Application of Local Density Functional Theory to the Study of Chemical Reactions

Abstract

It is now generally acknowledged that Local Density Functional (LDF) theory (Parr et al., 1989) yields descriptions of molecules and solids in their electronic ground states that are often superior to those obtained by standard ab initio Hartee-Fock (HF) theory, provided that oversimplified approximations to the potential (e.g. the muffin-tin potential) are avoided (Dahl et al., 1984). However it is not clear to what extent this conclusion remains valid when the system under consideration is not in its ground state. With regard to chemically significant problems, it is particularly interesting to determine whether LDF methods are capable of producing reliable descriptions of reaction pathways, i.e. transition states and energy barriers. With very few exceptions, LDF techniques have not previously been applied to the investigation of chemical reactions.