Electron transfer in symmetric complexes: Displaced oscillators and [Fe(CN)6Pt(NH3)4Fe(CN)6] 4- spectra

Margaret H. Hennessy, Ying Wu, Andrew Bruce Bocarsly, Zoltán G. Soos

Research output: Contribution to journalArticle

8 Scopus citations

Abstract

Resonance Raman enhancements yield reorganization energies and displacements of individual modes in electron-transfer (ET) spectra when modeled as displaced harmonic oscillators. The same approximations suffice for quantitative simulations of linear absorption, electroabsorption, or Raman excitation profiles (REPs) through the time autocorrelation function for an arbitrary number of displaced modes. Asymmetric absorption profiles in charge-transfer complexes provide both the reorganization energy and solvent broadening. The unusual ET spectra of the trinuclear title compound are associated with nearly localized valences, two excited states, and symmetry-breaking solvent perturbations. Displaced oscillators and diabatic states rationalize broad absorption, structured REPs, and second-derivative electroabsorption with reorganization energies and displacements found in related binuclear complexes. Both ag and bu modes are displaced in the centrosymmetric complex and excited-state splitting is related to small polarons. The 1800 cm-1 reorganization energy is an order of magnitude smaller than suggested for a single absorption. Raman enhancement data and displaced harmonic oscillators clarify special features of ET or solvents in centrosymmetric complexes.

Original languageEnglish (US)
Pages (from-to)8312-8319
Number of pages8
JournalJournal of Physical Chemistry A
Volume102
Issue number43
StatePublished - Oct 22 1998

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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