TY - JOUR
T1 - Electron transfer in symmetric complexes
T2 - Displaced oscillators and [Fe(CN)6Pt(NH3)4Fe(CN)6] 4- spectra
AU - Hennessy, Margaret H.
AU - Wu, Ying
AU - Bocarsly, Andrew Bruce
AU - Soos, Zoltán G.
PY - 1998/10/22
Y1 - 1998/10/22
N2 - 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.
AB - 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.
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U2 - 10.1021/jp981181i
DO - 10.1021/jp981181i
M3 - Article
AN - SCOPUS:0001662523
SN - 1089-5639
VL - 102
SP - 8312
EP - 8319
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 43
ER -