Elucidating solvent contributions to solution reactions with ab initio QM/MM methods.
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.
Type
Journal articleSubject
CatalysisComputer Simulation
Enzymes
Protein Conformation
Quantum Theory
Solutions
Solvents
Thermodynamics
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https://hdl.handle.net/10161/4075Published Version (Please cite this version)
10.1021/jp905886qPublication Info
Hu, Hao; & Yang, Weitao (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.This is constructed from limited available data and may be imprecise. To cite this
article, please review & use the official citation provided by the journal.
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Show full item recordScholars@Duke
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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