Investigation of the CH{sub 3}Cl + CN{sup −} reaction in water: Multilevel quantum mechanics/molecular mechanics study
Journal Article
·
· Journal of Chemical Physics
- School of Science, Qilu University of Technology, Jinan 250353 (China)
- College of Physics and Electronics, Shandong Normal University, Jinan 250014 (China)
The CH{sub 3}Cl + CN{sup −} reaction in water was studied using a multilevel quantum mechanics/molecular mechanics (MM) method with the multilevels, electrostatic potential, density functional theory (DFT) and coupled-cluster single double triple (CCSD(T)), for the solute region. The detailed, back-side attack S{sub N}2 reaction mechanism was mapped along the reaction pathway. The potentials of mean force were calculated under both the DFT and CCSD(T) levels for the reaction region. The CCSD(T)/MM level of theory presents a free energy activation barrier height at 20.3 kcal/mol, which agrees very well with the experiment value at 21.6 kcal/mol. The results show that the aqueous solution has a dominant role in shaping the potential of mean force. The solvation effect and the polarization effect together increase the activation barrier height by ∼11.4 kcal/mol: the solvation effect plays a major role by providing about 75% of the contribution, while polarization effect only contributes 25% to the activation barrier height. Our calculated potential of mean force under the CCSD(T)/MM also has a good agreement with the one estimated using data from previous gas-phase studies.
- OSTI ID:
- 22490847
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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