On the Origins of the Linear Free Energy Relationships: Exploring the Nature of the Off-Diagonal Coupling Elements in S(N)2 Reactions.

ABSTRACT: Understanding the relationship between the adiabatic free energy profiles of chemical reactions and the underlining diabatic states is central to the description of chemical reactivity. The diabatic states form the theoretical basis of Linear Free Energy Relationships (LFERs) and thus play a major role in physical organic chemistry and related fields. However, the theoretical justification for some of the implicit LFER assumptions has not been fully established by quantum mechanical studies. This study follows our earlier works(1,2) and uses the ab initio frozen density functional theory (FDFT) method(3) to evaluate both the diabatic and adiabatic free energy surfaces and to determine the corresponding off-diagonal coupling matrix elements for a series of S(N)2 reactions. It is found that

SUBMITTER: Rosta E 

PROVIDER: S-EPMC3544163 | biostudies-literature | 2012

REPOSITORIES: biostudies-literature