Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions

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Hauptverfasser: Sayer, Thomas, Montoya-Castillo, Andrés
Format: Preprint
Veröffentlicht: 2024
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author Sayer, Thomas
Montoya-Castillo, Andrés
author_facet Sayer, Thomas
Montoya-Castillo, Andrés
contents Multitime quantum correlation functions are central objects in physical science, offering a direct link between experimental observables and the dynamics of an underlying model. While experiments such as 2D spectroscopy and quantum control can now measure such quantities, the accurate simulation of such responses remains computationally expensive and sometimes impossible, depending on the system's complexity. A natural tool to employ is the generalized quantum master equation (GQME), which can offer computational savings by extending reference dynamics at a comparatively trivial cost. However, dynamical methods that can tackle chemical systems with atomistic resolution, such as those in the semiclassical hierarchy, often suffer from poor accuracy, limiting the credence one might lend to their results. By combining work on the accuracy-boosting formulation of semiclassical memory kernels with recent work on the multitime GQME, here we show for the first time that one can exploit a multitime semiclassical GQME to dramatically improve both the accuracy of coarse mean-field Ehrenfest dynamics and obtain orders of magnitude efficiency gains.
format Preprint
id arxiv_https___arxiv_org_abs_2405_08983
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions
Sayer, Thomas
Montoya-Castillo, Andrés
Chemical Physics
Quantum Physics
Multitime quantum correlation functions are central objects in physical science, offering a direct link between experimental observables and the dynamics of an underlying model. While experiments such as 2D spectroscopy and quantum control can now measure such quantities, the accurate simulation of such responses remains computationally expensive and sometimes impossible, depending on the system's complexity. A natural tool to employ is the generalized quantum master equation (GQME), which can offer computational savings by extending reference dynamics at a comparatively trivial cost. However, dynamical methods that can tackle chemical systems with atomistic resolution, such as those in the semiclassical hierarchy, often suffer from poor accuracy, limiting the credence one might lend to their results. By combining work on the accuracy-boosting formulation of semiclassical memory kernels with recent work on the multitime GQME, here we show for the first time that one can exploit a multitime semiclassical GQME to dramatically improve both the accuracy of coarse mean-field Ehrenfest dynamics and obtain orders of magnitude efficiency gains.
title Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions
topic Chemical Physics
Quantum Physics
url https://arxiv.org/abs/2405.08983