VIBRATIONAL PREDISSOCIATION DYNAMICS OF THE (HEBR2)-BR-79, VAN-DER-WAALS MOLECULE NEAR THE B-STATE DISSOCIATION LIMIT - BINDING-ENERGIES, LIFETIMES, AND IMPLICATIONS FOR THE RARE GAS-HALOGEN POTENTIAL

被引:58
作者
JAHN, DG
CLEMENT, SG
JANDA, KC
机构
[1] Department of Chemistry, University of California, Irvine
关键词
D O I
10.1063/1.468181
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Excitation spectra of the (HeBr2)-Br-79 complex have been obtained for the B state vibrational levels upsilon' = 34-48 using the pump-probe spectroscopic technique. The Delta upsilon = - 1 channel for vibrational predissociation is closed for levels upsilon'= 45 and higher. The B and X state van der Waals binding energies are determined to be 13.5+/-1.0 and 17.0+/-1.5 cm(-1), respectively. Lifetimes for vibrational predissociation were found to range from 5.3 ps for upsilon' = 34 to 1.8 ps for upsilon' = 44. For upsilon' = 45 the lifetime increases to 3.8 ps due to the closing of the Delta upsilon = - 1 dissociation channel. The lifetimes are consistent with the momentum gap law using a Morse parameter equal to 1.9+/-0.1 Angstrom(-1). The trend of increasing blue shifts as upsilon' increases reverses at upsilon' = 40. This appears to indicate that the He-Br interaction changes dramatically when the Br-Br separation becomes larger than 4.0 Angstrom. Based on the results presented here, we have reevaluated previous data for the HeI2 molecule, and suggest that the ground-state binding energy be revised to 17.6+/-1.0 cm(-1) from the currently accepted value of 18.8 cm(-1).
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页码:283 / 291
页数:9
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