Work

Hybrid Diagonal Approximation in Time‐Dependent Auxiliary Density Functional Theory

Year: 2025

Type: article

Abstract: A hybrid diagonal approximation (HDA) for time-dependent auxiliary density functional theory (TD-ADFT) is presented. This newly implemented method allows the use of global and range-separated hybrid functionals in TD-ADFT for the calculation of vertical excitation energies and corresponding oscillator strengths. To preserve the exceptional computational efficiency and low-order scaling of TD-ADFT, only the diagonal elements of exact exchange are included in the TD-ADFT matrices. For singlet excitations, this approximation reaches accuracies comparable to four-center electron repulsion integral (ERI) implementations, albeit with a fraction of the computational cost. For triplet excitations, larger deviations are found with the HDA. Despite additional integral calculations, the low-order scaling of TD-ADFT is preserved with the HDA. We explain this by the intact index alignment between the ERIs and the excitation vectors, which remains unaltered in TD-ADFT with the HDA.

Source: Journal of Computational Chemistry

DOI: 10.1002/jcc.70210

Authors: Kevin O. Pérez‐Becerra, Jesús N. Pedroza‐Montero, Mark R. Pederson, Luis I. Hernández‐Segura, Andreas M. Köster

Institutions: Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, Central Michigan University, The University of Texas at El Paso

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

Estimated APC paid: $4,520

Funders: U.S. Department of Energy, Office of Science, Basic Energy Sciences