ISSN:
1432-2234
Keywords:
Key words: Menshutkin reaction
;
Solvation effect
;
RISM-SCF
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract. The free-energy profile for the Menshutkin-type reaction NH3 + CH3Cl → NH3CH3 + + 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/s002140050487
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