Direct dynamics simulations of photoexcited charge-transfer-to-solvent states of the I−(H2O)6 cluster

Direct molecular dynamics simulations have been carried out to understand the relaxation dynamics of photoexcited charge-transfer-to-solvent (CTTS) states for the I−(H2O)6 cluster and the subsequent excess electron stabilization dynamics by solvent molecules. Due to a small singlet-triplet splitting, the lowest triplet potential energy surface at the B3LYP-level calculations was used to model the CTTS singlet excited-state surface. Two book-type structures, which correspond to the lowest ground-state minimum-energy geometries, were vertically excited with the initial kinetic energy being zero. Although these two structures have a very similar geometry, it was found that the excess electron localization dynamics was totally different.

Graphical abstractDirect molecular dynamics simulations have been carried out to understand the relaxation dynamics of photoexcited charge-transfer-to-solvent (CTTS) states for the I−(H2O)6 cluster and the subsequent excess electron stabilization dynamics by solvent molecules.Download full-size image