Many-body exchange effects in clusters of rare gases with a chromophore: He2CO2

Jacek Jakowski; Grzegorz Chałasiński; M. M. Szczȩśniak; Sławomir M. Cybulski

doi:10.1016/S0301-0104(98)00335-8

Many-body exchange effects in clusters of rare gases with a chromophore: He₂CO₂

Jacek Jakowski, Grzegorz Chałasiński, M. M. Szczȩśniak, Sławomir M. Cybulski

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Abstract

The many-body exchange effects up to the 5-body have been analyzed in terms of possible mechanisms by which the intermolecular electron exchange is carried out. The terms corresponding to single (SE), triple (TE), double (DE), and quadruple (QE) exchanges are identified, and their diagrammatic interpretation given. It is demonstrated that they require different physical interpretations, as well as display different angular and radial behaviors. The 3-body SE and TE terms were calculated ab initio, and analyzed for a variety of geometries of the He₂CO₂ cluster. The anisotropy of SE over the wide range of configurations is consistent with the electrostatic model of the exchange quadrupole of He₂, interacting with the permanent quadrupole of CO₂. The behavior of TE may be rationalized by considering the Pauli-principle-induced distortion of the monomers involved. The influence of the CO₂ asymmetric stretch on the SE, TE, and on the total exchange non-additivity has also been evaluated and discussed. The TE 4-body term in He₃CO₂ has been calculated and compared with the SE 3-body terms.

Original language	English
Pages (from-to)	573-591
Number of pages	19
Journal	Chemical Physics
Volume	239
Issue number	1-3
DOIs	https://doi.org/10.1016/S0301-0104(98)00335-8
State	Published - Dec 15 1998
Externally published	Yes

Funding

This work was supported by the Polish Committee for Scientific Research KBN (Grant No. 12-501/VII/BW-1301/36/95) and by the National Science Foundation (Grant No. CHE-9527099 and CHE-9616683). Some of the calculations were carried out at the Interdisciplinary Center of Modeling, University of Warsaw. Special thanks are due to Drs. Bogumil Jeziorski, Leszek Stolarczyk, and Krzysztof Szalewicz for reading and commenting on the manuscript.

Funders	Funder number
Polish Committee for Scientific Research KBN	12-501/VII/BW-1301/36/95
National Science Foundation

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title = "Many-body exchange effects in clusters of rare gases with a chromophore: He2CO2",

abstract = "The many-body exchange effects up to the 5-body have been analyzed in terms of possible mechanisms by which the intermolecular electron exchange is carried out. The terms corresponding to single (SE), triple (TE), double (DE), and quadruple (QE) exchanges are identified, and their diagrammatic interpretation given. It is demonstrated that they require different physical interpretations, as well as display different angular and radial behaviors. The 3-body SE and TE terms were calculated ab initio, and analyzed for a variety of geometries of the He2CO2 cluster. The anisotropy of SE over the wide range of configurations is consistent with the electrostatic model of the exchange quadrupole of He2, interacting with the permanent quadrupole of CO2. The behavior of TE may be rationalized by considering the Pauli-principle-induced distortion of the monomers involved. The influence of the CO2 asymmetric stretch on the SE, TE, and on the total exchange non-additivity has also been evaluated and discussed. The TE 4-body term in He3CO2 has been calculated and compared with the SE 3-body terms.",

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T1 - Many-body exchange effects in clusters of rare gases with a chromophore

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AU - Jakowski, Jacek

AU - Chałasiński, Grzegorz

AU - Szczȩśniak, M. M.

AU - Cybulski, Sławomir M.

PY - 1998/12/15

Y1 - 1998/12/15

N2 - The many-body exchange effects up to the 5-body have been analyzed in terms of possible mechanisms by which the intermolecular electron exchange is carried out. The terms corresponding to single (SE), triple (TE), double (DE), and quadruple (QE) exchanges are identified, and their diagrammatic interpretation given. It is demonstrated that they require different physical interpretations, as well as display different angular and radial behaviors. The 3-body SE and TE terms were calculated ab initio, and analyzed for a variety of geometries of the He2CO2 cluster. The anisotropy of SE over the wide range of configurations is consistent with the electrostatic model of the exchange quadrupole of He2, interacting with the permanent quadrupole of CO2. The behavior of TE may be rationalized by considering the Pauli-principle-induced distortion of the monomers involved. The influence of the CO2 asymmetric stretch on the SE, TE, and on the total exchange non-additivity has also been evaluated and discussed. The TE 4-body term in He3CO2 has been calculated and compared with the SE 3-body terms.

AB - The many-body exchange effects up to the 5-body have been analyzed in terms of possible mechanisms by which the intermolecular electron exchange is carried out. The terms corresponding to single (SE), triple (TE), double (DE), and quadruple (QE) exchanges are identified, and their diagrammatic interpretation given. It is demonstrated that they require different physical interpretations, as well as display different angular and radial behaviors. The 3-body SE and TE terms were calculated ab initio, and analyzed for a variety of geometries of the He2CO2 cluster. The anisotropy of SE over the wide range of configurations is consistent with the electrostatic model of the exchange quadrupole of He2, interacting with the permanent quadrupole of CO2. The behavior of TE may be rationalized by considering the Pauli-principle-induced distortion of the monomers involved. The influence of the CO2 asymmetric stretch on the SE, TE, and on the total exchange non-additivity has also been evaluated and discussed. The TE 4-body term in He3CO2 has been calculated and compared with the SE 3-body terms.

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ER -

Many-body exchange effects in clusters of rare gases with a chromophore: He₂CO₂

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