Augmented Gaussian-orbital basis for atomic-cluster calculations within the density-functional formalism: Application to Cu/sub 2/
The principle of augmentation, used to introduce inner-atom core structure into slowly varying basis functions, is applied to Gaussian orbitals to define a new basis set for highly accurate total-energy calculations for atomic clusters within the density-functional formalism. Diffuse Gaussian-orbital tails are matched continuously and differentiably to inner-atom numeric radial functions at the atomic-sphere radius. Major advantages of Gaussian-orbital basis sets are acquired without the need for numerous Gaussians of large exponent for the core region. The numeric functions used inside the atom permit essentially exact solutions for that region. Procedures are described which recover use of the efficient integral algorithms for the Gaussian-orbital-tail matrix elements. The interactions over the structured inner-atom region are treated by efficient integrand smoothing and integration procedures for the sphere. The new augmented Gaussian basis removes the primary limitations on the use of Gaussian orbitals for heavy atoms. As an illustration the method is applied to the copper dimer in an all-electron framework within the local-spin-density approximation (LSDA). The calculated binding energy, equilibrium separation, and first ionization potential of Cu/sub 2/ are within 2% of experiment within the X..cap alpha.. model. Excitation energies are better described within more recent refined exchange-correlation functionals. These all-electron results show the LSDA model predicts a slightly contracted bond length for Cu/sub 2/, consistent with bulk LSDA calculations for the 3d transition-metal series.
- Research Organization:
- Metals and Ceramics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831
- OSTI ID:
- 5599021
- Journal Information:
- Phys. Rev. B: Condens. Matter; (United States), Vol. 28:10
- Country of Publication:
- United States
- Language:
- English
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