RISM-SCF study of the free-energy profile of the Menshutkin-type reaction NH3 + CH3Cl → NH3CH+3 + Cl- in aqueous solution

Kazunari Naka, Hirofumi Sato, Akihiro Morita, Fumio Hirata, Shigeki Kato

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The free-energy profile for the Menshutkin-type reaction NH3 + CH3Cl → NH3CH+3 + Cl- in aqueous solution is studied using the RISM-SCF method. The effect of electron correlation on the free-energy profile is estimated by the RISM-MP2 method at the HF optimized geometries along the reaction coordinate. Solvation was found to have a large influence on the vibrational frequencies at the reactant, transition state and product; these vibrational frequencies are utilized to calculate the zero-point energy correction of the free-energy profile. The computed barrier height and reaction exothermicity are in reasonable agreement with those of experiment and previous calculations. The change of solvation structure along the reaction path is represented by radial distribution functions between solute-solvent atomic sites. The mechanisms of the reaction are discussed from the view points of solute electronic and solvation structures.

Original languageEnglish
Pages (from-to)165-169
Number of pages5
JournalTheoretical Chemistry Accounts
Volume102
Issue number1-6
DOIs
Publication statusPublished - 1999 Jun
Externally publishedYes

Keywords

  • Menshutkin reaction
  • RISM-SCF
  • Solvation effect

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'RISM-SCF study of the free-energy profile of the Menshutkin-type reaction NH<sub>3</sub> + CH<sub>3</sub>Cl → NH<sub>3</sub>CH<sup>+</sup><sub>3</sub> + Cl<sup>-</sup> in aqueous solution'. Together they form a unique fingerprint.

  • Cite this