Density Functional Theory

Density Functional Theory

Density functional theory (DFT) is a quantum mechanical modelling method used in physics and chemistry to investigate the electronic structure (principally the ground state) of many-body systems, in particular atoms, molecules, and the condensed phases. With this theory, the properties of a many-electron system can be determined by using functionals, i.e. functions of another function, which in this case is the spatially dependent electron density. Hence the name density functional theory comes from the use of functionals of the electron density. DFT is among the most popular and versatile methods available in condensed-matter physics, computational physics, and computational chemistry.

DFT has been very popular for calculations in solid-state physics since the 1970s. However, DFT was not considered accurate enough for calculations in quantum chemistry until the 1990s, when the approximations used in the theory were greatly refined to better model the exchange and correlation interactions. In many cases the results of DFT calculations for solid-state systems agree quite satisfactorily with experimental data. Computational costs are relatively low when compared to traditional methods, such as Hartree–Fock theory and its descendants based on the complex many-electron wavefunction.

Despite recent improvements, there are still difficulties in using density functional theory to properly describe intermolecular interactions, especially van der Waals forces (dispersion); charge transfer excitations; transition states, global potential energy surfaces and some other strongly correlated systems; and in calculations of the band gap in semiconductors. Its incomplete treatment of dispersion can adversely affect the accuracy of DFT (at least when used alone and uncorrected) in the treatment of systems which are dominated by dispersion (e.g. interacting noble gas atoms) or where dispersion competes significantly with other effects (e.g. in biomolecules). The development of new DFT methods designed to overcome this problem, by alterations to the functional or by the inclusion of additive terms, is a current research topic.