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Huzinaga projection embedding for efficient and accurate energies of systems with localized spin-densities

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0076493· OSTI ID:1979005
 [1];  [2];  [2];  [2]
  1. University of Minnesota, Minneapolis, MN (United States); Univ. of Minnesota, Minneapolis, MN (United States)
  2. University of Minnesota, Minneapolis, MN (United States)
+ Show Author Affiliations
We demonstrate the accuracy and efficiency of the restricted open-shell and unrestricted formulation of the absolutely localized Huzinaga projection operator embedding method. Restricted open-shell and unrestricted Huzinaga projection embedding in the full system basis is formally exact to restricted open-shell and unrestricted Kohn–Sham density functional theory, respectively. By utilizing the absolutely localized basis, we significantly improve the efficiency of the method while maintaining high accuracy. Furthermore, the absolutely localized basis allows for high accuracy open-shell wave function methods to be embedded into a closed-shell density functional theory environment. The open-shell embedding method is shown to calculate electronic energies of a variety of systems to within 1 kcal/mol accuracy of the full system wave function result. For certain highly localized reactions, such as spin transition energies on transition metals, we find that very few atoms are necessary to include in the wave function region in order to achieve the desired accuracy. This extension further broadens the applicability of our absolutely localized Huzinaga level-shift projection operator method to include open-shell species. Here, we apply our method to several representative examples, such as spin splitting energies, catalysis on transition metals, and radical reactions.
Research Organization:
University of Minnesota, Minneapolis, MN (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1979005
Alternate ID(s):
OSTI ID: 1843524
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 156; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
Kohn-Sham density functional theory
adsorption
chemical physics
coupled-cluster methods
exchange correlation functionals
operator theory
subsystem density functional theory