On-the-fly CASPT2 surface hopping dynamics

Abstract: We report the development of programs for on-the-fly surface hopping dynamics simulations in the gas and condensed phases on the potential energy surfaces computed by multistate multireference perturbation theory (XMS-CASPT2) with full internal contraction. On-the-fly nonadiabatic dynamics simulations are made possible by improving the algorithm for XMS-CASPT2 nuclear energy gradient and derivative coupling evaluation. The program is interfaced to a surface hopping dynamics program, Newton-X, and a classical molecular dynamics package, tinker, to realize such simulations. On-the-fly XMS-CASPT2 surface-hopping dynamics simulations of 9H-adenine and an anionic GFP model chromophore (para-hydroxybenzilideneimidazolin-5-one) in water are presented to demonstrate the applicability of our program to sizable systems. Our program is implemented in the bagel package, which is publicly available under the GNU General Public License.