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Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?

[Image: see text] The performance of the most recent density functionals is assessed for charge-transfer (CT) excitations using comprehensive intra- and intermolecular CT benchmark sets with high-quality reference values. For this comparison, the state-of-the-art range-separated (RS) and long-range-...

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Autores principales: Mester, Dávid, Kállay, Mihály
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8908740/
https://www.ncbi.nlm.nih.gov/pubmed/35200021
http://dx.doi.org/10.1021/acs.jctc.1c01307
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author Mester, Dávid
Kállay, Mihály
author_facet Mester, Dávid
Kállay, Mihály
author_sort Mester, Dávid
collection PubMed
description [Image: see text] The performance of the most recent density functionals is assessed for charge-transfer (CT) excitations using comprehensive intra- and intermolecular CT benchmark sets with high-quality reference values. For this comparison, the state-of-the-art range-separated (RS) and long-range-corrected (LC) double hybrid (DH) approaches are selected, and global DH and LC hybrid functionals are also inspected. The correct long-range behavior of the exchange–correlation (XC) energy is extensively studied, and various CT descriptors are compared as well. Our results show that the most robust performance is attained by RS-PBE-P86/SOS-ADC(2), as it is suitable to describe both types of CT excitations with outstanding accuracy. Furthermore, concerning the intramolecular transitions, unexpectedly excellent results are obtained for most of the global DHs, but their limitations are also demonstrated for bimolecular complexes. Despite the outstanding performance of the LC-DH methods for common intramolecular excitations, serious deficiencies are pointed out for intermolecular CT transitions, and the wrong long-range behavior of the XC energy is revealed. The application of LC hybrids to such transitions is not recommended in any respect.
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spelling pubmed-89087402022-03-11 Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches? Mester, Dávid Kállay, Mihály J Chem Theory Comput [Image: see text] The performance of the most recent density functionals is assessed for charge-transfer (CT) excitations using comprehensive intra- and intermolecular CT benchmark sets with high-quality reference values. For this comparison, the state-of-the-art range-separated (RS) and long-range-corrected (LC) double hybrid (DH) approaches are selected, and global DH and LC hybrid functionals are also inspected. The correct long-range behavior of the exchange–correlation (XC) energy is extensively studied, and various CT descriptors are compared as well. Our results show that the most robust performance is attained by RS-PBE-P86/SOS-ADC(2), as it is suitable to describe both types of CT excitations with outstanding accuracy. Furthermore, concerning the intramolecular transitions, unexpectedly excellent results are obtained for most of the global DHs, but their limitations are also demonstrated for bimolecular complexes. Despite the outstanding performance of the LC-DH methods for common intramolecular excitations, serious deficiencies are pointed out for intermolecular CT transitions, and the wrong long-range behavior of the XC energy is revealed. The application of LC hybrids to such transitions is not recommended in any respect. American Chemical Society 2022-02-24 2022-03-08 /pmc/articles/PMC8908740/ /pubmed/35200021 http://dx.doi.org/10.1021/acs.jctc.1c01307 Text en © 2022 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 Mester, Dávid
Kállay, Mihály
Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title_full Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title_fullStr Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title_full_unstemmed Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title_short Charge-Transfer Excitations within Density Functional Theory: How Accurate Are the Most Recommended Approaches?
title_sort charge-transfer excitations within density functional theory: how accurate are the most recommended approaches?
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8908740/
https://www.ncbi.nlm.nih.gov/pubmed/35200021
http://dx.doi.org/10.1021/acs.jctc.1c01307
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