Path Integral Simulations of Condensed-Phase Vibrational Spectroscopy

2024/06/28 by Stuart C. Althorpe · 25 citations
Environmental Science · Physics and Astronomy · #Climate variability and models #Computational physics #Computer science #Delocalized electron #Feynman diagram #Granularity #Materials science #Molecular dynamics #Molecular physics #Path integral formulation #Phase (matter) #Physics #Quantum #Quantum mechanics #Quantum, superfluid, helium dynamics #Spectral line #Spectroscopy #Spectroscopy and Quantum Chemical Studies #Statistical physics #Thermal #Thermodynamics

paper · doi:10.1146/annurev-physchem-090722-124705

published in Annual Review of Physical Chemistry 75(1), 397-420 (Annual Reviews)

openalex publication_date 2024/06/28 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

Recent theoretical and algorithmic developments have improved the accuracy with which path integral dynamics methods can include nuclear quantum effects in simulations of condensed-phase vibrational spectra. Such methods are now understood to be approximations to the delocalized classical Matsubara dynamics of smooth Feynman paths, which dominate the dynamics of systems such as liquid water at room temperature. Focusing mainly on simulations of liquid water and hexagonal ice, we explain how the recently developed quasicentroid molecular dynamics (QCMD), fast-QCMD, and temperature-elevated path integral coarse-graining simulations (Te PIGS) methods generate classical dynamics on potentials of mean force obtained by averaging over quantum thermal fluctuations. These new methods give very close agreement with one another, and the Te PIGS method has recently yielded excellent agreement with experimentally measured vibrational spectra for liquid water, ice, and the liquid-air interface. We also discuss the limitations of such methods.

Citations

• Reversible multiple time scale molecular dynamics
• Ring-Polymer Molecular Dynamics: Quantum Effects in Chemical Dynamics from Classical Trajectories in an Extended Phase Space
• Path integrals in the theory of condensed helium

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• Trotter simulation of vibrational Hamiltonians on a quantum computer
• h-CMD: An efficient hybrid fast centroid and quasi-centroid molecular dynamics method for the simulation of vibrational spectra

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• h-CMD: An efficient hybrid fast centroid and quasi-centroid molecular dynamics method for the simulation of vibrational spectra