Electronic structure of HgCl/sub 2/ and HgBr/sub 2/ and its relationship to photodissociation

Journal Article · Fri Feb 15 04:00:00 EST 1980 · J. Chem. Phys.; (United States)

OSTI ID:5613742

Wadt, W R

The low-lying excited states of HgCl/sub 2/ and HgBr/sub 2/ are investigated using effective core potentials in conjunction with a double-zeta plus polarization quality basis set and a moderate-size POL(1) CI wave function. A relativistic effective core potential is used for Hg, while nonrelativistic potentials are used for Cl and Br. The results are interpreted in terms of simple valence bond and molecular orbital pictures to give qualitative insight into the electronic structure of these species. The three lowest absorption features in HgCl/sub 2/ and HgBr/sub 2/ are assigned as 1 /sup 1/Pi/sub u/, 1 /sup 1/..sigma../sup +//sub u/, and 2 /sup 1/..sigma../sup +//sub u/, respectively. The initial two are assigned for the first time. Correlation and energy-level diagrams are used to explain the previous photodissociation experiments. The results are discussed briefly in relation to the development of mercury halide lasers. Finally, the recent experimental work of Husain, Wiesenfeld, and Zare on HgBr/sub 2/, reported in the following paper, confirms in detail our calculations on the 1 /sup 1/..sigma../sup +//sub u/ state which gives rise to the second absorption band.

• Research Organization: Theoretical Division, University of California, Los Alamos Scientific Laboratory, Los Alamos, New Mexico 87545
• OSTI ID: 5613742
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 72:4; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
BROMIDES
BROMINE COMPOUNDS
CHLORIDES
CHLORINE COMPOUNDS
CONFIGURATION INTERACTION
DISSOCIATION
ELECTRONIC STRUCTURE
ENERGY LEVELS
EXCITED STATES
HALIDES
HALOGEN COMPOUNDS
MERCURY BROMIDES
MERCURY CHLORIDES
MERCURY COMPOUNDS
MERCURY HALIDES
SPECTRA