Automatic Differentiation for the Direct Minimization Approach to the Hartree–Fock Method
Naruki Yoshikawa, Masato Sumita
Abstract
Automatic differentiation (AD) 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 AD is more efficient than the forward-mode, eigenvalue calculation in the self-consistent field (SCF) method has impeded the use of the reverse-mode AD. Here, we propose a method to directly minimize Hartree-Fock energy under the orthonormality constraint of the molecular orbitals using reverse-mode AD by avoiding eigenvalue calculation. According to our validation, the proposed method was more stable than the conventional SCF method and achieved comparable accuracy.
Topics & Concepts
OrthonormalityHartree–Fock methodEigenvalues and eigenvectorsConstraint (computer-aided design)Automatic differentiationMode (computer interface)AlgorithmMinificationComputer scienceMathematicsQuantum mechanicsPhysicsMathematical optimizationOrthonormal basisGeometryOperating systemComputationSpectroscopy and Quantum Chemical StudiesElectron Spin Resonance StudiesMolecular spectroscopy and chirality