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Theoretical study of the negative ions of HBr and HI

Journal Article · · Phys. Rev. A; (United States)

Relativistic-configuration-interaction (RCI) and complete-active-space (CAS) multiconfiguration self-consistent-field (MCSCF)/CI calculations are performed for the low-lying anion states of HBr/sup -/ and HI/sup -/. At both the RCI and CASSCF/CI levels of theory, the /sup 2/..sigma../sup +/ anion states are found to be repulsive in the Franck-Condon regions of the HX /sup 1/..sigma../sup +/ states and bound relative to the H+X/sup -/ asymptotes at r>r/sub e/ of the parent neutral states. The HI molecule is predicted to have a slightly positive adiabatic electron affinity, and electron attachment in this system is considered in a Langevin model. Electronic transition moments between the /sup 2/..sigma../sub 1/2//sup +/ and /sup 2/Pi/sub 1/2/ states of HBr/sup -/ and HI/sup -/ are calculated in order to examine the origins of nonadiabatic H/sup -/ fragment production observed in dissociative-attachment experiments on HBr.

Research Organization:
Department of Chemistry, Arizona State University, Tempe, Arizona 85287-1604
OSTI ID:
6873261
Journal Information:
Phys. Rev. A; (United States), Journal Name: Phys. Rev. A; (United States) Vol. 38:12; ISSN PLRAA
Country of Publication:
United States
Language:
English