Abstract

We have explored the relationships between the reaction force F(ξ), the reaction force constant κ(ξ) and the projected force constants of the intramolecular proton transfer HO-N{double bond, long}S → O{double bond, long}N-SH along the intrinsic reaction coordinate ξ. The structural changes and energetics associated with the reaction are analyzed in terms of the three regions defined by F(ξ): reactant, transition and product. The significance of the similarity between κ(ξ) and the variation of the force constant associated to the reaction coordinate mode, kξ(ξ), is discussed in detail. © 2008 Elsevier B.V. All rights reserved.