Several methods are proposed for determining the differences in structure and free energy for homologous transition states in a condensed phase. The first of these methods is based upon the well-known simplex optimization scheme. The second is a variant of the simplex method. The third method uses first and second derivatives of the free energy with respect to the molecular composition and the reaction coordinate. Free energy difference calculations are used on a simple model reaction in a Lennard-Jones liquid to display the problem of finding condensed phase transition states and to test the proposed algorithms.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry