Elucidating solvent contributions to solution reactions with ab initio QM/MM methods.

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2010-03-04

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Abstract

Computer simulations of reaction processes in solution in general rely on the definition of a reaction coordinate and the determination of the thermodynamic changes of the system along the reaction coordinate. The reaction coordinate often is constituted of characteristic geometrical properties of the reactive solute species, while the contributions of solvent molecules are implicitly included in the thermodynamics of the solute degrees of freedoms. However, solvent dynamics can provide the driving force for the reaction process, and in such cases explicit description of the solvent contribution in the free energy of the reaction process becomes necessary. We report here a method that can be used to analyze the solvent contributions to the reaction activation free energies from the combined QM/MM minimum free-energy path simulations. The method was applied to the self-exchange S(N)2 reaction of CH(3)Cl + Cl(-), showing that the importance of solvent-solute interactions to the reaction process. The results were further discussed in the context of coupling between solvent and solute molecules in reaction processes.

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10.1021/jp905886q

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Hu, Hao, and Weitao Yang (2010). Elucidating solvent contributions to solution reactions with ab initio QM/MM methods. J Phys Chem B, 114(8). pp. 2755–2759. 10.1021/jp905886q Retrieved from https://hdl.handle.net/10161/4075.

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Yang

Weitao Yang

Philip Handler Distinguished Professor of Chemistry

Prof. Yang, the Philip Handler Professor of Chemistry, is developing methods for quantum mechanical calculations of large systems and carrying out quantum mechanical simulations of biological systems and nanostructures. His group has developed the linear scaling methods for electronic structure calculations and more recently the QM/MM methods for simulations of chemical reactions in enzymes.


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