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Title

Time and frequency resolved dynamics of ArBr2

AuthorsCabrera, José; Bieler, Craig R.; McKinney, Natalie; Veer, Wytze E. van der; Pio, Jordan M.; Janda, Kenneth; Roncero, Octavio CSIC ORCID
KeywordsArgon compounds
Fourier transform spectra
Intramolecular mechanics
Ionisation potential
Isomerism
Molecular electronic states
Predissociation
Quasimolecules
Rotational states
Vibrational states
Issue Date25-Oct-2007
PublisherAmerican Institute of Physics
CitationJournal of Chemical Physics 127(16): 164309 (2007)
AbstractWe report the first spectroscopic observation of and vibrational predissociation dynamics for ArBr2. 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-Br2 bond energy D0 for the B state, ν'=19, is found to be 200 cm-1, yielding a D0(X) value of 213 cm-1. Product appearance rates are determined for ν'=16-25 of the B state of ArBr2. 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 ArBr2 undergoes vibrational predissociation (VP) in the sparse intramolecular vibrational relaxation regime. These observations are consistent with theoretical calculations that show that T-shaped ArBr2 undergoes VP in the sparse regime, such that lifetimes are strongly dependent on both the vibrational and rotational quantum numbers. As for ArI2, a linear isomer of ArBr2 is found to contribute a quasicontinuous background to the excitation spectra. Direct excitation of this continuum results in a very broad product vibrational distribution.
Description11 pages, 9 figures, 4 tables.-- PACS nrs.: 33.80.Gj; 33.20.Tp; 33.20.Sn.
Publisher version (URL)http://dx.doi.org/10.1063/1.2794332
URIhttp://hdl.handle.net/10261/14238
DOI10.1063/1.2794332
ISSN0021-9606
Appears in Collections:(CFMAC-IFF) Artículos

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