Density functional theory correlation energy

The ab initio methods used by most investigators include Hartree-Fock (FFF) and Density Functional Theory (DFT) [6, 7]. An ab initio method typically uses one of many basis sets for the solution of a particular problem. These basis sets are discussed in considerable detail in references [1] and [8]. DFT is based on the proof that the ground state electronic energy is determined completely by the electron density [9]. Thus, there is a direct relationship between electron density and the energy of a system. DFT calculations are extremely popular, as they provide reliable molecular structures and are considerably faster than FFF methods where correlation corrections (MP2) are included. Although intermolecular interactions in ion-pairs are dominated by dispersion interactions, DFT (B3LYP) theory lacks this term [10-14]. FFowever, DFT theory is quite successful in representing molecular structure, which is usually a primary concern. 

There have, however, been attempts to correlate Q-e values and hence reactivity ratios to, for example, c NMR chemical shifts 50 or the results of MO calculations 51153 and to provide a better theoretical basis for the parameters. Most recently, Zhan and Dixon153 applied density functional theory to demonstrate that Q values could be correlated to calculated values of the relative free energy for the radical monomer reaction (PA + Mn — PA ). The e values were correlated to values of the electronegativities of monomer and radical. 

Gritsenko, O. V., Schipper, P. R. T., Baerends, E. J., 1997, Exchange and Correlation Energy in Density Functional Theory. Comparison of Accurate DFT Quantities With Traditional Hartree-Fock Based Ones and Generalized Gradient Approximations for the Molecules Li2, N2, F2 , J. Chem. Phys., 107, 5007. 

Wesolowski, T. A., Parisel, O., Ellinger, Y., Weber, J., 1997, Comparative Study of Benzene---X (X = 02, N2, CO) Complexes Using Density Functional Theory The Importance of an Accurate Exchange-Correlation Energy Density at High Reduced Density Gradients , J. Phys. Chem. A, 101, 7818. 

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