Time and frequency resolved dynamics of ArBr2.
We report the first spectroscopic observation of and vibrational predissociation dynamics for ArBr(2). Measurements are reported for the linear and T-shaped isomers with time and frequency resolution near the Fourier limit of a 15 ps pulse. For the T-shaped isomer, the Ar-Br(2) bond energy D(0) for the B state, nu(')=19, is found to be 200 cm(-1), yielding a D(0)(X) value of 213 cm(-1). Product appearance rates are determined for nu(')=16-25 of the B state of ArBr(2). While the rate generally increases with increasing vibrational quantum number, the trend is not monotonic. Also, obtaining reproducible rates for any given vibrational level requires very careful control of the experimental conditions. The data suggest that ArBr(2) undergoes vibrational predissociation (VP) in the sparse intramolecular vibrational relaxation regime. These observations are consistent with theoretical calculations that show that T-shaped ArBr(2) undergoes VP in the sparse regime, such that lifetimes are strongly dependent on both the vibrational and rotational quantum numbers. As for ArI(2), a linear isomer of ArBr(2) is found to contribute a quasicontinuous background to the excitation spectra. Direct excitation of this continuum results in a very broad product vibrational distribution.
Cabrera
Jose
J
Department of Chemistry and Institute of Surface and Interface Science, University of California, Irvine, California 92697-2025, USA.
Bieler
Craig R
CR
McKinney
Natalie
N
van der Veer
Wytze E
WE
Pio
Jordan M
JM
Janda
Kenneth
K
Roncero
Octavio
O