Finite temperature electronic structure of Diamond and Silicon

Abstract

The electron-phonon interaction contribution to the electronic energies is included in density functional total energy calculations with ab initio pseudopotentials via the formalism of Allen [Phys. Rev. B, 18 5217 (1978)] to obtain the temperature dependent electronic structure of diamond and silicon. This method allows us to obtain the thermally-averaged ab initio electronic structure in a straightforward and computationally inexpensive way. Our investigations on the finite temperature electronic structure of diamond and silicon bring out that a new criterion, that of temperature transferability, is required in the input ab initio pseudopotentials for temperature dependent studies. The temperature transferability of the Troullier-Martins pseudopotentials used in this work is strongly dependent on the cut-off radius and the inclusion of the unbound 3d 0 state. The finite temperature indirect band gaps are highly sensitive to the choice of cut-off radius used in the pseudopotentials. The finite temperature band structures and density of states show that thermal vibrations affect the electron energies throughout the valence and conduction band. We compare our results on the band gap shifts with that due to the Debye-Waller term in the Allen-Heine theory and discuss the observed differences in the zero point and high temperature band gap shifts. Although, the electron energy shifts in the highest occupied valence band and lowest unoccupied conduction band enable to obtain the changes in the indirect and direct band gaps at finite temperatures, the shifts in other electronic levels with temperature enable investigations into the finite temperature valence charge distribution in the bonding region. Thus, we demonstrate that the Allen theory provides a simple and theoretically justified formalism to obtain finite temperature valence electron charge densities that go beyond the rigid pseudo-atom approximation.

Ti interstitial flows giving rutile TiO2 reoxidation process enhancement in (001) surface

“…[34] actually estimates the volumes of defects as (ρ,V)=(2.206, 6.765) for the charged state (+4) while (ρ,V)=(1.773, 7.690) for the neutral state, where ρ and V denote the amount of accompanying charge and the volume of a defect (in Å 3 ), respectively. An earlier experiment [13] supporting c ⊥ as the preferred path was actually performed at high temperatures raging from 1000 to 1500 K. It is shown through simulation [35] that the electronic distribution in the valence region is expanded with high temperatures. The high temperature experiment suggests a less positively charged defect favoring the c ⊥ path.…”