title: Temporal characteristics of the S1 and T1 thiophosgene Cl2CS in the gas phase: Comparison of the T1 decay with theoretical predictions.
abstract: The picosecond optical-optical double resonance experiment in a supersonic free jet as well as the vapor-phase phosphorescence indicates that the decay of T(1) Cl(2)CS belongs to the intermediate case of the classification scheme for electronic relaxation. The A(fast)/A(slow) pre-exponential ratio in the biexponential T(1) decay is much greater under picosecond excitation than under nanosecond excitation. In vapor phase at low pressure, the phosphorescence exhibits a decay time that varies with the coherence width of the laser used for excitation. Both the T(1) and the S(1) decay times of Cl(2)CS depend strongly on temperature, indicating that Coriolis coupling plays an important role in mode mixing (intramolecular vibrational redistribution).
authors.affiliation: Department of Chemistry and The Center for Laser and Optical Spectroscopy, The University of Akron, Akron, Ohio 44325-3601, USA. fujiwara@uakron.edu
authors.forename: Takashige
authors.initials: T
authors.lastname: Fujiwara
authors.forename: Edward C
authors.initials: EC
authors.lastname: Lim