Trajectory Surface Hopping Approach to Condensed-Phase Nonradiative Relaxation Dynamics Using Divide-and-Conquer Spin-Flip Time-Dependent Density-Functional Tight Binding.

Nonradiative relaxation of excited molecules is central to many crucial issues in photochemistry. Condensed phases are typical contexts in which such problems are considered, and the nonradiative relaxation dynamics are expected to be significantly affected by interactions with the environment, for example, a solvent. We developed a nonadiabatic molecular dynamics simulation technique that can treat the nonradiative relaxation and explicitly include the environment in the calculations without a heavy computational burden. Specifically, we combined trajectory surface hopping with Tully's fewest-switches algorithm, a tight-binding approximated version of spin-flip time-dependent density-functional theory, and divide-and-conquer (DC) spatial fragmentation scheme. Numerical results showed that this method can treat systems with thousands of atoms within reasonable computational resources, and the error arising from DC fragmentation is negligibly small. Using this method, we obtained molecular insights into the solvent dependence of the photoexcited-state dynamics of trans-azobenzene, which demonstrate the importance of the environment for condensed-phase nonradiative relaxation.