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Title: Using projection operators with maximum overlap methods to simplify challenging self-consistent field optimization

Journal Article · · Journal of Computational Chemistry
DOI: https://doi.org/10.1002/jcc.26797 · OSTI ID:1976344
 [1];  [2]; ORCiD logo [2]; ORCiD logo [2]
  1. University of California, Merced, CA (United States); OSTI
  2. University of California, Merced, CA (United States)
+ Show Author Affiliations

Maximum overlap methods are effective tools for optimizing challenging ground- and excited-state wave functions using self-consistent field models such as Hartree-Fock and Kohn-Sham density functional theory. Nevertheless, such models have shown significant sensitivity to the user-defined initial guess of the target wave function. Here in this work, a projection operator framework is defined and used to provide a metric for non-aufbau orbital selection in maximum-overlap-methods. The resulting algorithms, termed the Projection-based Maximum Overlap Method (PMOM) and Projection-based Initial Maximum Overlap Method (PIMOM), are shown to perform exceptionally well when using simple user-defined target solutions based on occupied/virtual molecular orbital permutations. This work also presents a new metric that provides a simple and conceptually convenient measure of agreement between the desired target and the current or final SCF results during a calculation employing a maximum-overlap method.

Research Organization:
University of California, Merced, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014437
OSTI ID:
1976344
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Journal Issue: 6 Vol. 43; ISSN 0192-8651
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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