Strong non-adiabatic effects in C2D4+

✍ Scribed by H. Köppel; L.S. Cederbaum; W. Domcke

• Publisher: Elsevier Science
• Year: 1984
• Tongue: English
• Weight: 449 KB
• Volume: 110
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(84)87072-4

✦ Synopsis

It is demonstrated that the second band in the photoelectron spectrum of CaD, is subject to strong non-adiabatic effects, as was previously found for CzH4. The calculation yields a dense and irrcr&ar vibronic line structure, the line density exceeding that expected front the Fran&-Condon principle by two orders of ma:gitude. The feasibility of extracting vibrational frequencies from peak spacings of the envelope of such complex bands is critically examined. The profound impact which conical intersections of molecular potential-ener,~ surfaces [l-3] exert on the nuclear motion has been well estabhshed in recent years [4-91. For realistic values of the electron-vibrational coupling constants [9] these leads to a highly non-adiabatic nuclear motion which manifests itself, e.g., in a complex and erratic vibronic line structure of the corresponding electronic band [S-l?] or in an ultrafast non-radiative decay [7,13,14].