Reactions in viscous media: potential and free energy surfaces in solvent–solute coordinates

Abstract

We propose a universal definition of reaction-specific solvent coordinate, described in terms of molecular-dynamic trajectories of the solvent and suitable for a variety of reactions in viscous solvents. We then use molecular dynamics simulations to obtain two-dimensional potential energy and free energy surfaces of model liquid phase isomerisation reactions in solvent–solute coordinates and discuss factors determining their topography.

Keywords:

• reaction-specific solvent coordinate
• molecular-dynamic trajectories
• molecular dynamics simulations

Acknowledgement

Financial support by the Natural Sciences and Engineering Council of Canada and by the University of the Fraser Valley is gratefully acknowledged. We would also like to acknowledge the use of the computational resources of WestGrid. The authors are also grateful to Ms Elna Deglint for assistance with preparation of Figure 10.