Bonding in the first-row diatomic molecules within the local spin-density approximation

Journal Article · Sun Aug 15 04:00:00 EDT 1982 · Phys. Rev. B: Condens. Matter; (United States)

DOI:https://doi.org/10.1103/PhysRevB.26.1781· OSTI ID:6704831

Painter, G S; Averill, F W

The Hohenberg-Kohn-Sham density-functional equations in the local spin-density approximation (LSDA) have been solved with essentially no loss of accuracy for dimers of the first row of the Periodic Table with the use of a fully-self-consistent spin-polarized Gaussian-orbital approach. Spectroscopic constants (binding energies, equilibrium separations, and ground-state vibrational frequencies) have been derived from the calculated potential-energy curves. Intercomparison of results obtained using the exchange-correlation functionals of Slater (scaled exchange or X..cap alpha..), Gunnarsson and Lundqvist (GL), and Vosko, Wilk, and Nusair (VWN) permits assessment of the relative merits of each and serves to identify general shortcomings in the LSDA. Basic trends are similar for each functional, but the treatment of the spin dependence of the exchange-correlation energy in the GL and VWN functionals yields a variation of the binding energy across the series which is more systematic than that in the X..cap alpha.. approximation. Agreement between the present results and those of Dunlap, Connolly, and Sabin in the X..cap alpha.., approximation confirms the accuracy of the variational charge-density-fit procedure used in the latter work. The refinements in correlation treatment within the VWN functional are reflected in improvements in binding energies which are only slight for most dimers in the series. This behavior is attributed to the error remaining in the exchange channel within the LSDA and demonstrates the necessity for self-interaction corrections for more accurate binding-energy determinations. Within the current LSDA, absolute accuracies of the VWN functional for the first-row dimers are within 2.3 eV for binding energies, 0.07 a.u. for bond lengths, and approx.200 cm/sup -1/ for vibrational frequencies.

• Research Organization: Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830
• DOE Contract Number: W-7405-ENG-26
• OSTI ID: 6704831
• Journal Information: Phys. Rev. B: Condens. Matter; (United States), Journal Name: Phys. Rev. B: Condens. Matter; (United States) Vol. 26:4; ISSN PRBMD
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
ANGULAR MOMENTUM
BINDING ENERGY
CORRELATION FUNCTIONS
DENSITY
DIMERS
ENERGY
EXCHANGE INTERACTIONS
FUNCTIONALS
FUNCTIONS
GAUSS FUNCTION
INTERACTIONS
MOLECULAR STRUCTURE
ORIENTATION
PARTICLE PROPERTIES
PHYSICAL PROPERTIES
SELF-CONSISTENT FIELD
SLATER METHOD
SPIN
SPIN ORIENTATION