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Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics

[Image: see text] We demonstrate that a conditional wave function theory enables a unified and efficient treatment of the equilibrium structure and nonadiabatic dynamics of correlated electron–ion systems. The conditional decomposition of the many-body wave function formally recasts the full interac...

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Autores principales: Albareda, Guillermo, Lively, Kevin, Sato, Shunsuke A., Kelly, Aaron, Rubio, Angel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8675140/
https://www.ncbi.nlm.nih.gov/pubmed/34752108
http://dx.doi.org/10.1021/acs.jctc.1c00772
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author Albareda, Guillermo
Lively, Kevin
Sato, Shunsuke A.
Kelly, Aaron
Rubio, Angel
author_facet Albareda, Guillermo
Lively, Kevin
Sato, Shunsuke A.
Kelly, Aaron
Rubio, Angel
author_sort Albareda, Guillermo
collection PubMed
description [Image: see text] We demonstrate that a conditional wave function theory enables a unified and efficient treatment of the equilibrium structure and nonadiabatic dynamics of correlated electron–ion systems. The conditional decomposition of the many-body wave function formally recasts the full interacting wave function of a closed system as a set of lower-dimensional (conditional) coupled “slices”. We formulate a variational wave function ansatz based on a set of conditional wave function slices and demonstrate its accuracy by determining the structural and time-dependent response properties of the hydrogen molecule. We then extend this approach to include time-dependent conditional wave functions and address paradigmatic nonequilibrium processes including strong-field molecular ionization, laser-driven proton transfer, and nuclear quantum effects induced by a conical intersection. This work paves the road for the application of conditional wave function theory in equilibrium and out-of-equilibrium ab initio molecular simulations of finite and extended systems.
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spelling pubmed-86751402021-12-17 Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics Albareda, Guillermo Lively, Kevin Sato, Shunsuke A. Kelly, Aaron Rubio, Angel J Chem Theory Comput [Image: see text] We demonstrate that a conditional wave function theory enables a unified and efficient treatment of the equilibrium structure and nonadiabatic dynamics of correlated electron–ion systems. The conditional decomposition of the many-body wave function formally recasts the full interacting wave function of a closed system as a set of lower-dimensional (conditional) coupled “slices”. We formulate a variational wave function ansatz based on a set of conditional wave function slices and demonstrate its accuracy by determining the structural and time-dependent response properties of the hydrogen molecule. We then extend this approach to include time-dependent conditional wave functions and address paradigmatic nonequilibrium processes including strong-field molecular ionization, laser-driven proton transfer, and nuclear quantum effects induced by a conical intersection. This work paves the road for the application of conditional wave function theory in equilibrium and out-of-equilibrium ab initio molecular simulations of finite and extended systems. American Chemical Society 2021-11-09 2021-12-14 /pmc/articles/PMC8675140/ /pubmed/34752108 http://dx.doi.org/10.1021/acs.jctc.1c00772 Text en © 2021 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 Albareda, Guillermo
Lively, Kevin
Sato, Shunsuke A.
Kelly, Aaron
Rubio, Angel
Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title_full Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title_fullStr Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title_full_unstemmed Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title_short Conditional Wave Function Theory: A Unified Treatment of Molecular Structure and Nonadiabatic Dynamics
title_sort conditional wave function theory: a unified treatment of molecular structure and nonadiabatic dynamics
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8675140/
https://www.ncbi.nlm.nih.gov/pubmed/34752108
http://dx.doi.org/10.1021/acs.jctc.1c00772
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