Large Second-Order Optical Nonlinearities in Open-Shell Chromophores. Planar Metal Complexes and Organic Radical Ion Aggregates

摘要: Attempts to discover molecular chromophores with large hyperpolarizabilities have largely focused on closed-shell organic species. This contribution explores the use of sum over states (SOS) perturbation theory and computationally efficient intermediate neglect differential overlap (INDO) model Hamiltonian, combined single configuration interaction (SCI) techniques, calculate frequency-dependent quadratic both coordination complexes radical ion chromophore aggregates having open-shell doublet ground state electronic structures. The correct evaluation lowest-lying excited has been tested by comparison experimental optical spectra. In cases considered here, INDO/SCI-SOS method provides a good description linear transitions an adequate prediction second-order nonlinearity. It is seen that larger nonlinearities systems states, as compared those hav...