Work

Time-Dependent Particle-Breaking Hartree–Fock Model for Electronically Open Molecules

Year: 2025

Type: article

Abstract: We develop the time-dependent particle-breaking Hartree-Fock (TDPBHF) model to describe excited states and linear response properties of electronically open molecules. This work represents the first step toward building a wave function-based response theory framework for electronically open quantum systems equivalent to that of closed quantum systems. In the limit of particle conservation, TDPBHF reduces to standard time-dependent Hartree-Fock theory. We illustrate the TDPBHF model by computing valence absorption spectra and frequency-dependent electric dipole polarizabilities for a set of small- to medium-sized organic molecules. The particle-breaking interactions are observed to nonuniformly redshift the excitation energies and induce qualitative changes in the absorption profile. In addition, the mixing of multiple excitations in the TDPBHF wave function is observed to dampen the divergence of the response function in the vicinity of resonance energies.

Source: The Journal of Physical Chemistry A

DOI: 10.1021/acs.jpca.5c00810

Authors: Jacob Pedersen, Bendik Støa Sannes, Regina Paul née Matveeva, Sonia Coriani, Ida-Marie Høyvik

Institutions: Norwegian University of Science and Technology, Technical University of Denmark

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid