Resonance Raman intensity analysis investigation of metal–metal bonded transitions: an examination of the 1A2u ← 1A1g (5dσ* → 6pσ) transition of Pt2(P2O5H2)44−

✍ Scribed by King Hung Leung; David Lee Phillips; Chi-Ming Che; Vincent M. Miskowski

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 131 KB
• Volume: 30
• Category: Article
• ISSN: 0377-0486
• DOI: 10.1002/(sici)1097-4555(199911)30:11<987::aid-jrs471>3.0.co;2-3

✦ Synopsis

A preliminary resonance Raman intensity analysis study of the 1 A 2u

→ 1 A 1g (5ds * → 6ps) transition of (n-Bu 4 N) 4 [Pt 2 (P 2 O 5 H 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 1 A 2u 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-Bu 4 N) 4 [Pt 2 (P 2 O 5 H 2 ) 4 ] which suggested that the Pt-Pt bond length changes by about 0.21 Å in the 1;3 A 2u 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.