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.

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• Variational vibrational states of HCOOH
• Bound and unbound rovibrational states of the methane-argon dimer
• Fingerprint region of the formic acid dimer: variational vibrational computations in curvilinear coordinates
• Simulating electric field interactions with polar molecules using spectroscopic databases
• Hyperfine-resolved rotation-vibration line list of ammonia (NH${}_3$)
• CH${}_4\cdot$F${}^{-}$ revisited: Full-dimensional ab initio potential energy surface and variational vibrational states

Cited by in corpus (11)

• HF trimer: 12D fully coupled quantum calculations of HF-stretch excited intramolecular and intermolecular vibrational states using contracted bases of intramolecular and intermolecular eigenstates
• Computing excited states of molecules using normalizing flows
• Variational Vibrational States of Methanol (12D)
• Vibrational infrared and Raman spectrum of HCOOH from variational computations
• Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states
• Computing excited eigenstates using inexact Lanczos methods and tree tensor network states
• Transferability and interpretability of vibrational normalizing-flow coordinates
• Exact quantum dynamics of methanol: full-dimensional ab initio potential energy surface of spectroscopic quality and variational vibrational states
• Methane dimer rovibrational states and Raman transition moments
• Strong parity-violation effects induced by large-amplitude motions: A quantum-dynamics study of substituted chiral methanols
• Rovibrational computation of H${}_3^{+}$ with permutationally invariant Pekeris coordinates