Models for the spectra of bridged mixed-valence dimers

Mary Jo Ondrechen,

Mary Jo Ondrechen

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

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Jaeju Ko,

Jaeju Ko

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

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Li-Tai Zhang,

Li-Tai Zhang

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

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Mary Jo Ondrechen,

Mary Jo Ondrechen

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

Search for more papers by this author

Jaeju Ko,

Jaeju Ko

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

Search for more papers by this author

Li-Tai Zhang,

Li-Tai Zhang

Department of Chemistry, Northeastern University, Boston, Massachusetts 02115, USA

Search for more papers by this author

First published: 18/23 March 1985

https://doi.org/10.1002/qua.560280837

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Abstract

Models for the spectra of bridged mixed-valence dimers, which generally exhibit broad, intense bands in the visible or near infrared regions, are discussed. The two-site model of Piepho, Krausz and Schatz (PKS) [S.B. Piepho, E.R. Krausz, and P.N. Schatz, J. Am. Chem. Soc. 100, 2996–3005 (1978)] is reviewed and compared with a three-site model which explicitly includes the bridging species. We show that when there is a strongly-coupled electronic state on the bridge, the totally symmetric vibrational motion is very important in the vibronic coupling problem for these complexes. Along the vibrational sum coordinate, the potential surfaces for the upper and lower states in the intervalence transfer transition may be treated approximately as two harmonic oscillators with displaced minima. At low temperatures, the transition intensities are given by a Poisson distribution.

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