Solvation enthalpies of the proton in polar and non-polar solvents: Theoretical study
Lenka Rottmannová *, Peter Škorňa, Ján Rimarčík, Vladimír Lukeš, Erik Klein
Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology in Bratislava, Radlinského 9, SK-812 37 Bratislava, Slovakia
E-mail: * lenka.rottmannova@stuba.sk
Abstract: In spite of the importance of proton transfer in solution-phase processes, there is still no systematic theoretical study of proton solvation enthalpies. We have investigated the solvation enthalpies of the proton in seven solvents of various polarities (benzene, chloroform, acetone, methanol, ethanol, DMSO, water) using the Integral Equation Formalism Polarized Continuum Model (IEF-PCM). All computations were performed at the B3LYP and BHLYP levels of theory with aug-cc-pVDZ, aug-cc-pVTZ and aug-cc-pVQZ basis sets. Our calculations have shown that the B3LYP and BHLYP functionals provide similar solvation enthalpies. Finally, differences in the solvation enthalpy of the proton values stemming from the various basis sets do not exceed 6 kJ mol–1, with exception of DMSO and chloroform. Distance between H+ and the acceptor atom of the solvent molecule is the shortest in the case of water. It has been also found that the B3LYP distances are slightly longer.
Keywords: DFT, IEF-PCM, proton solvation enthalpy, solvent
Full paper in Portable Document Format: acs_0146.pdf
Acta Chimica Slovaca, Vol. 6, No. 1, 2013, pp. 60—63, DOI: 10.2478/acs-2013-0011