Semiclassical description of nuclear quantum effects in solvated and condensed phase molecular systems

Abstract

In this perspective we deal with the challenge of investigating nuclear quantum effects in solvated and condensed phase molecular systems in a computationally affordable way. To this end, semiclassical methods are promising theoretical approaches, as we demonstrate through vibrational spectroscopy and reaction kinetics. We show that quantum vibrational features can be found in hydrates of carbonyl compounds and microsolvated amino acids, and we report quantum estimates of the low-temperature reaction rate constant of a unimolecular reaction taking place in a noble-gas matrix. The hallmark of semiclassical methods is their ability to include nuclear quantum effects into classical molecular dynamics simulations. For this reason, unlike other popular methods, semiclassical approaches are able to account also for real-time quantum contributions and are expected to point out the importance of nuclear quantum effects in complex systems for a wider range of chemical properties.