Capturing dynamic correlation with variational explicitly correlated wavefunctions - Ward, Nicholas John; Martinez, Todd J. (Todd Joseph), 1968-; Fayer, Michael D; Markland, Thomas E; Stanford University, Department of Chemistry (2017)
In this dissertation, we describe, implement, and test wavefunctions that describe short-range, so called dynamic correlation effects through the use of explicitly correlated geminal pair functions. We present both a single-configuration explicitly correlated analogue of a Hartree-Fock wavefunction, and a multi- configurational variant, a Geminal-augmented Complete Active Space Self Consistent Field method. These methods are designed to efficiently include dynamic correlation effects during variational optimization of the wavefunction, rather than resorting to a post hoc perturbation description. We test both methods on a number of model systems and show that the geminal-augmented wavefunction is capable of describing short-range correlation effects. In addition, we present a fully exact implementation of the algorithms necessary to evaluate the many-electron integrals that arise in explicitly correlated wavefunctions.
Submitted to the Department of Chemistry.
Thesis (Ph.D.)--Stanford University, 2017.
Rights: (c) Copyright 2017 by Nicholas John Ward
Rights: This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
Keywords: theses