Exact quantum dynamics developments for floppy molecular systems and complexes

TL;DR

This paper reviews advanced quantum nuclear motion methods for accurately modeling complex molecular motions, addressing computational challenges and providing detailed solutions for high-dimensional, large-amplitude quantum systems.

Contribution

It offers a comprehensive review of current methodologies, identifies bottlenecks, and discusses solution strategies for solving the nuclear Schrödinger equation in complex molecular systems.

Findings

Highlights technical details and computational results.

Analyzes limiting models and spectroscopic concepts.

Provides numerical examples illustrating methodology.

Abstract

Molecular rotation, vibration, internal rotation, isomerization, tunneling, intermolecular dynamics of weakly and strongly interacting systems, intra-to-inter-molecular energy transfer, hindered rotation and hindered translation over surfaces are important types of molecular motions. Their fundamentally correct and detailed description can be obtained by solving the nuclear Schr\"odinger equation on a potential energy surface. Many of the chemically interesting processes involve quantum nuclear motions which are `delocalized' over multiple potential energy wells. These `large-amplitude' motions in addition to the high dimensionality of the vibrational problem represent challenges to the current (ro)vibrational methodology. A review of the quantum nuclear motion methodology is provided, current bottlenecks of solving the nuclear Schr\"odinger equation are identified, and solution strategies are reviewed. Technical details, computational results, and analysis of these results in terms of limiting models and spectroscopically relevant concepts are highlighted for selected numerical examples.