Weinhold's QCE model - A modified parameter fit. Model study of liquid methanol based on MP2 cluster geometries

Gergely Matisz, Walter M.F. Fabian, Anne Marie Kelterer, Sándor Kunsági-Máté

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The quantum cluster equilibrium (QCE) theory was applied for liquid methanol using MP2(fc)/6-31+G(d,p) cluster geometries and MP2/6-311++G(d,p) energies. Three approaches for the determination of the empirical parameters inherent in the QCE model, amf and bxv, were considered, while the molar volumes of both the liquid and the vapor were obtained from experiment. Model 1, in which amf and bxv were optimized for the vapor and liquid phase, respectively, gave the best results for thermochemical parameters (constant pressure heat capacity C and entropy S) of methanol, especially for the liquid state. In line with Pauling's suggestions concerning the structure of liquid methanol, cyclic hexamers cyclo-(MeOH)6 are the dominant species, even near the boiling point (∼50%) increasing to ∼90% at the freezing temperature.

Original languageEnglish
Pages (from-to)103-109
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Volume956
Issue number1-3
DOIs
Publication statusPublished - Sep 1 2010

Keywords

  • Entropy
  • Heat capacity
  • Liquid methanol
  • MP2 calculations
  • Quantum cluster equilibrium theory
  • Structure

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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