Resonance Raman intensity analysis investigation of metal-metal bonded transitions: An examination of the1A2u ← 1A1g (5dσ* → 6pσ) transition of Pt2(P2O5H2)4 4-

Abstract

A preliminary resonance Raman intensity analysis study of the 1A2u ← 1A1g (5dσ* → 6pσ) transition of (n-Bu4N)4[Pt2(P2O5H 2)4] in acetonitrile solution at room temperature is reported. The absolute resonance Raman and absorption intensities were simultaneously simulated using wavepacket calculations and a simple model. The best fit parameters indicate that the Pt - Pt bond length changes by about 0.225 Å in the initially excited 1A2u state relative to the ground state. This is in good agreement with previous studies on the vibronically structured absorption and emission spectra of low-temperature crystalline (n-Bu4N)4[Pt2(P2O5H 2)4] which suggested that the Pt - Pt bond length changes by about 0.21 Å in the 1,3A2u states. The resonance Raman intensity analysis demonstrated here can be generally applied to metal-metal bonded electronic transitions for compounds and sample conditions (such as room temperature liquids for many samples) which do not exhibit any vibronic structure. Copyright © 1999 John Wiley & Sons, Ltd.