Electron correlation effects in reduced or oxidized mixed-valency molecules

Paul D. Hale; M. A. Ratner; G. L. Hofacker

doi:10.1016/0009-2614(85)80414-0

Electron correlation effects in reduced or oxidized mixed-valency molecules

Paul D. Hale^*, M. A. Ratner, G. L. Hofacker

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

The vibronic model ordinarily written for mixed-valence molecules predicts an intervalence transfer (IVT) frequency which, in the limit of delocalized states, is unchanged upon reduction by one further electron. This is in sharp disagreement with experiment, but can be remedied, qualitatively, by adding one-site Coulomb repulsion which shifts the analog of the IVT into the near ultraviolet, and an exchange term which produces the correct ordering of the energy levels, thus making a transition analogous to IVT spin-forbidden.

Original language	English (US)
Pages (from-to)	264-268
Number of pages	5
Journal	Chemical Physics Letters
Volume	119
Issue number	4
DOIs	https://doi.org/10.1016/0009-2614(85)80414-0
State	Published - Sep 6 1985

Funding

We are grateful to the Chemistry Division of the NSF for partial support of this research.

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/0009-2614(85)80414-0

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title = "Electron correlation effects in reduced or oxidized mixed-valency molecules",

abstract = "The vibronic model ordinarily written for mixed-valence molecules predicts an intervalence transfer (IVT) frequency which, in the limit of delocalized states, is unchanged upon reduction by one further electron. This is in sharp disagreement with experiment, but can be remedied, qualitatively, by adding one-site Coulomb repulsion which shifts the analog of the IVT into the near ultraviolet, and an exchange term which produces the correct ordering of the energy levels, thus making a transition analogous to IVT spin-forbidden.",

author = "Hale, \{Paul D.\} and Ratner, \{M. A.\} and Hofacker, \{G. L.\}",

note = "Funding Information: We are grateful to the Chemistry Division of the NSF for partial support of this research.",

year = "1985",

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doi = "10.1016/0009-2614(85)80414-0",

language = "English (US)",

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T1 - Electron correlation effects in reduced or oxidized mixed-valency molecules

AU - Hale, Paul D.

AU - Ratner, M. A.

AU - Hofacker, G. L.

N1 - Funding Information: We are grateful to the Chemistry Division of the NSF for partial support of this research.

PY - 1985/9/6

Y1 - 1985/9/6

N2 - The vibronic model ordinarily written for mixed-valence molecules predicts an intervalence transfer (IVT) frequency which, in the limit of delocalized states, is unchanged upon reduction by one further electron. This is in sharp disagreement with experiment, but can be remedied, qualitatively, by adding one-site Coulomb repulsion which shifts the analog of the IVT into the near ultraviolet, and an exchange term which produces the correct ordering of the energy levels, thus making a transition analogous to IVT spin-forbidden.

AB - The vibronic model ordinarily written for mixed-valence molecules predicts an intervalence transfer (IVT) frequency which, in the limit of delocalized states, is unchanged upon reduction by one further electron. This is in sharp disagreement with experiment, but can be remedied, qualitatively, by adding one-site Coulomb repulsion which shifts the analog of the IVT into the near ultraviolet, and an exchange term which produces the correct ordering of the energy levels, thus making a transition analogous to IVT spin-forbidden.

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U2 - 10.1016/0009-2614(85)80414-0

DO - 10.1016/0009-2614(85)80414-0

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VL - 119

SP - 264

EP - 268

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 4

ER -

Electron correlation effects in reduced or oxidized mixed-valency molecules

Abstract

Funding

ASJC Scopus subject areas

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