79 research outputs found

    Piecewise linearity in the GWGW approximation for accurate quasiparticle energy predictions

    Full text link
    We identify the deviation from the straight line error (DSLE) -- i.e., the spurious non-linearity of the total energy as a function of fractional particle number -- as the main source for the discrepancy between experimental vertical ionization energies and theoretical quasiparticle energies, as obtained from the GWGW and GWGW+SOSEX approximations to many-body perturbation theory (MBPT). For self-consistent calculations, we show that GWGW suffers from a small DSLE. Conversely, for perturbative G0W0G_0W_0 and G0W0G_0W_0+SOSEX calculations the DSLE depends on the starting point. We exploit this starting-point dependence to reduce (or completely eliminate) the DSLE. We find that the agreement with experiment increases as the DSLE reduces. DSLE-minimized schemes, thus, emerge as promising avenues for future developments in MBPT

    Measuring excitation-energy transfer with a real-time time-dependent density functional theory approach

    Full text link
    We investigate the time an electronic excitation travels in a supermolecular setup using a measurement process in an open quantum-system framework. The approach is based on the stochastic Schr\"odinger equation and uses a Hamiltonian from time-dependent density functional theory (TDDFT). It treats electronic-structure properties and intermolecular coupling on the level of TDDFT, while it opens a route to the description of dissipation and relaxation via a bath operator that couples to the dipole moment of the density. Within our study, we find that in supermolecular setups small deviations of the electronic structure from the perfectly resonant case have only minor influence on the pathways of excitation-energy transfer, thus lead to similar transfer times. Yet, sizable defects cause notable slowdown of the energy spread

    First steps towards achieving both ultranonlocality and a reliable description of electronic binding in a meta-generalized gradient approximation

    Get PDF
    It has been demonstrated that a meta-generalized gradient approximation (meta-GGA) to the exchange-correlation energy of density functional theory can show a pronounced derivative discontinuity and significant ultranonlocality similar to exact exchange, and can accurately predict the band gaps of many solids. We here investigate whether within the meta-GGA form these properties are compatible with a reasonable accuracy for electronic binding energies. With the help of two transparent and inexpensive correlation functional constructions we demonstrate that this is the case. We report atomization energies, show that reliable bond lengths are obtained for many systems, and find promising results for reaction barrier heights, while keeping the strong derivative discontinuity and ultranonlocality, and thus accuracy for band gaps

    Magnetic moment quenching in small Pd clusters in solution

    Get PDF
    Small palladium clusters in vacuum show pronounced magnetic moments. With the help of Born–Oppenheimer molecular dynamics simulations based on density functional theory, we investigate for the paradigmatic examples of the Pd13_{13} and the Pd8_8 cluster whether these magnetic moments prevail when the clusters are solvated. Our results show that the interaction with acetophenone quenches the magnetic moment. The reduction of the magnetic moment is a direct consequence of the electronic interaction between the Pd clusters and the solvent molecules, and not an indirect effect due to a different cluster geometry being stabilized by the solvation shell

    Photoelectron spectra of anionic sodium clusters from time-dependent density-functional theory in real-time

    Full text link
    We calculate the excitation energies of small neutral sodium clusters in the framework of time-dependent density-functional theory. In the presented calculations, we extract these energies from the power spectra of the dipole and quadrupole signals that result from a real-time and real-space propagation. For comparison with measured photoelectron spectra, we use the ionic configurations of the corresponding single-charged anions. Our calculations clearly improve on earlier results for photoelectron spectra obtained from static Kohn-Sham eigenvalues

    Simple iterative construction of the optimized effective potential for orbital functionals, including exact exchange

    Full text link
    For exchange-correlation functionals that depend explicitly on the Kohn-Sham orbitals, the potential V_{\mathrm{xc}\sigma}(\re) must be obtained as the solution of the optimized effective potential (OEP) integral equation. This is very demanding and has limited the use of orbital functionals like exact exchange. We demonstrate that the OEP can be obtained iteratively by solving a system of partial differential equations instead of an integral equation. This amounts to calculating the orbital shifts that exactify the Krieger-Li-Iafrate (KLI) approximation. Unoccupied orbitals do not need to be calculated. Accuracy and efficiency of the method are shown for atoms and clusters using the exact exchange energy. Counter-intuitive asymptotic limits of the exact OEP, not accessible from previous constructions, are presented.Comment: Physical Review Letters, accepted for publication. 4 pages, 1 figur
    • …
    corecore