title: Implementation and Validation of Fully Relativistic GW Calculations: Spin-Orbit Coupling in Molecules, Nanocrystals, and Solids.
abstract: We present an implementation of G0W0 calculations including spin-orbit coupling (SOC) enabling investigations of large systems, with thousands of electrons, and we discuss results for molecules, solids, and nanocrystals. Using a newly developed set of molecules with heavy elements (called GW-SOC81), we find that, when based upon hybrid density functional calculations, fully relativistic (FR) and scalar-relativistic (SR) G0W0 calculations of vertical ionization potentials both yield excellent performance compared to experiment, with errors below 1.9%. We demonstrate that while SR calculations have higher random errors, FR calculations systematically underestimate the VIP by 0.1 to 0.2 eV. We further verify that SOC effects may be well approximated at the FR density functional level and then added to SR G0W0 results for a broad class of systems. We also address the use of different root-finding algorithms for the G0W0 quasiparticle equation and the significant influence of including d electrons in the valence partition of the pseudopotential for G0W0 calculations. Finally, we present statistical analyses of our data, highlighting the importance of separating definitive improvements from those that may occur by chance due to a limited number of samples. We suggest the statistical analyses used here will be useful in the assessment of the accuracy of a large variety of electronic structure methods.
authors.affiliation: Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Peter
authors.initials: P
authors.lastname: Scherpelz
authors.affiliation: Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.|Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Marco
authors.initials: M
authors.lastname: Govoni
authors.affiliation: International Center for Materials Nanoarchitectonics, Global Research Center for Environment and Energy based on Nanomaterials Science, and Center for Materials Research by Information Integration, National Institute for Materials Science , 1-1 Namiki, Tsukuba 305-0044, Japan.
authors.forename: Ikutaro
authors.initials: I
authors.lastname: Hamada
authors.affiliation: Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.|Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Giulia
authors.initials: G
authors.lastname: Galli