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Published April 7, 2022 | Accepted Version + Published + Supplemental Material
Journal Article Open

Equilibrium–nonequilibrium ring-polymer molecular dynamics for nonlinear spectroscopy

Abstract

Two-dimensional Raman and hybrid terahertz-Raman spectroscopic techniques provide invaluable insight into molecular structures and dynamics of condensed-phase systems. However, corroborating experimental results with theory is difficult due to the high computational cost of incorporating quantum-mechanical effects in the simulations. Here, we present the equilibrium–nonequilibrium ring-polymer molecular dynamics (RPMD), a practical computational method that can account for nuclear quantum effects on the two-time response function of nonlinear optical spectroscopy. Unlike a recently developed approach based on the double Kubo transformed (DKT) correlation function, our method is exact in the classical limit, where it reduces to the established equilibrium-nonequilibrium classical molecular dynamics method. Using benchmark model calculations, we demonstrate the advantages of the equilibrium–nonequilibrium RPMD over classical and DKT-based approaches. Importantly, its derivation, which is based on the nonequilibrium RPMD, obviates the need for identifying an appropriate Kubo transformed correlation function and paves the way for applying real-time path-integral techniques to multidimensional spectroscopy.

Additional Information

© 2022 Author(s). Published under an exclusive license by AIP Publishing. Submitted: 2 February 2022; Accepted: 15 March 2022; Published Online: 7 April 2022. The authors thank Kenneth A. Jung, Roman Korol, and Jorge L. Rosa-Raíces for helpful discussions. T.B. acknowledges financial support from the Swiss National Science Foundation through the Early Postdoc Mobility Fellowship (Grant No. P2ELP2-199757). G.A.B. and T.F.M. gratefully acknowledge support from the National Science Foundation Chemical Structure, Dynamics and Mechanisms program (Grant No. CHE-1665467). The computations presented here were conducted in the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. Data Availability: The data that support the findings of this study are available from the corresponding author upon reasonable request. The authors have no conflicts to disclose.

Attached Files

Published - 131102_1_online.pdf

Accepted Version - 2111-02436.pdf

Supplemental Material - sm.pdf

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Additional details

Created:
October 9, 2023
Modified:
October 24, 2023