ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Ab initio calculations of rate constants. Reaction F^- + CH₃F = F...CH₃...F^-

I. Černušák, M. Urban, P. Čársky, and Ľ. Treindl

Department of Physical Chemistry, Faculty of Natural Sciences, Komenský University, 842 15Bratislava

Abstract: Absolute rate theory within rigid rotor—harmonic oscillator approximation was used for evaluation of the rate constant of the title reaction. In calculations of energy barrier extended basis set (DZ + P) was used with correlation effects included using the fourth-order many-body perturbation theory. Zero point energies and vibration partition functions were computed at the SCF4-31G level. Solvent effect was estimated by means of simple electrostatic continuum model. Reliability of both activation enthalpy at T = 0 К and rate constants is discussed using extrapolation of experimental results for similar reactions.

Full paper in Portable Document Format: 366a749.pdf

Chemical Papers 36 (6) 749–760 (1982)