The LEDO expansion for diatomic overlap densities: application to the density functional theory of molecules

The limited expansion of differential overlap (LEDO) approach for the expansion of diatomic overlap densities in terms of mono-centre densities is discussed in the context of density functional theory (DFT). It is shown that it leads to a particularly simple construction scheme for major parts of the secular matrix, i.e. the electron-electron interaction and the exchange-correlation potential: using the LEDO expansion coefficients, matrix elements between atomic orbitals located on different centres can be expressed in terms of the corresponding mono-centre elements, thus allowing the reduction of three-centre and four-centre integrals to two-centre integrals. This results in the first DFT method with formal N ² scaling for the construction of the secular matrix, with N being the dimension of the atomic orbital (AO) basis set. Test calculations show that numerical agreement with the results of conventional DFT calculations is excellent.