Resolving Photoinduced Femtosecond Three-Dimensional Solute–Solvent Dynamics through Surface Hopping Simulations
Severin Polonius, David Lehrner, Leticia González, Sebastian Mai
Abstract
7171-7186]. This method provides solvent-embedded, nonadiabatically coupled potential energy surfaces while scaling similarly to MM force fields. Here, we employ TSH with LVC/MM to unravel the photoinduced dynamics of two small thiocarbonyl compounds solvated in water. We describe how to estimate the number of trajectories required to produce nearly noise-free three-dimensional solvent distribution functions and present an analysis based on approximately 10,000 trajectories propagated for 3 ps. In the electronic ground state, both molecules exhibit in-plane hydrogen bonds to the sulfur atom. Shortly after excitation, these bonds are broken and reform perpendicular to the molecular plane on timescales that differ by an order of magnitude due to steric effects. We also show that the solvent relaxation dynamics is coupled to the electronic dynamics, including intersystem crossing. These findings are relevant to advance the understanding of the coupled solute-solvent dynamics of solvated photoexcited molecules, e.g., biologically relevant thio-nucleobases.