The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.
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7 February 2014
Research Article|
February 05 2014
Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl
Erich R. Kuechler;
Erich R. Kuechler
1BioMaPS Institute and Department of Chemistry and Chemical Biology,
Rutgers University
, Piscataway, New Jersey 08854-8087, USA
2Department of Chemistry,
University of Minnesota
, Minneapolis, Minnesota 55455-0431, USA
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Darrin M. York
Darrin M. York
a)
1BioMaPS Institute and Department of Chemistry and Chemical Biology,
Rutgers University
, Piscataway, New Jersey 08854-8087, USA
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a)
Electronic mail: york@biomaps.rutgers.edu
J. Chem. Phys. 140, 054109 (2014)
Article history
Received:
October 11 2013
Accepted:
January 13 2014
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Citation
Erich R. Kuechler, Darrin M. York; Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl− attack on CH3Cl. J. Chem. Phys. 7 February 2014; 140 (5): 054109. https://doi.org/10.1063/1.4863344
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