Structure.pptVIP

Order-N methods rely heavily on the sparsity of the Hamiltonian and overlap matrices Fourier transform of the atomic orbitals The Fourier transform of a convolution in real space is a product in reciprocal space The goal now is to compute the Fourier coefficients of the atomic functions Introducing the plane wave expansion in spherical harmonics and operating * Javier Junquera Code structure: calculation of matrix elements of H and S. Direct diagonalization José M. Soler = N?? N N?? N N?? 1 N?? 1 Most important reference followed in this lecture Goal: solve the one-particle Kohn-Sham Schr?dinger-like equation Introducing the expansion into the Kohn-Sham equation, we arrive to the secular equation Expansion of the eigenvectors in a basis of localized atomic orbitals where the coefficients , and are the dual orbital of : Derivation of the secular equation at Gamma Inserting the expansion of the eigenvector into the Kohn-Sham equation Multiplying by at the left in both sides and integrating over all space Transposing everything to the left hand side term The one-particle Kohn-Sham hamiltonian The standard Kohn-Sham one-electron hamiltonian might be written as Kinetic energy operator Exchange-correlation potential (Assume LDA approach) Hartree potential Transforming the semilocal pseudopotential form into the fully nonlocal separable Kleinman-Bylander form Electronic charge density = sum of spherical atomic densities + deformation charge density (bonding) Populate basis function with appropriate valence atomic charges exactly vanishes beyond The local part is screened by the potential generated by an atomic electron density Neutral atom potential Vanishes exactly ar rc CORE VALENCE Potential outside the sphere vanishes (Gauss theorem ? generated by the total charge inside the sphere = 0 if neutral atom) The hamiltonian computed in SIESTA, combination of two and three center matrix elements KB pseud