Non-Variational Orbital Optimization Techniques for the AP1roG Wave Function

K. Boguslawski, P. Tecmer, P.W. Ayers, P. Bultinck, S. De Baerdemacker, D. Van Neck
Journal of Chemical Theory and Computation (JCTC)
10 (11), 4873-4882
2014
A1

Abstract 

We introduce new nonvariational orbital optimization schemes for the antisymmetric product of one-reference orbital geminal (AP1roG) wave function (also known as pair-coupled cluster doubles) that are extensions to our recently proposed projected seniority-two (PS2-AP1roG) orbital optimization method [ J. Chem. Phys. 2014, 140, 214114)]. These approaches represent less stringent approximations to the PS2-AP1roG ansatz and prove to be more robust approximations to the variational orbital optimization scheme than PS2-AP1roG. The performance of the proposed orbital optimization techniques is illustrated for a number of well-known multireference problems: the insertion of Be into H2, the automerization process of cyclobutadiene, the stability of the monocyclic form of pyridyne, and the aromatic stability of benzene.