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Journal of Molecular Modeling

, Volume 17, Issue 11, pp 2995–3004 | Cite as

Car-Parrinello and path integral molecular dynamics study of the hydrogen bond in the acetic acid dimer in the gas phase

  • Piotr Durlak
  • Sławomir Berski
  • Zdzisław Latajka
Original Paper

Abstract

In the paper are described studies of the double proton transfer (DPT) processes in the cyclic dimer of acetic acid in the gas phase using Car-Parrinello (CPMD) and path integral molecular dynamics (PIMD). Structures, energies and proton trajectories have been determined. The results show the double proton transfer in 450 K. In the classical dynamics (CPMD) a clear process mechanism can be identified, where asynchronized DPT arises due to coupling between the O-H stretching oscillator and several low energy intermolecular vibrational modes. The DPT mechanism is also asynchronic when quantum tunneling has been allowed in the simulation. It has been found that the calculated values of barrier height for the proton transfer depends very strongly on the used approaches. Barrier received from the free-energy profile at the CPMD level is around 4.5 kcal mol-1 whereas at the PIMD level is reduced to 1 kcal mol-1. The nature of bonding in acetic acid dimer and rearrangement of electron density due to the proton movement has been also studied by the topological analysis of Electron Localization Function and Electron Localizability Indicator function.

Keywords

Acetic acid dimer (AAD) Double proton transfer (DPT) Electron localisation function (ELF) Electron localizability indicator (ELI) Hydrogen bond Path integrals molecular dynamics (PIMD) Quantum effects 

Abbreviations

B3LYP

Becke, Lee, Yang and Parr generalized hybrid functional

CPMD

Car-Parrinello molecular dynamics

DFT

Density functional theory

DPT

Double proton transfer

ELF

Electron Localisation Function

ELI

Electron Localizability Indicator function

MP2

Second-order Møller-Plesset perturbation method

PBE

Perdew, Burke and Ernzerhof generalized gradient functional

PCG

Preconditioned conjugate gradient method

PIMD

Path integral molecular dynamics

PI10

Ten polymer-beads model

Notes

Acknowledgments

The authors would like to gratefully acknowledge the Ministry of Science and Higher Education of Poland for the support of this research; Grant No. NN 204 0958 33. Thanks also are due to the Academic Computer Centre in Gdansk (CI TASK) for the use of the Galera-ACTION Cluster and the Wroclaw Centre for Networking and Supercomputing (WCSS) for the use of the Nova Cluster.

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Piotr Durlak
    • 1
  • Sławomir Berski
    • 1
  • Zdzisław Latajka
    • 1
  1. 1.Faculty of ChemistryUniversity of WrocławWrocławPoland

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