Optimum basis sets of spherical Gaussian functions and their structure for high-precision calculations of the energies of molecules in the Hartree-Fock approximation
- Cite this article as:
- Glushkov, V.N. Opt. Spectrosc. (2006) 100: 807. doi:10.1134/S0030400X06060014
- 46 Downloads
Specific features of the construction of variationally optimized basis sets providing a high accuracy in calculations of molecular energies in the Hartree-Fock approximation are described. Equations for the optimization of basis sets are obtained for systems with closed and open electronic shells and the structure of an energy hypersurface in the space of nonlinear parameters is considered. The structure of optimum basis sets is studied to develop simple models for generation of orbital exponents and centers of atomic functions. It is shown that, for different molecules, there exist characteristic features of optimum basis sets that are retained with increasing size of a set. Possible strategies for generation of the parameters of basis sets are proposed and preliminary results of their application to the calculation of the ground-state energies of simple diatomic molecules are discussed.