Ultrastrong coupling limit to quantum mean force Gibbs state for anharmonic environment

The equilibrium state of a quantum system can deviate from the Gibbs state if the system-environment (SE) coupling is not weak. An analytical expression for this mean force Gibbs state (MFGS) is known in the ultrastrong coupling (USC) regime for the Caldeira-Leggett (CL) model that assumes a harmonic environment. Here, we derive analytical expressions for the MFGS in the USC regime for more general SE models. For all the generalized models considered here, we find the USC state to be diagonal in the basis set by the SE interaction, just like in the CL case. While for the generic model considered, the corresponding USC-MFGS is found to alter from the CL result, we do identify a class of models more general than the CL model for which the CL-USC result remains unchanged. We also provide numerical verification for our results. These results provide key tools for the study of strong coupling quantum thermodynamics and several quantum chemistry and biology problems under more realistic SE models, going beyond the CL model.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2024-11-04
DOI
https://doi.org/10.1063/5.0223734
Citations
2
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
0.68
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article

Ultrastrong coupling limit to quantum mean force Gibbs state for anharmonic environment

Prem Kumar, Sibasish Ghosh
2 citations
The Journal of Chemical Physics
Spectroscopy and Quantum Chemical Studies
0.68
article

Ultrastrong coupling limit to quantum mean force Gibbs state for anharmonic environment

Prem Kumar, Sibasish Ghosh
article en
2 citations

Abstract

The equilibrium state of a quantum system can deviate from the Gibbs state if the system-environment (SE) coupling is not weak. An analytical expression for this mean force Gibbs state (MFGS) is known in the ultrastrong coupling (USC) regime for the Caldeira-Leggett (CL) model that assumes a harmonic environment. Here, we derive analytical expressions for the MFGS in the USC regime for more general SE models. For all the generalized models considered here, we find the USC state to be diagonal in the basis set by the SE interaction, just like in the CL case. While for the generic model considered, the corresponding USC-MFGS is found to alter from the CL result, we do identify a class of models more general than the CL model for which the CL-USC result remains unchanged. We also provide numerical verification for our results. These results provide key tools for the study of strong coupling quantum thermodynamics and several quantum chemistry and biology problems under more realistic SE models, going beyond the CL model.

The Journal of Chemical PhysicsVol. 161(17)
Homi Bhabha National Institute (IN), Institute of Mathematical Sciences (IN)
Openalex Percentile: Top 30%
Spectroscopy and Quantum Chemical Studies
0.68
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