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Azulene Revisited: Picosecond Decay of the S 1 State in the Gas Phase and in Solution
Author(s) -
Huppert Dan,
Jortner Joshua,
Rentzepis P. M.
Publication year - 1977
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197700044
Subject(s) - azulene , chemistry , picosecond , excited state , intramolecular force , relaxation (psychology) , vibrational energy relaxation , excitation , internal conversion , molecule , atomic physics , photochemistry , molecular physics , stereochemistry , optics , physics , spectral line , psychology , social psychology , laser , organic chemistry , quantum mechanics , astronomy
In this paper we report the results of an experimental study of picosecond time‐resolved relaxation dynamics of the S 1 state of the azulene molecule in solution and in the low pressure gas phase, utilizing consecutive two‐photon excitation S 0 → S 1 ( v ) → S 2 (or S 3 ), with the exciting and the monitoring picosecond pulses chosen at the same wavelength. The nonradiative electronic relaxation times for azulene in solution were τ nr = 4 ± 3 ps for S ( v = 5), excited at 530 nm, and τ nr = 3 ± 2 ps for S ( v = 2), excited at 625 nm, while for the “isolated” molecule case τ nr = 4 ± 3 ps for S ( v = 2), excited at 625 nm. The electronic relaxation rate of the S 1 manifold exhibits only a weak dependence on the excess vibrational energy E v up to E v = 4800 cm −1 . The electronic relaxation rate is practically unaffected by solvent perturbations, as appropriate for the statistical limit of intramolecular radiationless transitions.