TITLE:
Quantum-Mechanical Information Content of Multiples Hartree-Fock Solutions. The Multi-Reference Hartree-Fock Configuration Interaction Method
AUTHORS:
Luiz Augusto Carvalho Malbouisson, Antonio Moreira de Cerqueira Sobrinho, Micael Dias de Andrade
KEYWORDS:
Multiple Hartree-Fock Solutions, Quantum Mechanical Information Content, Multi-Reference Hartre-Fock Configuration Interaction Method
JOURNAL NAME:
Journal of Modern Physics,
Vol.5 No.7,
April
29,
2014
ABSTRACT: The Hartree-Fock equation is non-linear and
has, in principle, multiple solutions. The ωth HF extreme and its associated virtual spin-orbitals furnish an orthogonal base Bω of the full configuration
interaction space. Although all
Bω
bases generate the same CI space, the corresponding configurations of each
Bω
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
Bω
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
Bω
bases, searching
identify the factors that allowed obtain the good results cited above