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The dipole moment of ions is not uniquely defined. We chose the center of gravity as the origin of the dipole moment vector which is equivalent to the center of the bridge.
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56
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At the UHF level, all radical cations show strong charge localization at one triarylamine center and an asymmetrical structure. This broken symmetry effect is an inherent artifact of the UHF method.
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57
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+ in MeCN which should lead to a triarylamine localized asymmetric structure according to our experimental observations but remains in fact symmetrically delocalized.
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+ and the conclusions concerning the bridge mediated hopping remain valid because the electronic coupling has only a minor influence on the topology of the PES in these cases.
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61
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+ in MeCN solvent by the COSMO method gave a symmetrical structure similar to the one in the gas phase. We assume this to be an artifact of the AMI parametrization, as explained in footnote 57.
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