History of the development of the Half-Projected Hartree-Fock method.
Application to the calculation of excited states of the same symmetry as
the ground state
Abstract
Spin projected wave functions are known as generalizations of the
Hartree-Fock wave function. Among them, the Half-Projected Hartree-Fock
(HPHF) model represents a good compromise between the restricted (RHF)
and unrestricted (UHF) Hartree-Fock methods. The HPHF wave function is a
nearly pure wave function of spin and recovers a small part of the spin
correlation energy. This paper reviews the history of the HPHF theory,
not only from the conceptual point of view but also providing a
compilation of the publications of this method over the years until now.
In addition, the extension of the HPHF method to the calculation of
non-orthogonal excited states to the ground state will be treated. The
variational collapse during the calculation of singlet excited states
with the same symmetry as the ground state is avoided by orthogonalizing
the excited orbital to the corresponding occupied orbital. As an
example, the potential energy surface of the S0 ground and 1S1(n, π∗)
first excited state of the formic acid HCOOH are calculated. Formic acid
exhibits complex energy surfaces with respect two large amplitude
motions, the torsional rotation of the O-H group and the waving
out-of-plane angle of the H atom. In the excited state, the molecule
adopts a pyramidal structure. The obtained energy results are fitted to
curves that can be used for the calculation of the theoretical spectrum.