Exact quantum dynamics developments for floppy molecular systems and complexes

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 Schrödinger 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 Schrödinger 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.

References in corpus (6)

• Simulating chemistry using quantum computers
• Towards breaking the curse of dimensionality in (ro)vibrational computations of molecular systems with multiple large-amplitude motions
• Rovibrational quantum dynamical computations for deuterated isotopologues of the methane-water dimer
• Variational vibrational states of HCOOH
• Fingerprint region of the formic acid dimer: variational vibrational computations in curvilinear coordinates
• CH${}_4\cdot$F${}^{-}$ revisited: Full-dimensional ab initio potential energy surface and variational vibrational states