Reactive path integral quantum simulations of molecules solvated in superfluid helium

Abstract

A hybrid ab initio path integral molecular dynamics/bosonic path integral Monte Carlo simulation method has been developed, implemented and tested, which allows for the reactive simulations of molecules, clusters or complexes solvated by superfluid 4He. The simulation takes into account “on-the-fly” the electronic structure and thus the chemical reactivity of the solutes, in conjunction with the Bose–Einstein statistics, and thus the superfluid character of this peculiar solvent. This enables investigations into cryochemical reactions taking place in helium nanodroplets, such as those used in helium nanodroplet isolation (HENDI) spectroscopy.