Compact sum-of-products form of the molecular electronic Hamiltonian based on canonical polyadic decomposition

• Verfasst von: Sasmal, Sudip [VerfasserIn]
• Verfasst von: Schröder, Markus [VerfasserIn]
• Verfasst von: Vendrell, Oriol [VerfasserIn]
• Titel: Compact sum-of-products form of the molecular electronic Hamiltonian based on canonical polyadic decomposition
• Verf.angabe: Sudip Sasmal, Markus Schröder, and Oriol Vendrell
• E-Jahr: 2024
• Jahr: 14 February 2024
• Umfang: 18 S.
• Illustrationen: Illustrationen
• Fussnoten: Online veröffentlicht: 12. Februar 2024 ; Gesehen am 20.03.2024
• Titel Quelle: Enthalten in: The journal of chemical physics
• Ort Quelle: Melville, NY : American Institute of Physics, 1933
• Jahr Quelle: 2024
• Band/Heft Quelle: 160(2024), 6, Artikel-ID 064109, Seite 064109-1-064109-18
• ISSN Quelle: 1089-7690
• DOI: doi:10.1063/5.0192012
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 188389090X

Abstract

We propose an approach to represent the second-quantized electronic Hamiltonian in a compact sum-of-products (SOP) form. The approach is based on the canonical polyadic decomposition of the original Hamiltonian projected onto the sub-Fock spaces formed by groups of spin-orbitals. The algorithm for obtaining the canonical polyadic form starts from an exact sum-of-products, which is then optimally compactified using an alternating least squares procedure. We discuss the relation of this specific SOP with related forms, namely the Tucker format and the matrix product operator often used in conjunction with matrix product states. We benchmark the method on the electronic dynamics of an excited water molecule, trans-polyenes, and the charge migration in glycine upon inner-valence ionization. The quantum dynamics are performed with the multilayer multiconfiguration time-dependent Hartree method in second quantization representation. Other methods based on tree-tensor Ansätze may profit from this general approach.