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Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms

[Image: see text] In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrödi...

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Autores principales: Grobas Illobre, P., Marsili, M., Corni, S., Stener, M., Toffoli, D., Coccia, E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8515806/
https://www.ncbi.nlm.nih.gov/pubmed/34486881
http://dx.doi.org/10.1021/acs.jctc.1c00211
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author Grobas Illobre, P.
Marsili, M.
Corni, S.
Stener, M.
Toffoli, D.
Coccia, E.
author_facet Grobas Illobre, P.
Marsili, M.
Corni, S.
Stener, M.
Toffoli, D.
Coccia, E.
author_sort Grobas Illobre, P.
collection PubMed
description [Image: see text] In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrödinger equation, we developed and implemented the time-resolved induced density of the electronic wavepacket, the time-resolved formulation of the differential projection density of states (ΔPDOS), and of transition contribution map (TCM) to look at the single-electron orbital occupation and localization change in time. Moreover, to further quantify the possible charge transfer, we also defined the energy-integrated ΔPDOS and the fragment-projected TCM. We have used time-dependent density-functional theory (TDDFT), as implemented in ADF software, and the Bethe–Salpeter equation, as provided by MolGW package, for the description of the electronic excited states. This suite of postprocessing tools also provides the time evolution of the electronic states of the system of interest. To illustrate the usefulness of these postprocessing tools, excited-state populations have been computed for HBDI (the chromophore of GFP) and DNQDI molecules interacting with a sequence of two pulses. Time-resolved descriptors have been applied to study the time-resolved electron dynamics of HBDI, DNQDI, LiCN (being a model system for dipole switching upon highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) electronic excitation), and Ag(22). The computational analysis tools presented in this article can be employed to help the interpretation of fast and ultrafast spectroscopies on molecular, supramolecular, and composite systems.
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spelling pubmed-85158062021-10-15 Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms Grobas Illobre, P. Marsili, M. Corni, S. Stener, M. Toffoli, D. Coccia, E. J Chem Theory Comput [Image: see text] In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrödinger equation, we developed and implemented the time-resolved induced density of the electronic wavepacket, the time-resolved formulation of the differential projection density of states (ΔPDOS), and of transition contribution map (TCM) to look at the single-electron orbital occupation and localization change in time. Moreover, to further quantify the possible charge transfer, we also defined the energy-integrated ΔPDOS and the fragment-projected TCM. We have used time-dependent density-functional theory (TDDFT), as implemented in ADF software, and the Bethe–Salpeter equation, as provided by MolGW package, for the description of the electronic excited states. This suite of postprocessing tools also provides the time evolution of the electronic states of the system of interest. To illustrate the usefulness of these postprocessing tools, excited-state populations have been computed for HBDI (the chromophore of GFP) and DNQDI molecules interacting with a sequence of two pulses. Time-resolved descriptors have been applied to study the time-resolved electron dynamics of HBDI, DNQDI, LiCN (being a model system for dipole switching upon highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) electronic excitation), and Ag(22). The computational analysis tools presented in this article can be employed to help the interpretation of fast and ultrafast spectroscopies on molecular, supramolecular, and composite systems. American Chemical Society 2021-09-06 2021-10-12 /pmc/articles/PMC8515806/ /pubmed/34486881 http://dx.doi.org/10.1021/acs.jctc.1c00211 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 Grobas Illobre, P.
Marsili, M.
Corni, S.
Stener, M.
Toffoli, D.
Coccia, E.
Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title_full Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title_fullStr Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title_full_unstemmed Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title_short Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms
title_sort time-resolved excited-state analysis of molecular electron dynamics by tddft and bethe–salpeter equation formalisms
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8515806/
https://www.ncbi.nlm.nih.gov/pubmed/34486881
http://dx.doi.org/10.1021/acs.jctc.1c00211
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