Quasiparticle energy spectra of alkali-metal clusters: All-electron first-principles calculations

A good approximation to the one-electron self-energy operator in the calculation of quasiparticle energy spectra including the first ionization potential (IP) and electron affinity (EA) is to expand it as a simple product of a one-particle Green's function G and a dynamically screened Coulomb interaction W, namely, GW approximation. We developed a spin-polarized version of the all-electron GW approach and applied it to the first-principles calculation of quasiparticle energy spectra of alkali-metal clusters (Na(n) and K(n), n=1 -8). Our all-electron mixed basis approach, in which wave functions are expressed as a linear combination of numerical atomic orbitals and plane waves, enables us to compare the absolute values of the singly (or highest) occupied molecular orbital and the lowest unoccupied molecular orbital levels with available experimental IPs and EAs. The agreements with the corresponding experimental values are fairly good. Comparing with the non-spin-polarized results of Na(2n) and K(2n) (n=1 -4), we discuss the effect of spin polarization as well as the cluster size dependence of IPs or EAs. (c) 2008 American Institute of Physics.