caa a22 4500 605487421 CHVBK 20210128100450.0 cr unu---uuuuu 210128e20150701xx s 000 0 eng 10.1007/s00214-015-1681-z doi (NATIONALLICENCE)springer-10.1007/s00214-015-1681-z The effects of internal molecular dynamics on the evaporation/condensation of n -dodecane [Elektronische Daten] [Rasoul Nasiri, Vladimir Gun'ko, Sergei Sazhin] 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. Springer-Verlag Berlin Heidelberg, 2015 Internal molecular dynamics (IMD) effects nationallicence Statistical mechanics method nationallicence Evaporation/condensation nationallicence Conformerisation phenomena nationallicence Reactive force field (ReaxFF) nationallicence Semi-empirical PM7 method nationallicence Density functional theory (DFT) nationallicence Nasiri Rasoul Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut Gun'ko Vladimir Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut Sazhin Sergei Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/7(2015-07-01), 1-12 1432-881X 134:7<1 2015 134 214 https://doi.org/10.1007/s00214-015-1681-z text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1681-z text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Nasiri Rasoul Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut NATIONALLICENCE 700 1- Gun'ko Vladimir Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut NATIONALLICENCE 700 1- Sazhin Sergei Sir Harry Ricardo Laboratories, Centre for Automotive Engineering, School of Computing, Engineering and Mathematics, University of Brighton, BN2 4GJ, Brighton, UK aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/7(2015-07-01), 1-12 1432-881X 134:7<1 2015 134 214