Nonadiabatic Field with Triangle Window Functions on Quantum Phase Space
Recent progress on the coordinate-momentum (CPS) formulation of finite-state quantum systems has revealed that the triangle window function approach is an isomorphic representation of the exact population-population correlation function of the two-state system. We use the triangle window (TW) functi...
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| Published in: | The journal of physical chemistry letters Vol. 15; no. 20; p. 5452 |
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| Main Authors: | , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
23.05.2024
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| ISSN: | 1948-7185, 1948-7185 |
| Online Access: | Get more information |
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| Summary: | Recent progress on the
coordinate-momentum
(CPS) formulation of finite-state quantum systems has revealed that the triangle window function approach is an isomorphic representation of the exact population-population correlation function of the two-state system. We use the triangle window (TW) function and the CPS mapping kernel element to formulate a novel useful representation of discrete electronic degrees of freedom (DOFs). When it is employed with nonadiabatic field (NaF) dynamics, a new variant of the NaF approach (i.e., NaF-TW) is proposed. The NaF-TW expression of the population of any adiabatic state is always positive semidefinite. Extensive benchmark tests of model systems in both the condensed phase and gas phase demonstrate that the NaF-TW approach is able to faithfully capture the dynamical interplay between electronic and nuclear DOFs in a broad region, including where the states remain coupled all the time, as well as where the bifurcation characteristic of nuclear motion is important. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1948-7185 1948-7185 |
| DOI: | 10.1021/acs.jpclett.4c00793 |