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The effects of internal molecular dynamics on the evaporation/condensation of n-dodecane

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Abstract

The effects of conformerisation and internal molecular dynamics of n-dodecane conformers on energy transfers between gas and liquid phases are investigated. Bond energies, Gibbs free energies of internal dynamics of a set of n-dodecane conformers, and energies of the molecules colliding with the surface of an n-dodecane nanodroplet are studied using quantum chemical calculations (DFT with ωB97X-D/cc-pVTZ and semi-empirical PM7) and ReaxFF method. The results of the analysis show that the accuracy of the methods increases as we move from the application of PM7 to the application of ReaxFF and then to DFT. Different temperature dependencies of internal Gibbs free energies of conformers in the gas and liquid phases are expected to affect the heat and mass transfer processes between them. The calculations for the gas and liquid (using the quantum solvation model; SMD) phases show significant differences in the internal dynamics of conformers and demonstrate an entropy–enthalpy competition in the evaporation/condensation of an ensemble of the conformers.

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Acknowledgments

The authors are grateful to Professor Truhlar’s group to provide us the MSTor program, Professor Martin J. Field (University of Grenoble, IBS) for useful discussions, and the EPSRC (UK) (Grants EP/J006793/1 and EP/L00202) for their financial support of this project. The use of NSCCS (http://www.nsccs.ac.uk/) and HECToR/ARCHER (http://www.archer.ac.uk/) supercomputers is gratefully acknowledged.

Conflict of interest

The authors declare no competing financial interests.

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Authors and Affiliations

  1. Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, Brighton, BN2 4GJ, UK

    Rasoul Nasiri, Vladimir M. Gun’ko & Sergei S. Sazhin

  2. Chuiko Institute of Surface Chemistry, 17 General Naumov Street, Kiev, 03164, Ukraine

    Vladimir M. Gun’ko

Authors
  1. Rasoul Nasiri
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  2. Vladimir M. Gun’ko
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  3. Sergei S. Sazhin
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Correspondence to Sergei S. Sazhin.

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Nasiri, R., Gun’ko, V.M. & Sazhin, S.S. The effects of internal molecular dynamics on the evaporation/condensation of n-dodecane. Theor Chem Acc 134, 83 (2015). https://doi.org/10.1007/s00214-015-1681-z

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