English

Automatic Differentiation for the Direct Minimization Approach to the Hartree-Fock Method

Chemical Physics 2022-11-28 v2

Abstract

Automatic differentiation has become an important tool for optimization problems in computational science, and it has been applied to the Hartree-Fock method. Although the reverse-mode automatic differentiation is more efficient than the forward-mode, eigenvalue calculation in the self-consistent field method has impeded the use of the reverse-mode automatic differentiation. Here, we propose a method to directly minimize Hartree-Fock energy under the orthonormality constraint of the molecular orbitals using reverse-mode automatic differentiation by avoiding eigenvalue calculation. According to our validation, the proposed method was more stable than the conventional self-consistent field method and achieved comparable accuracy.

Keywords

Cite

@article{arxiv.2203.04441,
  title  = {Automatic Differentiation for the Direct Minimization Approach to the Hartree-Fock Method},
  author = {Naruki Yoshikawa and Masato Sumita},
  journal= {arXiv preprint arXiv:2203.04441},
  year   = {2022}
}
R2 v1 2026-06-24T10:06:44.485Z