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Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules

[Image: see text] A number of commonly available density functionals have been tested for their ability to describe the energetics and the geometry at conical intersections in connection with the spin-restricted ensemble referenced Kohn–Sham (REKS) method. The minimum energy conical intersections ha...

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Autor principal: Filatov, Michael
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2013
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3794441/
https://www.ncbi.nlm.nih.gov/pubmed/24124402
http://dx.doi.org/10.1021/ct400598b
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author Filatov, Michael
author_facet Filatov, Michael
author_sort Filatov, Michael
collection PubMed
description [Image: see text] A number of commonly available density functionals have been tested for their ability to describe the energetics and the geometry at conical intersections in connection with the spin-restricted ensemble referenced Kohn–Sham (REKS) method. The minimum energy conical intersections have been optimized for several molecular systems, which are widely used as paradigmatic models of photochemical rearrangements and models of biological chromophores. The results of the calculations are analyzed using the sign-change theorem of Longuet-Higgins and a method of elementary reaction coordinates of Haas et al. The latter approach helps to elucidate the differences between the geometries at conical intersections as predicted by the multireference wave function ab initio methods and by the density functional methods. Overall, the BH&HLYP density functional yields the best results for the conical intersection geometries and energetics.
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spelling pubmed-37944412013-10-10 Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules Filatov, Michael J Chem Theory Comput [Image: see text] A number of commonly available density functionals have been tested for their ability to describe the energetics and the geometry at conical intersections in connection with the spin-restricted ensemble referenced Kohn–Sham (REKS) method. The minimum energy conical intersections have been optimized for several molecular systems, which are widely used as paradigmatic models of photochemical rearrangements and models of biological chromophores. The results of the calculations are analyzed using the sign-change theorem of Longuet-Higgins and a method of elementary reaction coordinates of Haas et al. The latter approach helps to elucidate the differences between the geometries at conical intersections as predicted by the multireference wave function ab initio methods and by the density functional methods. Overall, the BH&HLYP density functional yields the best results for the conical intersection geometries and energetics. American Chemical Society 2013-09-06 2013-10-08 /pmc/articles/PMC3794441/ /pubmed/24124402 http://dx.doi.org/10.1021/ct400598b Text en Copyright © 2013 American Chemical Society Terms of Use (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html)
spellingShingle Filatov, Michael
Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title_full Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title_fullStr Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title_full_unstemmed Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title_short Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
title_sort assessment of density functional methods for obtaining geometries at conical intersections in organic molecules
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3794441/
https://www.ncbi.nlm.nih.gov/pubmed/24124402
http://dx.doi.org/10.1021/ct400598b
work_keys_str_mv AT filatovmichael assessmentofdensityfunctionalmethodsforobtaininggeometriesatconicalintersectionsinorganicmolecules