Constrained Nuclear-Electronic Orbital Time-Dependent Density Functional Theory for Excited-State Dynamics with Nuclear Quantum Effects
Abstract
Nuclear quantum effects can strongly influence excited-state processes involving light nuclei, yet their inclusion in practical molecular dynamics remains challenging. We develop constrained nuclear-electronic orbital time-dependent density functional theory (CNEO-TDDFT), which incorporates quantum-nuclear delocalization into full-dimensional effective excited-state potential energy surfaces while retaining the formal structure and computational scaling of conventional TDDFT. Analytic gradients are also developed, enabling efficient on-the-fly excited-state dynamics. CNEO-TDDFT substantially improves excited-state vibrational frequencies involving hydrogen motion and reduces the root-mean-square deviation from experiment from 113 cm−1 to 26 cm−1. For excited-state proton transfer in 10-hydroxybenzo[h]quinoline (HBQ), CNEO-TDDFT yields a characteristic transfer time of 14.0 fs, compared with 25.5 fs from conventional TDDFT, consistent with the experimentally inferred ultrafast timescale of 12±6 fs. These results establish CNEO-TDDFT as an accurate and efficient framework for excited-state dynamics with nuclear quantum effects.
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BibTeX
@misc{wang2026constrained,
title = {{Constrained Nuclear-Electronic Orbital Time-Dependent Density Functional Theory for Excited-State Dynamics with Nuclear Quantum Effects}},
author = {Yiwen Wang and Zehua Chen and Xi Xu and Yang Yang},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.21120},
eprint = {2610.21120},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.21120},
}
RIS
TY - UNPB
TI - Constrained Nuclear-Electronic Orbital Time-Dependent Density Functional Theory for Excited-State Dynamics with Nuclear Quantum Effects
AU - Yiwen Wang
AU - Zehua Chen
AU - Xi Xu
AU - Yang Yang
PY - 2026
DA - 2026/10/15
PB - arXiv
DO - 10.48550/arxiv.2610.21120
UR - https://arxiv.org/abs/2610.21120
AB - Nuclear quantum effects can strongly influence excited-state processes involving light nuclei, yet their inclusion in practical molecular dynamics remains challenging. We develop constrained nuclear-electronic orbital time-dependent density functional theory (CNEO-TDDFT), which incorporates quantum-nuclear delocalization into full-dimensional effective excited-state potential energy surfaces while retaining the formal structure and computational scaling of conventional TDDFT. Analytic gradients are also developed, enabling efficient on-the-fly excited-state dynamics. CNEO-TDDFT substantially improves excited-state vibrational frequencies involving hydrogen motion and reduces the root-mean-square deviation from experiment from 113 cm^−1 to 26 cm^−1. For excited-state proton transfer in 10-hydroxybenzo[h]quinoline (HBQ), CNEO-TDDFT yields a characteristic transfer time of 14.0 fs, compared with 25.5 fs from conventional TDDFT, consistent with the experimentally inferred ultrafast timescale of 12±6 fs. These results establish CNEO-TDDFT as an accurate and efficient framework for excited-state dynamics with nuclear quantum effects.
ER -