Density Functional Theory

DFT is a method of obtaining an approximate solution to the Schrdinger equation of

a many body system; below is a brief history of DFT:
1926: Old DFT was Thomas-Fermi theory and extensions.
50s and 60s: Slater and co-workers develop X as crude KS-LDA.
1965: Modern DFT begins with Kohn-Sham equations. By introducing orbitals, get
99% of the kinetic energy right, get accurate n(r), and only need to approximate a
small contribution, EXC[n].
1965: KS also suggested local density approximation (LDA) and gradient expansion
approximation.
1993: More modern functionals (GGAs and hybrids) shown to be usefully accurate
for thermochemistry
1998: Kohn and Pople win Nobel prize in chemistry
2010: DFT in materials science, geology, soil science, astrophysics, protein folding,
and nanoscience.
Essentially DFT is a theory that describe how electrons behave. According to
Rutherfords nuclear model atoms consist of a nucleus which is positively charged
and which constitute most of its mass, and then it has negatively charged electrons
buzzing around it making the atom electrically neutral. The motion of the electrons
and their spatial behaviour determines chemical properties of an atom and how it
reacts with other atoms, which molecule emerge as a result of this reaction and what
colour, taste and even the conductance; All these properties are determined by what
electrons are doing.
This model is really an unsophisticated one with electrons buzzing around a nucleus,
going in certain orbitals but to rigorously know what the electrons are doing we need
to apply principles of quantum mechanics and derive an equation that the electrons
can satisfy which can determine where they are at any point in time and space.
This prospect was discovered in 1920 using Schrdinger equation. Now using this
equation, we know exactly what the electrons are supposed to be doing. The
problem however with this equation is that it is impossible to solve for more than few
electrons because each electron interacts with all other electrons, so as more
chances of interactions are added, the larger the system you will have and this will
expand the problems to solve and it eventually becomes exponentially difficult to
model on a computer, especially considering systems that we are often interested in
such as biomolecular systems which have hundreds of thousands of electrons.
In 1964 it was repeatedly proven that all properties of this interacting system where
electrons are interacting with each other and are also attracted to the nucleus can be
obtained by simply looking at ground state electron density the probability of finding
any one of those electrons somewhere in space. This greatly simplified the problem
because it means that we can look at a non-interacting system a different system
which has exactly the same electron density but from this fictitious system we can

extract all properties of the true system such as total energy, forces, structure,
charge, density, dipole moments etc., as such the scaling problem is eliminated
because in this fictitious system the electrons do not interact they are just sitting
there, they are attracted to something that is holding them together but they do not
interact with each other. This enables us to really solve quantum mechanical
systems of hundreds and thousands of electrons and this is what DFT is all about.
This computational technique has impacted the field of nanoscience. The structure of
nano-devices is getting smaller and smaller and these quantum effects are getting
more important so scientist use DFT to model these effects. 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.
Below is a really simplistic diagram that depicts how DFT works:

References
L J D Frink, A G Salinger, M P Sears, J D Weinhold & A L Frischknecht. Numerical
challenges in the application of density functional theory to biology and
nanotechnology. J. Phys.: Condens. Matter 14 (2002) 1216712187
Kieron Burke. Perspective on density functional theory.The Journal of Chemical
Physics 136, 150901 (2012); doi: 10.1063/1.4704546
Jess Baldenebro-Lpez, Jos Castorena-Gonzlez, Norma Flores-Holgun, Jorge
Almaral-Snchez &Daniel Glossman-Mitnik. Computational Molecular Nanoscience
Study of the Properties of Copper Complexes for Dye-Sensitized Solar Cells. Int. J.
Mol. Sci. 2012, 13, 16005-16019