Vibrational dynamics of aniline (N2)1 clusters in their first excited singlet state

Abstract

The first excited singlet state S1 vibrational dynamics of aniline(N2)1 clusters are studied and compared to previous results on aniline(CH4)1 and aniline(Ar)1. Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) rates fall between the two extremes of the CH4 (fast IVR, slow VP) and Ar (slow IVR, fast VP) cluster results as is predicted by a serial IVR/VP model using Fermi’s golden rule to describe IVR processes and a restricted Rice–Ramsperger–Kassel–Marcus (RRKM) theory to describe unimolecular VP rates. The density of states is the most important factor determining the rates. Two product states, 00 and 10b1, of bare aniline and one intermediate state ∼(00) in the overall IVR/VP process are observed and time resolved measurements are obtained for the 000 and ∼(000) transitions. The results are modeled with the serial mechanism described above.