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Proton transfer dynamics in the propionic acid dimer from path integral molecular dynamics calculations

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Abstract

The double proton transfer process in the cyclic dimer of propionic acid in the gas phase was studied using a path integral molecular dynamics method. Structures, energies and proton trajectories were determined. Very large amplitude motions of the skeleton of a propionic acid molecule were observed during the simulations, and almost free rotation of the C2H5 group around the Cα-C bond. A double-well symmetric potential with a very small energy barrier was determined from the free energy profile for the proton motions. Infrared spectra for different isotopomers were calculated, and comparative vibrational analysis was performed. The vibrational results from CPMD appear to be in qualitative agreement with the experimental ones.

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Abbreviations

CPMD:

Car–Parrinello molecular dynamics

DFT:

Density functional theory

DPT:

Double proton transfer

IR:

Infrared spectrum

ISR:

Isotopic ratio

MP2:

Second-order Møller–Plesset perturbation method

UV:

Ultraviolet spectroscopy

PBE:

Perdew–Burke–Ernzerhof generalized gradient functional

PIMD:

Path integral molecular dynamics

PI8:

Eight polymer-bead model

PI16:

Sixteen polymer-bead model

SPT:

Single proton transfer

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Acknowledgments

The authors would like to gratefully acknowledge the Ministry of Science and Higher Education of Poland for supporting this research through grant no. NN 204 0958 33. Thanks also are due to the Academic Computer Centre in Gdansk (CI TASK) for allowing us to use the Galera-ACTION cluster, and the Wroclaw Centre for Networking and Supercomputing (WCSS) for permitting us to use the Nova Cluster. Dr. Matthew Farrow is gratefully acknowledged for editing and proofreading this manuscript.

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  1. Faculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383, Wrocław, Poland

    Piotr Durlak & Zdzisław Latajka

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  1. Piotr Durlak
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Correspondence to Piotr Durlak.

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Durlak, P., Latajka, Z. Proton transfer dynamics in the propionic acid dimer from path integral molecular dynamics calculations. J Mol Model 17, 2159–2168 (2011). https://doi.org/10.1007/s00894-010-0939-6

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