Developing the MTO Formalism

TL;DR

The paper introduces the Nth order muffin-tin orbital (NMTO) method, an advanced computational approach that improves accuracy and efficiency in solving the single-electron Schrödinger equation within muffin-tin potentials, without enlarging the basis set.

Contribution

It generalizes the TB-LMTO-ASA method to the NMTO method, simplifying the formalism and enhancing accuracy by using kinked partial waves and arbitrary energy points, all while maintaining a minimal basis set.

Findings

Substantial accuracy increase over LMTO-ASA

Efficient downfolding without increasing basis size

Applications demonstrating the method's effectiveness

Abstract

We review the simple linear muffin-tin orbital method in the atomic-spheres approximation and a tight-binding representation (TB-LMTO-ASA method), and show how it can be generalized to an accurate and robust Nth order muffin-tin orbital (NMTO) method without increasing the size of the basis set and without complicating the formalism. On the contrary, downfolding is now more efficient and the formalism is simpler and closer to that of screened multiple-scattering theory. The NMTO method allows one to solve the single-electron Schroedinger equation for a MT-potential -in which the MT-wells may overlap- using basis sets which are arbitrarily minimal. The substantial increase in accuracy over the LMTO-ASA method is achieved by substitution of the energy-dependent partial waves by so-called kinked partial waves, which have tails attached to them, and by using these kinked partial waves at N+1 arbitrary energies to construct the set of NMTOs. For N=1 and the two energies chosen infinitesimally close, the NMTOs are simply the 3rd-generation LMTOs. Increasing N, widens the energy window, inside which accurate results are obtained, and increases the range of the orbitals, but it does not increase the size of the basis set and therefore does not change the number of bands obtained. The price for reducing the size of the basis set through downfolding, is a reduction in the number of bands accounted for and -unless N is increased- a narrowing of the energy window inside which these bands are accurate. A method for obtaining orthonormal NMTO sets is given and several applications are presented.