---
_id: '66553'
abstract:
- lang: eng
  text: <jats:p>Stimulated by the renewed interest and recent developments in semiempirical
    quantum chemical (SQC) methods for noncovalent interactions, we examine the properties
    of liquid water under ambient conditions by means of molecular dynamics (MD) simulations,
    both with the conventional neglect of diatomic differential overlap-type methods,
    e.g., AM1 and PM6, and with DFTB-type (density-functional tight-binding) methods,
    e.g., DFTB2 and GFN-xTB (Geometry-Frequency-Noncovalent eXtended Tight-Binding).
    Besides the original parameter sets, some specifically reparameterized SQC methods
    (denoted as AM1-W, PM6-fm, and DFTB2-iBi) targeting various smaller water systems
    ranging from molecular clusters to bulk are considered as well. The quality of
    these different SQC methods for describing liquid water properties under ambient
    conditions is assessed by comparison with well-established experimental data and
    also with BLYP-D3 density functional theory-based ab initio MD simulations. Our
    analyses reveal that static and dynamic properties of bulk water are poorly described
    by all considered SQC methods with the original parameters, regardless of the
    underlying theoretical models, with most of the methods suffering from too weak
    hydrogen bonds and hence predicting a far too fluid water with highly distorted
    hydrogen bond kinetics. Meanwhile, the reparameterized force-matched PM6-fm method
    is shown to be able to quantitatively reproduce the static and dynamic features
    of liquid water and thus can be used as a computationally efficient alternative
    to electronic structure-based MD simulations for liquid water that requires extended
    length and time scales. DFTB2-iBi predicts a slightly overstructured water with
    reduced fluidity, whereas AM1-W gives an amorphous ice-like structure for water
    under ambient conditions.</jats:p>
article_number: '034124'
author:
- first_name: Xin
  full_name: Wu, Xin
  id: '77439'
  last_name: Wu
- first_name: Hossam
  full_name: Elgabarty, Hossam
  id: '60250'
  last_name: Elgabarty
  orcid: 0000-0002-4945-1481
- first_name: Vahideh
  full_name: Alizadeh, Vahideh
  last_name: Alizadeh
- first_name: Andrés
  full_name: Henao, Andrés
  last_name: Henao
- first_name: Frederik
  full_name: Zysk, Frederik
  last_name: Zysk
- first_name: Christian
  full_name: Plessl, Christian
  id: '16153'
  last_name: Plessl
  orcid: 0000-0001-5728-9982
- first_name: Sebastian
  full_name: Ehlert, Sebastian
  last_name: Ehlert
- first_name: Jürg
  full_name: Hutter, Jürg
  last_name: Hutter
- first_name: Thomas D.
  full_name: Kühne, Thomas D.
  last_name: Kühne
citation:
  ama: Wu X, Elgabarty H, Alizadeh V, et al. Benchmarking semiempirical quantum chemical
    methods on liquid water. <i>The Journal of Chemical Physics</i>. 2026;165(3).
    doi:<a href="https://doi.org/10.1063/5.0343753">10.1063/5.0343753</a>
  apa: Wu, X., Elgabarty, H., Alizadeh, V., Henao, A., Zysk, F., Plessl, C., Ehlert,
    S., Hutter, J., &#38; Kühne, T. D. (2026). Benchmarking semiempirical quantum
    chemical methods on liquid water. <i>The Journal of Chemical Physics</i>, <i>165</i>(3),
    Article 034124. <a href="https://doi.org/10.1063/5.0343753">https://doi.org/10.1063/5.0343753</a>
  bibtex: '@article{Wu_Elgabarty_Alizadeh_Henao_Zysk_Plessl_Ehlert_Hutter_Kühne_2026,
    title={Benchmarking semiempirical quantum chemical methods on liquid water}, volume={165},
    DOI={<a href="https://doi.org/10.1063/5.0343753">10.1063/5.0343753</a>}, number={3034124},
    journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Wu,
    Xin and Elgabarty, Hossam and Alizadeh, Vahideh and Henao, Andrés and Zysk, Frederik
    and Plessl, Christian and Ehlert, Sebastian and Hutter, Jürg and Kühne, Thomas
    D.}, year={2026} }'
  chicago: Wu, Xin, Hossam Elgabarty, Vahideh Alizadeh, Andrés Henao, Frederik Zysk,
    Christian Plessl, Sebastian Ehlert, Jürg Hutter, and Thomas D. Kühne. “Benchmarking
    Semiempirical Quantum Chemical Methods on Liquid Water.” <i>The Journal of Chemical
    Physics</i> 165, no. 3 (2026). <a href="https://doi.org/10.1063/5.0343753">https://doi.org/10.1063/5.0343753</a>.
  ieee: 'X. Wu <i>et al.</i>, “Benchmarking semiempirical quantum chemical methods
    on liquid water,” <i>The Journal of Chemical Physics</i>, vol. 165, no. 3, Art.
    no. 034124, 2026, doi: <a href="https://doi.org/10.1063/5.0343753">10.1063/5.0343753</a>.'
  mla: Wu, Xin, et al. “Benchmarking Semiempirical Quantum Chemical Methods on Liquid
    Water.” <i>The Journal of Chemical Physics</i>, vol. 165, no. 3, 034124, AIP Publishing,
    2026, doi:<a href="https://doi.org/10.1063/5.0343753">10.1063/5.0343753</a>.
  short: X. Wu, H. Elgabarty, V. Alizadeh, A. Henao, F. Zysk, C. Plessl, S. Ehlert,
    J. Hutter, T.D. Kühne, The Journal of Chemical Physics 165 (2026).
date_created: 2026-07-21T15:34:09Z
date_updated: 2026-07-21T15:43:42Z
doi: 10.1063/5.0343753
intvolume: '       165'
issue: '3'
language:
- iso: eng
main_file_link:
- open_access: '1'
oa: '1'
project:
- _id: '52'
  name: Computing Resources Provided by the Paderborn Center for Parallel Computing
publication: The Journal of Chemical Physics
publication_identifier:
  issn:
  - 0021-9606
  - 1089-7690
publication_status: published
publisher: AIP Publishing
status: public
title: Benchmarking semiempirical quantum chemical methods on liquid water
type: journal_article
user_id: '77439'
volume: 165
year: '2026'
...