Benchmarking Time-Dependent Density Functional Theory Plus One Double (TDDFT-1D) for Potential Energy Surfaces
Year: 2026
Type: preprint
Abstract: Time-dependent density functional theory plus one double (TDDFT-1D) improves on conventional TDDFT by including one specially chosen doubly excited electronic configuration. In this study, we evaluate the ability of that method to describe the ground-and excited-state potential energy surfaces (PESs) of selected model compounds relevant to photochemistry. We find that its accuracy is highly dependent on the given test case. For some systems with relatively little multiconfigurational character, the calculated PESs coincide very closely with benchmark data derived from high-level wavefunction-based calculations. In the most favorable cases–methylene and azomethane–and with specific choices of adjustable simulation parameters, TDDFT-1D PESs follow the benchmark data to around 0.2 eV. For some others, the calculated PESs are distorted to a varying degree. In order to pave the way for future studies employing TDDFT-1D, we identify some specific situations where it may potentially fail, and which should be therefore avoided.
Source: ChemRxiv
Authors: Michał Andrzej Kochman, Bo Durbeej
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7223176021