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Equilibrium–nonequilibrium ring-polymer molecular dynamics for nonlinear spectroscopy

Begušić, Tomislav and Tao, Xuecheng and Blake, Geoffrey A. and Miller, Thomas F., III (2022) Equilibrium–nonequilibrium ring-polymer molecular dynamics for nonlinear spectroscopy. Journal of Chemical Physics, 156 (13). Art. No. 131102. ISSN 0021-9606. doi:10.1063/5.0087156.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Begušić, Tomislav0000-0002-7942-4134
Tao, Xuecheng0000-0003-2907-3839
Blake, Geoffrey A.0000-0003-0787-1610
Miller, Thomas F., III0000-0002-1882-5380
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.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Swiss National Science Foundation (SNSF)P2ELP2-199757
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:13
Record Number:CaltechAUTHORS:20220223-214612882
Persistent URL:
Official Citation:Tomislav Begušić, Xuecheng Tao, Geoffrey A. Blake, and Thomas F. Miller III, "Equilibrium–nonequilibrium ring-polymer molecular dynamics for nonlinear spectroscopy", J. Chem. Phys. 156, 131102 (2022)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:113566
Deposited By: George Porter
Deposited On:24 Feb 2022 22:13
Last Modified:12 Apr 2022 20:57

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