Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

Hiromi Nakai, Atsushi Ishikawa

    Research output: Contribution to journalArticle

    13 Citations (Scopus)

    Abstract

    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

    Original languageEnglish
    Article number174106
    JournalJournal of Chemical Physics
    Volume141
    Issue number17
    DOIs
    Publication statusPublished - 2014 Nov 7

    Fingerprint

    Thermochemistry
    thermochemistry
    Solvation
    solvation
    proposals
    harmonics
    Liquids
    Water
    liquids
    formic acid
    water
    ideal gas
    Gibbs free energy
    ethyl alcohol
    Ethanol
    Gases
    Molecules
    translational motion
    Boiling point
    boiling

    ASJC Scopus subject areas

    • Physics and Astronomy(all)
    • Physical and Theoretical Chemistry

    Cite this

    Quantum chemical approach for condensed-phase thermochemistry : Proposal of a harmonic solvation model. / Nakai, Hiromi; Ishikawa, Atsushi.

    In: Journal of Chemical Physics, Vol. 141, No. 17, 174106, 07.11.2014.

    Research output: Contribution to journalArticle

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