ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
A series of controlled multiple collision chemiluminescent and laser induced fluorescent studies confirm the long-range collisional stabilization of high temperature group IIA dihalide complexes of some considerable spatial extent. The relaxation process demonstrates that the pseudocontinuum emissions observed under near single collision conditions [J. Chem. Phys. 102, 7425 (1995)] correspond to the overlap of a closely spaced, highly excited, rovibronic distribution. Controlled relaxation reveals the first vibrationally resolved electronic emission for the dihalides. The vibronic structure of the observed emission spectra correlates well with expectations based on the molecular electronic structure of the ground and low-lying electronic states of the dihalides. The vibronically resolved emission from the Sr+IClHe→SrICl* and mixed halogen Sr+Cl2, Br2→HeSrCl2*+SrBr2* reactions provides strong support for the formation of a collisionally stabilized dihalide complex. These results, correlated with near single collision studies, form a basis for the discussion of (1) the kinetics of formation of the dihalide complexes and (2) the implications of long-range collisional stabilization. Current theories may not accurately model these observations. Dihalide complex formation as it influences the energy partitioning to metal monohalide excited states may account for the discrepancies between those monohalide bond strengths determined by mass spectrometry and chemiluminescent techniques. © 1995 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.469056
Permalink
