Quantum-Mechanical Information Content of Multiples Hartree-Fock Solutions. The Multi-Reference Hartree-Fock Configuration Interaction Method

Abstract

The Hartree-Fock equation is non-linear and has, in principle, multiple solutions. The th ω HF extreme and its associated virtual spin-orbitals furnish an orthogonal base B ω of the full configuration interaction space. Although all B ω bases generate the same CI space, the corresponding configurations of each B ω base have distinct quantum-mechanical information contents. In previous works, we have introduced a multi-reference configuration interaction method, based on the multiple extremes of the Hartree-Fock problem. This method was applied to calculate the permanent electrical dipole and quadrupole moments of some small molecules using minimal and double, triple and polarized double-zeta bases. In all cases were possible, using a reduced number of configurations, to obtain dipole and quadrupole moments in close agreement with the experimental values and energies without compromising the energy of the state function. These results show the positive effect of the use of the multi-reference Hartree-Fock bases that allowed a better extraction of quantum mechanical information from the several B ω bases. But to extend these ideas for larger systems and atomic bases, it is necessary to develop criteria to build the multireference Hartree-Fock bases. In this project, we are beginning a study of the non-uniform distribution of quantum-mechanical information content of the B ω bases, searching identify the factors that allowed obtain the good results cited above.