Direct Energy Minimization Based on Exponential Transformation in Density Functional Calculations of Finite and Extended Systems

Aleksei V. Ivanov, Elvar Ö. Jónsson, Tejs Vegge, Hannes Jónsson*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The energy minimization involved in density functional calculations of electronic systems can be carried out using an exponential transformation that preserves the orthonormality of the orbitals. The energy of the system is then represented as a function of the elements of a skew-Hermitian matrix that can be optimized directly using unconstrained minimization methods. An implementation based on the limited memory Broyden-Fletcher-Goldfarb-Shanno approach with inexact line search and a preconditioner is presented and the performance compared with that of the commonly used self-consistent field approach. Results are presented for the G2 set of 148 molecules, liquid water configurations with up to 576 molecules and some insulating crystals. A general preconditioner is presented that is applicable to systems with fractional orbital occupation as is, for example, needed in the k-point sampling for periodic systems. This exponential transformation direct minimization approach is found to outperform the standard implementation of the self-consistent field approach in that all the calculations converge with the same set of parameter values and it requires less computational effort on average. The formulation of the exponential transformation and the gradients of the energy presented here are quite general and can be applied to energy functionals that are not unitary invariant such as self-interaction corrected functionals.
Original languageEnglish
Article number108047
JournalComputer Physics Communications
Volume267
Number of pages7
ISSN0010-4655
DOIs
Publication statusPublished - 2021

Keywords

  • Optimization
  • Density functional theory
  • Unitary transformation
  • Exponential transform
  • Electronic structure

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