Total-energy minimization of few-body electron systems in the real-space finite-difference scheme.

A practical and high-accuracy computation method to search for ground states of few-electron systems is presented on the basis of the real-space finite-difference scheme. A linear combination of Slater determinants is employed as a many-electron wavefunction, and the total-energy functional is described in terms of overlap integrals of one-electron orbitals without the constraints of orthogonality and normalization. In order to execute a direct energy minimization process of the energy functional, the steepest-descent method is used. For accurate descriptions of integrals which include bare-Coulomb potentials of ions, the time-saving double-grid technique is introduced. As an example of the present method, calculations for the ground state of the hydrogen molecule are demonstrated. An adiabatic potential curve is illustrated, and the accessibility and accuracy of the present method are discussed.