The generalized quantum master equation (GQME) approach provides a powerful general-purpose framework for simulating the inherently quantum mechanical dynamics of a subset of electronic reduced density matrix elements of interest in complex molecular systems. Previous studies have found that combining the GQME approach with quasiclassical mapping Hamiltonian (QC/MH) methods can dramatically improve the accuracy of electronic populations obtained via those methods. In this paper, we perform a complimentary study of the advantages offered by the GQME approach for simulating the dynamics of electronic coherences, which play a central role in optical spectroscopy, quantum information science, and quantum technology. To this end, we focus on cases where the electronic coherences predicted for the spin-boson benchmark model by direct application of various QC/MH methods are inaccurate. We find that similar to the case of electronic populations, combining the QC/MH methods with the GQME approach can dramatically improve the accuracy of the electronic coherences obtained via those methods. We also provide a comprehensive analysis of how the performance of GQMEs depends on the choice of projection operator and electronic basis and show that the accuracy and feasibility of the GQME approach can benefit from casting the GQME in terms of the eigen-basis of the observable of interest.
Skip Nav Destination
Article navigation
28 October 2024
Research Article|
October 22 2024
Combining the generalized quantum master equation approach with quasiclassical mapping Hamiltonian methods to simulate the dynamics of electronic coherences Available to Purchase
Special Collection:
Algorithms and Software for Open Quantum System Dynamics
Yudan Liu
;
Yudan Liu
(Conceptualization, Formal analysis, Software, Visualization, Writing – original draft, Writing – review & editing)
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
Search for other works by this author on:
Ellen Mulvihill
;
Ellen Mulvihill
(Conceptualization, Formal analysis, Methodology, Software, Writing – review & editing)
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
Search for other works by this author on:
Eitan Geva
Eitan Geva
a)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – review & editing)
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
Yudan Liu
Conceptualization, Formal analysis, Software, Visualization, Writing – original draft, Writing – review & editing
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
Ellen Mulvihill
Conceptualization, Formal analysis, Methodology, Software, Writing – review & editing
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
Eitan Geva
Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – review & editing
a)
Department of Chemistry, University of Michigan
, Ann Arbor, Michigan 48109, USA
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 161, 164101 (2024)
Article history
Received:
August 07 2024
Accepted:
October 04 2024
Citation
Yudan Liu, Ellen Mulvihill, Eitan Geva; Combining the generalized quantum master equation approach with quasiclassical mapping Hamiltonian methods to simulate the dynamics of electronic coherences. J. Chem. Phys. 28 October 2024; 161 (16): 164101. https://doi.org/10.1063/5.0232462
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
Related Content
Simulating the dynamics of electronic observables via reduced-dimensionality generalized quantum master equations
J. Chem. Phys. (January 2022)
Combining the mapping Hamiltonian linearized semiclassical approach with the generalized quantum master equation to simulate electronically nonadiabatic molecular dynamics
J. Chem. Phys. (August 2019)
Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions
J. Chem. Phys. (July 2024)
Efficient formulation of multitime generalized quantum master equations: Taming the cost of simulating 2D spectra
J. Chem. Phys. (January 2024)