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

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 Hückel 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-f

SUBMITTER: Lehtola S 

PROVIDER: S-EPMC6727215 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature