Theoretical Chemistry Accounts

, Volume 124, Issue 5–6, pp 319–330 | Cite as

Structural and electronic structure differences due to the O–H···O and O–H···S bond formation in selected benzamide derivatives: a first-principles molecular dynamics study

  • Aneta JezierskaEmail author
  • Jarosław J. Panek
  • Riccardo Mazzarello
Regular Article


Density functional theory-based methods were employed to obtain static and dynamical descriptions of the molecular properties of 2-hydroxy-N-methylbenzamide and 2-hydroxy-N-methylthiobenzamide; compounds containing O–H···O and O–H···S strong, intramolecular hydrogen bonds. These compounds are important as analogues of commercial analgesic and antipyretic medicines. In the current study the classical Kohn–Sham method was applied to develop static models describing the geometric parameters and proton potentials. The topological analysis of the electron density was performed via atoms in molecules theory. Subsequently, Car–Parrinello molecular dynamics investigations were performed in vacuo and in the solid state. The geometric and spectroscopic properties were investigated and compared with available experimental data. The influence of quantum effects on the intramolecular hydrogen bond properties were studied via path integral molecular dynamics in the solid state for 2-hydroxy-N-methylbenzamide. We found that the proton behavior depends strongly on the type of acceptor: the sulfur-containing bridge has significantly smaller proton flexibility than the oxygen-bearing analogue, which is reflected in the electronic structure and bridge dynamics.


Intramolecular hydrogen bond Atoms in molecules Car–Parrinello molecular dynamics (CPMD) Path integrals molecular dynamics (PIMD) 



We would like to thank Dr. Harald Forbert (Ruhr-Universität Bochum) for the program for dipole moment transformations. We also gratefully acknowledge the Academic Computer Center (TASK) in Gdańsk and the Poznań Supercomputing and Networking Center (PCSS) for providing CPU time and facilities.

Supplementary material

214_2009_612_MOESM1_ESM.pdf (189 kb)
Supplementary material 1 (PDF 190 kb)


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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Aneta Jezierska
    • 1
    • 2
    Email author
  • Jarosław J. Panek
    • 2
  • Riccardo Mazzarello
    • 3
  1. 1.National Institute of ChemistryLjubljanaSlovenia
  2. 2.Faculty of ChemistryUniversity of WrocławWrocławPoland
  3. 3.Computational Science, Department of Chemistry and Applied BiosciencesETH ZurichLuganoSwitzerland

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