Abstract
A preliminary resonance Raman intensity analysis study of the 1A2u← 1A1g (5dσ*→ 6pσ) transition of (n-Bu4N)4[Pt2(P2O5H2)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(P2O5H2)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.
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