Exact-Exchange-Based Quasiparticle Calculations

Density Functional Theory Home

The description of excited states in solids is a challenging and important problem in condensed matter physics since excited states are needed to determine transport and optical properties of materials. Untill the mid-eighties, a commonly used way to determine, for example, band structures of materials was based on density functional theory in the Kohn-Sham formulation using the local density approximation. This approach maps the many-body problem onto a system of non-interacting, fictitious Kohn-Sham particles. While the eigenvalues that result from the solution of the single-particle Kohn-Sham equations have no physical meaning within the frame work of the theory they compare rather well with experiment. The most notable exception is the band gap of insulators which is generally 0.5 - 2.0 eV too small compared to experiment.

Very recently, new density functional methods have been presented in the literature whose energy gaps generally agree much better with experiment than the LDA. One such method, which has been studied in much detail for semiconductors, is the so-called exact-exchange density functional theory which allows the determination of the exact local Kohn-Sham potential. In particular, self-interaction errors due to incomplete cancellation of the self-Hartree and the self-exchange potentials are eliminated in exact exchange density functioanl theory. Using exact-exchange calculations in combination with LDA or generalized gradient approximation (GGA) correlation functionals leads to energy gaps and structural properties (lattice constant, cohesive energy, bulk modulus, etc.) of standard semiconductors that agree well with experiment.

An alternative way to describe the excited states of materials is provided by compuational many-body theory using the dynamically screened or GW approximation (GWA). In the GWA, the electronic self-energy, which describes exchange and correlation beyond the Hartree approximation, is expressed as the product of a single-particle propagator G and a screened interaction W. In principle, the GWA requires the self-consistent solution of a set of four coupled integral equations as is discussed in more detail in the paper. However, GWA calculations that are non-self-consistent, use LDA energies and wave functions as input, and neglect the imaginary part of the self-energy describe the experimental electronic structure of sp bonded semiconductors and insulators generally to within 0.1 to 0.5 eV.

Here we test the accuracy of wave functions and energies obtained using exact-exchange plus LDA correlation density functional calculations as input for quasiparticle calculations. We choose eight standard sp bonded semiconductors for our test. These provide a hard test, since LDA plus GWA calculations work very well in these systems. Overall, we find electronic energies that agree with LDA plus GWA calculations and experiment.

Talk on EXX-based quasiparticle calculations.
Paper on EXX-based quasiparticle calculations.

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Exact-Exchange-Based Quasiparticle Calculations
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Edited by: aulbur@mps.ohio-state.edu