Electronic structure and dissociation curves for the ground states of Tl/sub 2/ and Tl/sub 2//sup +/ from relativistic effective potential calculations
The dissociation curves for the ground states of Tl/sub 2/ and Tl/sub 2//sup +/ were computed using a generalization of the molecular relativistic ..omega..--..omega.. coupling formalism of Lee, Ermler, and Pitzer. Relativistic effects, as represented by the Dirac equation, were introduced using effective potentials generated from atomic Dirac--nFock wave functions using a generalization of the improved effective potential formulation of Christiansen, Lee, and Pitzer. Our calculations show that the ground state of Tl/sub 2//sup +/ is 1/2/sub g/ with computed D/sub e/ and R/sub e/ values of 0.58 eV and 3.84 A. For Tl/sub 2/ we find that the ground state is 0/sub u//sup -/ but the 0/sub g//sup +/ and the 1/sub u/ states are only slightly higher in energy; the potential curves for these states are repulsive to about 3.5 A and then essentially flat beyond that radius. While corrections for correlation will increase D/sub e/ somewhat, Tl/sub 2/ is only weakly bound in any of these states which dissociate to normal atoms. The cause is undoubtedly related to the large spin-orbit splitting between the 6p/sub 1/2/ and 6p/sub 3/2/ thallium spinors.
- Research Organization:
- Department of Chemistry and Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
- OSTI ID:
- 6680196
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 74:2
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
THALLIUM
DISSOCIATION ENERGY
ELECTRONIC STRUCTURE
DIMERS
DIRAC EQUATION
DISSOCIATION
GROUND STATES
RELATIVITY THEORY
DIFFERENTIAL EQUATIONS
ELEMENTS
ENERGY
ENERGY LEVELS
EQUATIONS
FIELD THEORIES
GENERAL RELATIVITY THEORY
METALS
WAVE EQUATIONS
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory