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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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Formato: | Online Artículo Texto |
Lenguaje: | English |
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American Chemical Society
2013
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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. |
format | Online Article Text |
id | pubmed-3794441 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2013 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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 |