Geometry Relaxation of Photoexcited States in Conjugated Molecules

The random phase approximation combined with semiempirical Hamiltonians is applied to compute and analyze electronic structure and excited state adiabatic potentials of several conjugated molecules. Calculated excited state energies and parameters of molecular adiabatic surfaces characterize the coupled dynamics of vibrational and electronic degrees of freedom. The analysis identifies the specific torsional and bond-stretching nuclear motions that dominate the excited state relaxation and lead to self-localized excitations. This approach is an inexpensive and numerically efficient method of computing molecular excited state adiabatic surfaces and modeling femto-to-pico second time-dependent photoexcitation processes along chosen trajectories.