caa a22 4500 605488444 CHVBK 20210128100455.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s00214-014-1613-3 doi (NATIONALLICENCE)springer-10.1007/s00214-014-1613-3 Quantum mechanical and molecular mechanics approach with a multilayered-quantum representation study of solvent effects and potentials of mean force for the CH3CH2Cl+ClO− SN2 reaction in aqueous solution [Elektronische Daten] [Jingxue Zhang, Yulong Xu, Jing Lv, Dunyou Wang] The bimolecular nucleophilic substitution reaction of CH3CH2Cl+ClO− in aqueous solution was investigated using a multilayered-quantum representation, quantum mechanical and molecular mechanics approach with an explicit water model. Ten configurations along the reaction pathway including reactant complex, transition state and product complex were analyzed in the presence of the aqueous solution. The obtained free energy activation barrier under the CCSD(T)/MM representation is 13.2kcal/mol, while it is 11.7kcal/mol under the DFT/MM representation which agrees very well with the DFT calculation, at 11.0kcal/mol, with a polarizable continuum solvent model. The solvent effects including the solvation free energy contribution and the polarization effect raise the free activation barrier by 9.8kcal/mol. The rate constant, at 298K, is 5.27×10−17cm3/molecule/s which is about seven orders of magnitude smaller than that in the gas phase (1.10×10−10cm3/molecule/s). All in all, the aqueous solution plays an essential role in shaping the reaction pathway for this reaction in water. Springer-Verlag Berlin Heidelberg, 2015 Potential of mean force nationallicence Free energy nationallicence Activation barrier nationallicence Solvent effects nationallicence Quantum mechanical/molecular mechanics nationallicence Zhang Jingxue College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut Xu Yulong College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut Lv Jing College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut Wang Dunyou College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-7 1432-881X 134:2<1 2015 134 214 https://doi.org/10.1007/s00214-014-1613-3 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-014-1613-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Zhang Jingxue College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut NATIONALLICENCE 700 1- Xu Yulong College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut NATIONALLICENCE 700 1- Lv Jing College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut NATIONALLICENCE 700 1- Wang Dunyou College of Physics and Electronics, Shandong Normal University, 250014, Jinan, China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/2(2015-02-01), 1-7 1432-881X 134:2<1 2015 134 214