A Perspective on the Investigation of Spectroscopy and Kinetics of Complex Molecular Systems with Semiclassical...

In this Perspective we show that semiclassical methods provide a rigorous hierarchical way to study the vibrational spectroscopy and kinetics of complex molecular systems. The time averaged approach to spectroscopy and the semiclassical transition state theory for kinetics, which have been first adopted and then further developed in our group, provide accurate quantum results on rigorous physical grounds and can be applied even when dealing with a large number of degrees of freedom. In spectroscopy, the multiple coherent, divide-and-conquer, and adiabatically switched semiclassical approaches have practically permitted overcoming issues related to the convergence of results. In this Perspective we demonstrate the possibility of studying the semiclassical vibrational spectroscopy of a molecule adsorbed on an anatase (101) surface, a system made of 51 atoms. In kinetics, the semiclassical transition state theory is able to account for anharmonicity and the coupling between the reactive and bound modes. Our group has developed this technique for practical applications involving the study of phenomena like kinetic isotope effect, heavy atom tunneling, and elusive conformer lifetimes. Here, we show that our multidimensional anharmonic quantum approach is able to tackle on-the-fly the thermal kinetic rate constant of a 135 degree-of-freedom system. Overall, semiclassical methods open up the possibility to describe at the quantum mechanical level systems characterized by hundreds of degrees of freedom leading to the accurate spectroscopic and kinetic description of biomolecules and complex molecular systems.