2.54896 2.50491 H -2.17290 3.96211 1.97228 H -1.36875 3.22250 3.36772 H -0.09735 5.26383 -1.51322 H -0.51116 4.55757 -3.08622 H 1.80066 4.20905 -3.54483 H 2.21145 4.96805 -2.01311 H 5.33448 0.20422 -2.43983 H 5.68118 0.98488 -0.88593 H 4.81289 3.03051 -1.74106 H 4.42755 2.24543 -3.26611 Neutral pHE6 geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1307.783032 Hartree Sum of electronic and zero-point Energies= -1307.276867 Sum of electronic and thermal Energies= -1307.252569 Sum of electronic and thermal Enthalpies= -1307.251625 Sum of electronic and thermal Free Energies= -1307.330167 Coordinates in ang: C 1.78084 -0.65221 0.27931 C 0.59956 -1.40480 0.47395 C -0.52835 -1.43079 -0.50722 C -1.68905 -0.63324 -0.37881 C -1.86351 0.39850 0.70967 C 0.72421 2.23157 0.25590 C 1.97890 0.28403 -0.88867 C 0.51994 -2.20802 1.60727 C -0.46997 -2.32736 -1.56974 C 2.78332 -0.78850 1.23269 C -2.69343 -0.81962 -1.32167 C -1.48665 -2.49151 -2.50481 C 1.53459 -2.32177 2.55204 C -1.82561 1.85317 0.19722 H -2.82507 0.24000 1.20195 H -1.09938 0.24969 1.46962 C 1.97754 1.77588 -0.49510 H 2.93567 0.06306 -1.36592 H 1.21019 0.09371 -1.63462 H 2.10104 2.36994 -1.40503 H 2.85398 1.96840 0.12419 C -0.56178 2.21517 -0.58656 H -2.69762 2.01634 -0.43657 H -1.93344 2.52170 1.05603 H -0.69921 3.19391 -1.05189 H -0.45965 1.50876 -1.41159 H 0.60441 1.59543 1.13401 H 0.88767 3.24008 0.64260 C -2.61994 -1.71929 -2.37921 C 2.68868 -1.59505 2.36127 O 0.60075 -3.14421 -1.81267 O -0.57170 -2.97250 1.91788 O -3.88476 -0.13959 -1.29585 O 3.99337 -0.14734 1.14851 C -4.55633 -0.39582 -2.54279 H -4.40739 0.46780 -3.19213 H -5.61679 -0.49987 -2.33291 C -3.91381 -1.65969 -3.14575 H -3.78036 -1.56920 -4.22274 H -4.51998 -2.54985 -2.96448 C -1.04511 -3.51903 -3.51192 H -0.79215 -3.05380 -4.46720 H -1.79142 -4.28698 -3.71000 C 0.19785 -4.09997 -2.81098 H 1.04202 -4.26053 -3.47506 H -0.03863 -5.03747 -2.30619 C -0.19256 -3.85185 2.99276 H 0.01651 -4.83463 2.56841 H -1.03901 -3.93261 3.66837 C 1.06785 -3.24881 3.64189 H 0.83048 -2.69825 4.55487 H 1.79337 -4.01772 3.90333 C 3.98667 -1.50887 3.11825 H 4.56674 -2.42788 3.01050 H 3.86010 -1.32557 4.18421 C 4.66224 -0.31818 2.41145 H 4.54019 0.60016 2.98711 H 5.71853 -0.46937 2.20937 pHE6 cation radical geometry B1LYP-40/6-31G(d), pcm(dichloromethane) Electronic Energy = -1307.602474 Hartree Sum of electronic and zero-point Energies= -1307.095577 Sum of electronic and thermal Energies= -1307.070970 Sum of electronic and thermal Enthalpies= -1307.070026 Sum of electronic and thermal Free Energies= -1307.151088 C 1.79716 -0.65235 0.28776 C 0.60252 -1.38106 0.48889 C -0.52582 -1.38854 -0.48541 C -1.65770 -0.60245 -0.37575 C -1.85735 0.44885 0.68089 C 0.75828 2.23927 0.23937 C 2.01574 0.27883 -0.88004 C 0.49224 -2.18496 1.61685 C -0.48303 -2.32009 -1.56019 C 2.78886 -0.80882 1.24712 C -2.68080 -0.81521 -1.34667 C -1.50951 -2.50887 -2.52418 C 1.50119 -2.31868 2.56493 C -1.79597 1.89356 0.13519 H -2.83304 0.29780 1.14436 H -1.11146 0.30552 1.45737 C 2.02015 1.77114 -0.48869 H 2.97625 0.04826 -1.34330 H 1.25807 0.09687 -1.64093 H 2.16636 2.36154 -1.39685 H 2.88666 1.95479 0.14631 C -0.51259 2.23233 -0.62668 H -2.65605 2.06127 -0.51322 H -1.91319 2.56756 0.98615 H -0.63381 3.21024 -1.09583 H -0.40165 1.52693 -1.45265 H 0.61935 1.61039 1.12002 H 0.92246 3.24796 0.62285 C -2.62565 -1.75017 -2.41111 C 2.66874 -1.61542 2.37634 O 0.54207 -3.11377 -1.75663 O -0.61511 -2.92403 1.91074 O -3.80759 -0.14175 -1.32494 O 4.00575 -0.19066 1.17172 C -4.67006 -0.55824 -2.42993 H -4.85124 0.33034 -3.02480 H -5.59842 -0.89284 -1.98087 C -3.90789 -1.66388 -3.18261 H -3.73659 -1.39984 -4.22492 H -4.44791 -2.60950 -3.16607 C -1.07193 -3.57979 -3.47604 H -1.01120 -3.20865 -4.49816 H -1.75780 -4.42564 -3.47233 C 0.31248 -3.96350 -2.92345 H 1.12846 -3.76496 -3.60947 H 0.37322 -4.98702 -2.57023 C -0.27450 -3.80061 3.00754 H -0.10974 -4.79724 2.59901 H -1.12580 -3.82935 3.68035 C 1.00864 -3.23769 3.65024 H 0.79458 -2.68556 4.56722 H 1.71266 -4.02923 3.90137 C 3.96209 -1.55211 3.14249 H 4.51939 -2.48571 3.04530 H 3.82761 -1.36017 4.20560 C 4.67312 -0.38233 2.43534 H 4.58112 0.54047 3.00803 H 5.72269 -0.56768 2.22916