Density functional theory/Introduction

Density functional theory (DFT) is a computational quantum mechanical modelling method used in physics, chemistry and materials science 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, dopant interactions and some other strongly correlated systems; and in calculations of the band gap and ferromagnetism 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 and inclusion of additional terms to account for both core and valence electrons or by the inclusion of additive terms, is a current research topic.

Overview of method

Although density functional theory has its conceptual roots in the Thomas–Fermi model, DFT was put on a firm theoretical footing by the two Hohenberg–Kohn theorems (H–K). The original H–K theorems held only for non-degenerate ground states in the absence of a magnetic field, although they have since been generalized to encompass these.

The first H–K theorem demonstrates that the ground state properties of a many-electron system are uniquely determined by an electron density that depends on only 3 spatial coordinates. It lays the groundwork for reducing the many-body problem of N electrons with 3N spatial coordinates to 3 spatial coordinates, through the use of functionals of the electron density. This theorem can be extended to the time-dependent domain to develop time-dependent density functional theory (TDDFT), which can be used to describe excited states.

The second H–K theorem defines an energy functional for the system and proves that the correct ground state electron density minimizes this energy functional.

Within the framework of Kohn–Sham DFT (KS DFT), the intractable many-body problem of interacting electrons in a static external potential is reduced to a tractable problem of non-interacting electrons moving in an effective potential. The effective potential includes the external potential and the effects of the Coulomb interactions between the electrons, e.g., the exchange and correlation interactions. Modeling the latter two interactions becomes the difficulty within KS DFT. The simplest approximation is the local-density approximation (LDA), which is based upon exact exchange energy for a uniform electron gas, which can be obtained from the Thomas–Fermi model, and from fits to the correlation energy for a uniform electron gas. Non-interacting systems are relatively easy to solve as the wavefunction can be represented as a Slater determinant of orbitals. Further, the kinetic energy functional of such a system is known exactly. The exchange-correlation part of the total-energy functional remains unknown and must be approximated.

Another approach, less popular than KS DFT but arguably more closely related to the spirit of the original H-K theorems, is orbital-free density functional theory (OFDFT), in which approximate functionals are also used for the kinetic energy of the non-interacting system.

Note: Recently, another foundation to construct the DFT without the Hohenberg–Kohn theorems is getting popular, that is, as a Legendre transformation from external potential to electron density. See, e.g., Density Functional Theory – an introduction, Rev. Mod. Phys. 78, 865–951 (2006), and references therein. A book, 'The Fundamentals of Density Functional Theory' written by H. Eschrig, contains detailed mathematical discussions on the DFT; there is a difficulty for N-particle system with infinite volume; however, we have no mathematical problems in finite periodic system (torus).