Assessment of Initial Guesses for Self-Consistent Field Calculations. Superposition of Atomic Potentials : Simple yet Efficient

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Lehtola , S 2019 , ' Assessment of Initial Guesses for Self-Consistent Field Calculations. Superposition of Atomic Potentials : Simple yet Efficient ' , Journal of Chemical Theory and Computation , vol. 15 , no. 3 , pp. 1593-1604 . https://doi.org/10.1021/acs.jctc.8b01089

Title: Assessment of Initial Guesses for Self-Consistent Field Calculations. Superposition of Atomic Potentials : Simple yet Efficient
Author: Lehtola, Susi
Contributor: University of Helsinki, Department of Chemistry
Date: 2019-03
Language: eng
Number of pages: 12
Belongs to series: Journal of Chemical Theory and Computation
ISSN: 1549-9618
URI: http://hdl.handle.net/10138/300678
Abstract: Electronic structure calculations, such as in the Hartree-Fock or Kohn-Sham density functional approach, require an initial guess for the molecular orbitals. The quality of the initial guess has a significant impact on the speed of convergence of the self-consistent field (SCF) procedure. Popular choices for the initial guess include the one-electron guess from the core Hamiltonian, the extended Huckel method, and the superposition of atomic densities (SAD). Here, we discuss alternative guesses obtained from the superposition of atomic potentials (SAP), which is easily implementable even in real-space calculations. We also discuss a variant of SAD which produces guess orbitals by purification of the density matrix that could also be used in real-space calculations, as well as a parameter-free variant of the extended Huckel method, which resembles the SAP method and is easy to implement on top of existing SAD infrastructure. The performance of the core Hamiltonian, the SAD, and the SAP guesses as well as the extended Huckel variant is assessed in nonrelativistic calculations on a data set of 259 molecules ranging from the first to the fourth periods by projecting the guess orbitals onto precomputed, converged SCF solutions in single- to triple-zeta basis sets. It is shown that the proposed SAP guess is the best guess on average. The extended Huckel guess offers a good alternative, with less scatter in accuracy.
Subject: INDEPENDENT-PARTICLE-MODEL
DENSITY-MATRIX MINIMIZATION
MOLECULAR-ORBITAL METHODS
KOHN-SHAM ORBITALS
HARTREE-FOCK
BASIS-SETS
FUNCTIONAL THEORY
SCF CALCULATIONS
EXTENDED HUCKEL
LESS-THAN
116 Chemical sciences
114 Physical sciences
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