Systematic calculations of the band structures of the rare-gas crystals neon, argon, krypton, and xenon

Abstract

Scalar relativistic self-consistent calculations of the band structure of Ne, Ar, Kr, and Xe have been performed with the augmented-plane-wave method using the Hedin-Lundqvist local-density (LD) expression for exchange and correlation. The trends with increasing atomic number in this inert-gas solid series are presented for the valence-band width, LD band gap, and for low-lying conduction-band eigenvalues. A simplified form of self-energy correction that accounts for dynamical exchange and correlation processes to the single-particle excitations is included. Comparisons are made with previous studies using diferent methods. The present approach is most reliable for valence-band properties and gives semiquantitative agreement with experimental values of the band-gap and conduction-band separations.

Band structures of rare-gas solids within theGWapproximation

“…The symbols n c + n v , core, and n v denote whether core plus valence, core-only, or valence-only states are included in the operators. widths ϳ0.9 eV, which are smaller than the experimental value of 1.3 eV, 19 but are in agreement with the value of 0.99 eV obtained by Bacalis et al 2 The two methods used for core-valence decoupling ͑Table III, columns 5 and 6͒ result in ⌫ 15v and ⌫ 1c quasiparticle energies which differ by only ϳ0.05 eV.…”

“…Results in the fourth and fifth columns are from all electron projector augmented wave ͑PAW͒ calculations. 2 the PWGGA functional in this work, while the LDA was used in the latter. Replacing the PWGGA by the LDA in our calculation, the valence-band maximum shifts from −10.27 eV ͑see Table III͒ to −9.23 eV, while the conduction bands were nearly unaffected, leading to lowering of the band gap from 9.51 eV to 8.55 eV, which agrees reasonably well with value of 8.09 eV obtained by Bacalis et al 2 When DFT and quasiparticle energies for Ne at X and L points are compared ͑Table IV͒, we find a widening of the valence bands by approximately 30%.…”

“…2 the PWGGA functional in this work, while the LDA was used in the latter. Replacing the PWGGA by the LDA in our calculation, the valence-band maximum shifts from −10.27 eV ͑see Table III͒ to −9.23 eV, while the conduction bands were nearly unaffected, leading to lowering of the band gap from 9.51 eV to 8.55 eV, which agrees reasonably well with value of 8.09 eV obtained by Bacalis et al 2 When DFT and quasiparticle energies for Ne at X and L points are compared ͑Table IV͒, we find a widening of the valence bands by approximately 30%. Our results for valence band energies and widths are in very good agreement with those reported earlier by Bacalis et al 2 A similar pattern of valence band widening for GW valence bands in Ne is found in Ar, and our results are again in good agreement with those of Bacalis et al 2 The energy difference of the first and second conduction bands at the ⌫ point ͑⌫ 25c Ј − ⌫ 1c ͒ in our GW calculation is ϳ2 eV smaller than in the projector augmented wave ͑PAW͒ 2 calculation for Ne, while the value of 8.21 eV for Ar agrees well with the value of 8.44 eV obtained by Bacalis et al This energy difference is sensitive to completeness of Gaussian orbital basis sets ͑see the Appendix͒ as the ⌫ 25c Ј state has significant amplitude in octahedral interstitial regions.…”

“…8 Some of these studies have included correlation effects in the band structure via many-body perturbation theory. 1,2,5,7,9 In this paper we present results of ab initio all electron and pseudopotential many-body calculations of the band structures of solid Ne and Ar using Gaussian orbital basis sets. Band structures are calculated using the GW approximation [10][11][12][13] and the dependence of particle-hole gaps and electron affinities on basis set and treatment of core electrons is investigated.…”

3pvalence photoelectron spectrum of Ar clusters

“…Qualitatively, the shape of our large cluster spectrum also agrees with the density of states calculated by Bacalis et al [38], although this work shows a more structured appearance with two peaks, split by approx. 1.3 eV (1/10 Ry).…”