Economical quasi-Newton unitary optimization of electronic orbitals

Abstract

We present an efficient quasi-Newton orbital solver optimized to reduce the number of gradient evaluations and other computational steps of comparable cost. The solver optimizes orthogonal orbitals by sequences of unitary rotations generated by the (preconditioned) limited-memory Broyden–Fletcher–Goldfarb–Shanno (L-BFGS) algorithm equipped with trust-region step restriction. The low-rank structure of the L-BFGS inverse Hessian is exploited when solving the trust-region problem. The efficiency of the proposed “Quasi-Newton Unitary Optimization with Trust-Region” (QUOTR) solver is compared to that of the standard Roothaan–Hall approach accelerated by the Direct Inversion of Iterative Subspace (DIIS), and other exact and approximate Newton solvers for mean-field (Hartree–Fock and Kohn–Sham) problems.

Graphical abstract: Economical quasi-Newton unitary optimization of electronic orbitals

Supplementary files

Article information

Article type
Paper
Submitted
15 Nov 2023
Accepted
19 Dec 2023
First published
19 Dec 2023

Phys. Chem. Chem. Phys., 2024, Advance Article

Economical quasi-Newton unitary optimization of electronic orbitals

S. A. Slattery, K. A. Surjuse, C. C. Peterson, D. A. Penchoff and E. F. Valeev, Phys. Chem. Chem. Phys., 2024, Advance Article , DOI: 10.1039/D3CP05557D

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