Dirac-fock basis set calculations for atoms and molecules

Conference · Mon Aug 05 04:00:00 EDT 1991 · AIP Conference Proceedings (American Institute of Physics); (United States)

OSTI ID:7034969

Mohanty, A K; Clementi, E ^[1]

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1. IBM Corporation Center for Scientific Engineering Computations Department 48B/428 Neighborhood Road Kingston, NY 12401 (United States)

We present Dirac-Hartree-Fock (DHF) atomic structure calculations of many-electron atoms (Z=2{minus}86) using kinetically balanced geometric basis sets of Gaussian functions. It is seen that variational collapse'' or bound failure does not occur if we impose the condition of kinetic balance between the large and the small component spinors along with proper boundary conditions for bound state orbitals. Furthermore, with a finite size nucleus model the DHF total energy for atoms converges more rapidly to the numerical Dirac-Fock (DF) limit with a fewer number basis functions than those calculations where point nucleus is assumed. By systematically extending the geometric basis sets, we have obtained the DHF total energies for all atoms (upto Z=86) within a few millihartrees of the numerical (DF) limit, with smooth convergence from above.

• OSTI ID: 7034969
• Report Number(s): CONF-910225--
• Conference Information: Journal Name: AIP Conference Proceedings (American Institute of Physics); (United States) Journal Volume: 233:1
• Country of Publication: United States
• Language: English

Related Subjects

664100* -- Theory of Electronic Structure of Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ATOMIC MODELS
BOUNDARY CONDITIONS
ELECTRONIC STRUCTURE
ENERGY LEVELS
GROUND STATES
HARTREE-FOCK METHOD
MATHEMATICAL MODELS
MOLECULAR MODELS
SELF-CONSISTENT FIELD
SPINORS