Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison

In the present paper we discuss and compare two different energy decomposition schemes: Mayer's Hartree-Fock energy decomposition into diatomic and monoatomic contributions [Chem. Phys. Lett. 382, 265 (2003)], and the Ziegler-Rauk dissociation energy decomposition [Inorg. Chem. 18, 1558 (1979)]...

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Detalles Bibliográficos
Autores: Vyboishchikov, Sergei F., Krapp, Andreas, Frenking, Gernot
Tipo de recurso: artículo
Fecha de publicación:2008
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/3318
Acceso en línea:http://hdl.handle.net/10256/3318
Access Level:acceso abierto
Palabra clave:Àtoms
Descomposició, Mètode de
Electrònica molecular
Electrostàtica
Física nuclear
Atoms
Decomposition method
Electrostatics
Molecular electronics
Nuclear physics
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spelling Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparisonVyboishchikov, Sergei F.Krapp, AndreasFrenking, GernotÀtomsDescomposició, Mètode deElectrònica molecularElectrostàticaFísica nuclearAtomsDecomposition methodElectrostaticsMolecular electronicsNuclear physicsIn the present paper we discuss and compare two different energy decomposition schemes: Mayer's Hartree-Fock energy decomposition into diatomic and monoatomic contributions [Chem. Phys. Lett. 382, 265 (2003)], and the Ziegler-Rauk dissociation energy decomposition [Inorg. Chem. 18, 1558 (1979)]. The Ziegler-Rauk scheme is based on a separation of a molecule into fragments, while Mayer's scheme can be used in the cases where a fragmentation of the system in clearly separable parts is not possible. In the Mayer scheme, the density of a free atom is deformed to give the one-atom Mulliken density that subsequently interacts to give rise to the diatomic interaction energy. We give a detailed analysis of the diatomic energy contributions in the Mayer scheme and a close look onto the one-atom Mulliken densities. The Mulliken density ρA has a single large maximum around the nuclear position of the atom A, but exhibits slightly negative values in the vicinity of neighboring atoms. The main connecting point between both analysis schemes is the electrostatic energy. Both decomposition schemes utilize the same electrostatic energy expression, but differ in how fragment densities are defined. In the Mayer scheme, the electrostatic component originates from the interaction of the Mulliken densities, while in the Ziegler-Rauk scheme, the undisturbed fragment densities interact. The values of the electrostatic energy resulting from the two schemes differ significantly but typically have the same order of magnitude. Both methods are useful and complementary since Mayer's decomposition focuses on the energy of the finally formed molecule, whereas the Ziegler-Rauk scheme describes the bond formation starting from undeformed fragment densitiesAmerican Institute of Physics2008info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10256/3318http://hdl.handle.net/10256/3318© Journal of Chemical Physics, 2008, vol. 129, núm. 14, 144111. Recuperat 29 març 2011,a http://link.aip.org/link/doi/10.1063/1.2989805Articles publicats (D-Q)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1063/1.2989805info:eu-repo/semantics/altIdentifier/issn/0021-9606info:eu-repo/semantics/altIdentifier/eissn/1089-7690Tots els drets reservatsinfo:eu-repo/semantics/openAccessoai:recercat.cat:10256/33182026-05-29T05:05:01Z
dc.title.none.fl_str_mv Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
title Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
spellingShingle Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
Vyboishchikov, Sergei F.
Àtoms
Descomposició, Mètode de
Electrònica molecular
Electrostàtica
Física nuclear
Atoms
Decomposition method
Electrostatics
Molecular electronics
Nuclear physics
title_short Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
title_full Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
title_fullStr Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
title_full_unstemmed Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
title_sort Two complementary molecular energy decomposition schemes: the Mayer and Ziegler-Rauk methods in comparison
dc.creator.none.fl_str_mv Vyboishchikov, Sergei F.
Krapp, Andreas
Frenking, Gernot
author Vyboishchikov, Sergei F.
author_facet Vyboishchikov, Sergei F.
Krapp, Andreas
Frenking, Gernot
author_role author
author2 Krapp, Andreas
Frenking, Gernot
author2_role author
author
dc.subject.none.fl_str_mv Àtoms
Descomposició, Mètode de
Electrònica molecular
Electrostàtica
Física nuclear
Atoms
Decomposition method
Electrostatics
Molecular electronics
Nuclear physics
topic Àtoms
Descomposició, Mètode de
Electrònica molecular
Electrostàtica
Física nuclear
Atoms
Decomposition method
Electrostatics
Molecular electronics
Nuclear physics
description In the present paper we discuss and compare two different energy decomposition schemes: Mayer's Hartree-Fock energy decomposition into diatomic and monoatomic contributions [Chem. Phys. Lett. 382, 265 (2003)], and the Ziegler-Rauk dissociation energy decomposition [Inorg. Chem. 18, 1558 (1979)]. The Ziegler-Rauk scheme is based on a separation of a molecule into fragments, while Mayer's scheme can be used in the cases where a fragmentation of the system in clearly separable parts is not possible. In the Mayer scheme, the density of a free atom is deformed to give the one-atom Mulliken density that subsequently interacts to give rise to the diatomic interaction energy. We give a detailed analysis of the diatomic energy contributions in the Mayer scheme and a close look onto the one-atom Mulliken densities. The Mulliken density ρA has a single large maximum around the nuclear position of the atom A, but exhibits slightly negative values in the vicinity of neighboring atoms. The main connecting point between both analysis schemes is the electrostatic energy. Both decomposition schemes utilize the same electrostatic energy expression, but differ in how fragment densities are defined. In the Mayer scheme, the electrostatic component originates from the interaction of the Mulliken densities, while in the Ziegler-Rauk scheme, the undisturbed fragment densities interact. The values of the electrostatic energy resulting from the two schemes differ significantly but typically have the same order of magnitude. Both methods are useful and complementary since Mayer's decomposition focuses on the energy of the finally formed molecule, whereas the Ziegler-Rauk scheme describes the bond formation starting from undeformed fragment densities
publishDate 2008
dc.date.none.fl_str_mv 2008
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10256/3318
http://hdl.handle.net/10256/3318
url http://hdl.handle.net/10256/3318
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1063/1.2989805
info:eu-repo/semantics/altIdentifier/issn/0021-9606
info:eu-repo/semantics/altIdentifier/eissn/1089-7690
dc.rights.none.fl_str_mv Tots els drets reservats
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Tots els drets reservats
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Institute of Physics
publisher.none.fl_str_mv American Institute of Physics
dc.source.none.fl_str_mv © Journal of Chemical Physics, 2008, vol. 129, núm. 14, 144111. Recuperat 29 març 2011,a http://link.aip.org/link/doi/10.1063/1.2989805
Articles publicats (D-Q)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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