Molecular structure of mercurous halides: Hg/sub 2/F/sub 2/ and Hg/sub 2/Cl/sub 2/

Journal Article · Wed Nov 05 00:00:00 EST 1980 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00543a001· OSTI ID:6652051

Kleier, D A; Wadt, W R

Ab initio generalized valence bond calculations using effective core potentials are presented for the ground state of (HgF)/sub 2/ and (HgCl)/sub 2/. Extensive calculations are also reported for HgF and compared with previous literature results for HgCl. In spite of the polar nature of the Hg-X bond in the monomer, which would favor a head-to-tail orientation of the dipoles in the dimer, a moderately strong covalent bond between the mercury atoms dictates a linear structure (X-Hg-Hg-X) for both fluoride and chloride. Comparison with solid-state data suggests that the Hg-X bonds shorten upon entering the gas phase. Stability toward disproportionation is problematical. Simple calculations predict the chloride to be about 0.6 eV more stable than Hg + HgCl/sub 2/, while the disproportionation of Hg/sub 2/F/sub 2/ is predicted to be nearly thermoneutral. Improved calculations shed some doubt on the stability of Hg/sub 2/Cl/sub 2/. An improved virtual orbital calculation has been performed to estimate where spectral evidence for the existence of Hg/sub 2/Cl/sub 2/ in the gas phase might be found. 5 tables. 2 figures.

• Research Organization: Los Alamos Scientific Lab., NM
• OSTI ID: 6652051
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 102:23
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MERCURY CHLORIDES
GROUND STATES
MOLECULAR STRUCTURE
MERCURY FLUORIDES
BINDING ENERGY
COVALENCE
VALENCE
CHLORIDES
CHLORINE COMPOUNDS
ENERGY
ENERGY LEVELS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
MERCURY COMPOUNDS
MERCURY HALIDES
400201* - Chemical & Physicochemical Properties