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

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.

Universal quantum viscosity in a unitary Fermi gas.

A Fermi gas of atoms with resonant interactions is predicted to obey universal hydrodynamics, in which the shear viscosity and other transport coefficients are universal functions of the density and temperature. At low temperatures, the viscosity has a universal quantum scale ħ n, where n is the density and ħ is Planck's constant h divided by 2π, whereas at high temperatures the natural scale is p(T)(3)/ħ(2), where p(T) is the thermal momentum. We used breathing mode damping to measure the shear viscosity at low temperature. At high temperature T, we used anisotropic expansion of the cloud to find the viscosity, which exhibits precise T(3/2) scaling. In both experiments, universal hydrodynamic equations including friction and heating were used to extract the viscosity. We estimate the ratio of the shear viscosity to the entropy density and compare it with that of a perfect fluid.