Efficient k.p method for first-principles calculation of Seebeck coefficient in quantum transport*

Thermoelectric properties of molecular junctions reveal fundamental aspects of nanoscale charge transport at interfaces and are relevant to potential organic/inorganic hybrid thermoelectric materials. Quantum transport calculations typically evaluate the Seebeck coefficient S by finite differences of the transmission as a function of energy. However, in ab initio calculations this quantity is difficult to converge for realistic systems and can require very large k-grids. We derive a new analytic-derivative method to evaluate S via k.p perturbation theory, implement it in a DFT-based scattering-state transport code, and apply it to calculations of molecular junctions. This technique improves k-point convergence by avoiding critical points in the lead bandstructure and allows more efficient calculations of Seebeck coefficients.