The two-site one-electron vibronic coupling model of Piepho, Krausz, and Schatz (PKS) for mixed-valence systems is extended to two-site two-electron dimeric systems. The full dynamic problem is solved and characterization of the system reduces to a simple matrix diagonalization. For strong vibronic coupling, a perturbation treatment is also presented which leads to simple analytical expressions for the eigenvalues and eigenfunctions. The model is used to fit the absorption, resonance Raman, and luminescence spectra of the one-dimensional chlorine-bridged mixed-valence compound [PtIIL4][PtIVL4Cl 2]Cl4·4H2O (L = ethylamine), Wolffram's Red Salt.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry