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Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes

[Image: see text] The interaction of quantum-mechanical systems with a fluctuating thermal environment (bath) is fundamental to molecular mechanics and energy transport/dissipation. Its complete picture requires mode-specific measurements of this interaction and an understanding of its nature. Here,...

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Autores principales: Seliya, Pankaj, Bonn, Mischa, Grechko, Maksim
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10544034/
https://www.ncbi.nlm.nih.gov/pubmed/37728562
http://dx.doi.org/10.1021/acs.jpclett.3c01974
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author Seliya, Pankaj
Bonn, Mischa
Grechko, Maksim
author_facet Seliya, Pankaj
Bonn, Mischa
Grechko, Maksim
author_sort Seliya, Pankaj
collection PubMed
description [Image: see text] The interaction of quantum-mechanical systems with a fluctuating thermal environment (bath) is fundamental to molecular mechanics and energy transport/dissipation. Its complete picture requires mode-specific measurements of this interaction and an understanding of its nature. Here, we present a combined experimental and theoretical study providing detailed insights into the coupling between a high-frequency vibrational two-level system and thermally excited terahertz modes. Experimentally, two-dimensional terahertz-infrared-visible spectroscopy reports directly on the coupling between quantum oscillators represented by CH(3) streching vibrations in liquid dimethyl sulfoxide and distinct low-frequency modes. Theoretically, we present a mixed quantum-classical formalism of the sample response to enable the simultaneous quantum description of high-frequency oscillators and a classical description of the bath. We derive the strength and nature of interaction and find different coupling between CH(3) stretch and low-frequency modes. This general approach enables quantitative and mode-specific analysis of coupled quantum and classical dynamics in complex chemical systems.
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spelling pubmed-105440342023-10-03 Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes Seliya, Pankaj Bonn, Mischa Grechko, Maksim J Phys Chem Lett [Image: see text] The interaction of quantum-mechanical systems with a fluctuating thermal environment (bath) is fundamental to molecular mechanics and energy transport/dissipation. Its complete picture requires mode-specific measurements of this interaction and an understanding of its nature. Here, we present a combined experimental and theoretical study providing detailed insights into the coupling between a high-frequency vibrational two-level system and thermally excited terahertz modes. Experimentally, two-dimensional terahertz-infrared-visible spectroscopy reports directly on the coupling between quantum oscillators represented by CH(3) streching vibrations in liquid dimethyl sulfoxide and distinct low-frequency modes. Theoretically, we present a mixed quantum-classical formalism of the sample response to enable the simultaneous quantum description of high-frequency oscillators and a classical description of the bath. We derive the strength and nature of interaction and find different coupling between CH(3) stretch and low-frequency modes. This general approach enables quantitative and mode-specific analysis of coupled quantum and classical dynamics in complex chemical systems. American Chemical Society 2023-09-20 /pmc/articles/PMC10544034/ /pubmed/37728562 http://dx.doi.org/10.1021/acs.jpclett.3c01974 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Seliya, Pankaj
Bonn, Mischa
Grechko, Maksim
Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title_full Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title_fullStr Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title_full_unstemmed Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title_short Experimental Access to Mode-Specific Coupling between Quantum Molecular Vibrations and Classical Bath Modes
title_sort experimental access to mode-specific coupling between quantum molecular vibrations and classical bath modes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10544034/
https://www.ncbi.nlm.nih.gov/pubmed/37728562
http://dx.doi.org/10.1021/acs.jpclett.3c01974
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