Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set

We present ab initio quantum-mechanical molecular-dynamics simulations of the liquid-metal--amorphous-semiconductor transition in Ge. Our simulations are based on (a) finite-temperature density-functional theory of the one-electron states, (b) exact energy minimization and hence calculation of the exact Hellmann-Feynman forces after each molecular-dynamics step using preconditioned conjugate-gradient techniques, (c) accurate nonlocal pseudopotentials, and (d) Nos\'e dynamics for generating a canonical ensemble. This method gives perfect control of the adiabaticity of the electron-ion ensemble and allows us to perform simulations over more than 30 ps. The computer-generated ensemble describes the structural, dynamic, and electronic properties of liquid and amorphous Ge in very good agreement with experiment. The simulation allows us to study in detail the changes in the structure-property relationship through the metal-semiconductor transition. We report a detailed analysis of the local structural properties and their changes induced by an annealing process. The geometrical, bonding, and spectral properties of defects in the disordered tetrahedral network are investigated and compared with experiment.

Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium.

The exact density functional for the ground-state energy is strictly self-interaction-free (i.e., orbitals demonstrably do not self-interact), but many approximations to it, including the local-spin-density (LSD) approximation for exchange and correlation, are not. We present two related methods for the self-interaction correction (SIC) of any density functional for the energy; correction of the self-consistent one-electron potenial follows naturally from the variational principle. Both methods are sanctioned by the Hohenberg-Kohn theorem. Although the first method introduces an orbital-dependent single-particle potential, the second involves a local potential as in the Kohn-Sham scheme. We apply the first method to LSD and show that it properly conserves the number content of the exchange-correlation hole, while substantially improving the description of its shape. We apply this method to a number of physical problems, where the uncorrected LSD approach produces systematic errors. We find systematic improvements, qualitative as well as quantitative, from this simple correction. Benefits of SIC in atomic calculations include (i) improved values for the total energy and for the separate exchange and correlation pieces of it, (ii) accurate binding energies of negative ions, which are wrongly unstable in LSD, (iii) more accurate electron densities, (iv) orbital eigenvalues that closely approximate physical removal energies, including relaxation, and (v) correct longrange behavior of the potential and density. It appears that SIC can also remedy the LSD underestimate of the band gaps in insulators (as shown by numerical calculations for the rare-gas solids and CuCl), and the LSD overestimate of the cohesive energies of transition metals. The LSD spin splitting in atomic Ni and $s\ensuremath{-}d$ interconfigurational energies of transition elements are almost unchanged by SIC. We also discuss the admissibility of fractional occupation numbers, and present a parametrization of the electron-gas correlation energy at any density, based on the recent results of Ceperley and Alder.

Self-interaction correction to density-functional approximations for many-electron systems

[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

The semiconductor ZnO has gained substantial interest in the research community in part because of its large exciton binding energy (60meV) which could lead to lasing action based on exciton recombination even above room temperature. Even though research focusing on ZnO goes back many decades, the renewed interest is fueled by availability of high-quality substrates and reports of p-type conduction and ferromagnetic behavior when doped with transitions metals, both of which remain controversial. It is this renewed interest in ZnO which forms the basis of this review. As mentioned already, ZnO is not new to the semiconductor field, with studies of its lattice parameter dating back to 1935 by Bunn [Proc. Phys. Soc. London 47, 836 (1935)], studies of its vibrational properties with Raman scattering in 1966 by Damen et al. [Phys. Rev. 142, 570 (1966)], detailed optical studies in 1954 by Mollwo [Z. Angew. Phys. 6, 257 (1954)], and its growth by chemical-vapor transport in 1970 by Galli and Coker [Appl. Phys. ...

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A comprehensive review of zno materials and devices

Electronic structure of ultrathin SinGen strained superlattices: The possibility of direct band gaps

We have calculated the pressure coefficients α of a few optical transitions in (001), (111), (110), and (201) GaP/InP ordered superlattices using ab initio methods. The equilibrium atomic geometries under hydrostatic pressure are obtained by direct minimization of the elastic enthalpy. We find that (i) the pressure coefficient of the lowest energy transition is uniformly high, due to the Γ1c character of the conduction‐band minimum; (ii) the pressure coefficient of the transition to the second lowest conduction state at Γ distinguishes the (111)‐oriented (CuPt) superlattice (α=4.0 meV/kbar) from the remaining structures (α≂−2 meV/kbar). This is so because in CuPt we have L folding, while in the other structures we have X folding; (iii) the calculated pressures for the Γ→X crossover are 45, 43, 12, and 16 kbar for the (001), (111), (110), and (201) superlattices, respectively. These trends reflect the zero‐pressure Γ1c–X1c energy separation and the Γ1c pressure coefficient of these structures.

Pressure dependence of optical transitions in ordered GaP/InP superlattices

We have contrasted the quantum confinement of (i) multiple quantum wells of flat GaAs and AlAs layers, i.e. $(\GaAs)_{m}/(\AlAs)_n/(\GaAs)_p/(\AlAs)_q$, with (ii) ``cylindrical Russian Dolls'' -- an equivalent sequence of wells and barriers arranged as concentric wires. Using a pseudopotential plane-wave calculation, we identified theoretically a set of numbers ($m,n,p$ and $q$) such that charge separation can exist in ``cylindrical Russian Dolls'': the CBM is localized in the inner GaAs layer, while the VBM is localized in the outer GaAs layer.

Predicion of charge separation in GaAs/AlAs cylindrical Russian Doll nanostructures

Density Functional Thermodynamics Description of Spin, Phonon and Displacement Degrees of Freedom in Antiferromagnetic-to-Paramagnetic Phase Transition in YNiO3

It is shown that the local-density formalism does not describe correctly the symmetry of the many-electron ground state of unrelaxed interstitial transition-atom impurities in silicon, but that a self-interaction correction to it produces the observed ground-state symmetries

Alex Zunger

Papers

Electronic structure of ultrathin SinGen strained superlattices: The possibility of direct band gaps

Pressure dependence of optical transitions in ordered GaP/InP superlattices

Predicion of charge separation in GaAs/AlAs cylindrical Russian Doll nanostructures

Density Functional Thermodynamics Description of Spin, Phonon and Displacement Degrees of Freedom in Antiferromagnetic-to-Paramagnetic Phase Transition in YNiO3

Applicability of the local-density theory to interstitial transition-metal impurities in silicon