Benchmarking Time-Dependent Density Functional Theory Plus One Double (TDDFT-1D) for Potential Energy Surfaces
- 1Institute of Physical Chemistry, Polish Academy of Sciences, Ul. Marcina Kasprzaka 44/52, Warszawa, Poland, 01-224
- 2Division of Theoretical Chemistry, Department of Physics, Chemistry and Biology (IFM
- 3Linköping University
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.
Related
- Bulk Boundary Condition for Semi-Infinite Surfaces in Density Functional Theory
- The inverse problem of time-dependent density functional theory on the torus
- Time-Dependent Density Functional Theory with Coulomb Interactions
- Dysfunctional Functionals and their Therapies in Time-Dependent Density Functional Theory
- V-Representability Beyond Singular Times in Time-Dependent Density Functional Theory: The Hubbard Dimer Case
BibTeX
@misc{kochman2026benchmarking,
title = {{Benchmarking Time-Dependent Density Functional Theory Plus One Double (TDDFT-1D) for Potential Energy Surfaces}},
author = {Michał Andrzej Kochman and Bo Durbeej},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010805/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010805/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Benchmarking Time-Dependent Density Functional Theory Plus One Double (TDDFT-1D) for Potential Energy Surfaces
AU - Michał Andrzej Kochman
AU - Bo Durbeej
PY - 2026
DA - 2026/10/21
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010805/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010805/v1
AB - 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.
ER -