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arXiv · 2203.04441

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

Naruki Yoshikawa·Masato Sumita
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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.

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Naruki Yoshikawa, Masato Sumita. 2022-03-08. Automatic Differentiation for the Direct Minimization Approach to the Hartree-Fock Method. https://doi.org/10.1021/acs.jpca.2c05922

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