Reaction free energies in organic solvents: Comparing different quantum mechanical methods

Ivan A. Konstantinov, Linda J Broadbelt

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

A variety of quantum mechanical (QM) methods, basis sets and solute cavity descriptions using the conductor-like polarisable continuum model for the modelling of reaction free energies in solution have been evaluated and compared. In order to test the performance of each QM level of theory and cavity model, five common types of organic reactions in different solvents have been considered. The study shows that the hybrid metageneralised-gradient approximation M05-2X functional, in conjunction with the MG3S basis set and UA0 or universal force field cavities, produces results in the best overall agreement with experimental data. In addition, within the UA0 formalism, explicit cavities should be built on the hydrogen atoms that undergo transformation during chemical reaction.

Original languageEnglish (US)
Pages (from-to)1197-1207
Number of pages11
JournalMolecular Simulation
Volume36
Issue number15
DOIs
StatePublished - Jan 1 2010

Keywords

  • ab initio
  • conductor-like polarisable continuum model
  • density functional theory
  • organic solvents
  • reaction free energies

ASJC Scopus subject areas

  • Chemistry(all)
  • Information Systems
  • Modeling and Simulation
  • Chemical Engineering(all)
  • Materials Science(all)
  • Condensed Matter Physics

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