English

Parameterized Attenuated Exchange for Generalized TDHF@$v_W$ Applications

Chemical Physics 2025-06-03 v2

Abstract

Building upon our previously developed time-dependent Hartree-Fock (TDHF)@vWv_W method, based on many-body perturbation theory and specifically the Bethe-Salpeter Equation (BSE), we introduce a parameterization scheme for the attenuated exchange kernel, vW(rr)v_W(|r - r'|). In the original method, vWv_W was determined individually for each system via an efficient stochastic short-time TD Hartree propagation for the screened Coulomb interaction, W(r,r)W(r,r'). The new parameterization leverages photochemical similarities in exciton binding energies (or exchange interaction attenuation) among molecules with comparable static dielectric responses. We parameterize the inverse dielectric function using a low-order polynomial with error function apodization, calibrated on a few representative molecules, each with its own vWv_W. Using only 7 parameters, the parameterized vWv_W is fully grid-independent and broadly applicable within a family of molecules. This enables TDHF@vWv_W that retains BSE-level accuracy, achieving a mean absolute error of 0.1\sim0.1 eV compared to experimental optical gaps and representing a five- to ten-fold improvement over conventional TD density functional theory or TDHF while reducing the cost to that of standard TDHF.

Keywords

Cite

@article{arxiv.2504.01285,
  title  = {Parameterized Attenuated Exchange for Generalized TDHF@$v_W$ Applications},
  author = {Barry Y. Li and Tim Duong and Tucker Allen and Nadine C. Bradbury and Justin R. Caram and Daniel Neuhauser},
  journal= {arXiv preprint arXiv:2504.01285},
  year   = {2025}
}
R2 v1 2026-06-28T22:43:12.549Z