Antisymmetric Transition Polarizability Induced by Intermodular Charge-Transfer Interactions

摘要

Antisymmetric vibrational transition polarizability induced by intermolecular charge-transfer interactions is proposed and studied by using group theory,especially time-reversal symmetry,and Milliken's theory of charge-transfer complexes.The results show that under the Born-Oppenheirner(B-O)approximation,the antisymmetric transition polarizability of even-electron systems with real represention ground states is zero.But when a donor-acceptor complex is formed by the partial or complete transfer of an electron from donor to acceptor,the acceptor(donor)can have nonzero antisymmetric transition polarizability.Thus charge-transfer-induced antisymmetric light scattering from the interaction even-electron systems,especially charge-transfer complexes,can exist,which is characteristic of charge-transfer interaction and processes.The theoretical results are associated qualitatively with anomalous Raman polarization experiment of anthracene anion-Na~+ ion complex and with the complexation enhancements of depolarization ratios of some substituted pyridineBri complexes.The connections of the charge-transfer-induced antisymmetric Raman tensors to sum-frequency vibrational spectroscopy(SFVS)in chiral solutions and in photoionization processes have been discussed.