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On the Finite Nuclear Effect and Gaussian Basis Sets for Four-Component Dirac Hartree-Fock Calculations

Journal Article · · ACS Symposium Series
 [1];  [2];  [2];  [2]
  1. Univ. of Washington, Seattle, WA (United States); University of Washington
  2. Univ. of Washington, Seattle, WA (United States)
+ Show Author Affiliations
In this perspective we describe an overview of Dirac Hartree-Fock theory, which is the foundation of relativistic quantum chemistry methods vital in the molecular modeling of heavy element chemistry and physics. A special emphasis was placed upon the physical connection between the finite nuclear model and the kinetic-balance condition between the large and small components. Additionally, we review the consequences of basis set choices for Dirac Hartree-Fock calculations in the restricted kinetic balance formalism, and show that the basis set limit does not have a hard lower bound due to the nature of the Hamiltonian, referred to in the literature as prolapse. Standard Gaussian basis set contraction schemes can break down in Dirac Hartree-Fock calculations, and special care must be taken for the description of core orbitals near the nucleus. The phenomena described in this perspective are vital for theoreticians and practitioners to understand when selecting a basis set for heavy element quantum chemical calculations using Dirac Hartree-Fock theory.
Research Organization:
Univ. of Washington, Seattle, WA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0021100
OSTI ID:
1870986
Journal Information:
ACS Symposium Series, Journal Name: ACS Symposium Series Vol. 2021; ISSN 0097-6156
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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