Exact density-functional potentials for time-dependent quasiparticles.

We calculate the exact Kohn-Sham potential that describes, within time-dependent density-functional theory, the propagation of an electron quasiparticle wave packet of nonzero crystal momentum added to a ground-state model semiconductor. The potential is observed to have a highly nonlocal functional dependence on the charge density, in both space and time, giving rise to features entirely lacking in local or adiabatic approximations. The dependence of the nonequilibrium part of the Kohn-Sham electric field on the local current and charge density is identified as a key element of the correct Kohn-Sham functional.

Functionality in single-molecule devices: model calculations and applications of the inelastic electron tunneling signal in molecular junctions.

We analyze how functionality could be obtained within single-molecule devices by using a combination of non-equilibrium Green's functions and ab initio calculations to study the inelastic transport properties of single-molecule junctions. First, we apply a full non-equilibrium Green's function technique to a model system with electron-vibration coupling. We show that the features in the inelastic electron tunneling spectra (IETS) of the molecular junctions are virtually independent of the nature of the molecule-lead contacts. Since the contacts are not easily reproducible from one device to another, this is a very useful property. The IETS signal is much more robust versus modifications at the contacts and hence can be used to build functional nanodevices. Second, we consider a realistic model of a organic conjugated molecule. We use ab initio calculations to study how the vibronic properties of the molecule can be controlled by an external electric field which acts as a gate voltage. The control, through the gate voltage, of the vibron frequencies and (more importantly) of the electron-vibron coupling enables the construction of functionality: nonlinear amplification and/or switching is obtained from the IETS signal within a single-molecule device.

Nonequilibrium electronic structure of interacting single-molecule nanojunctions: vertex corrections and polarization effects for the electron-vibron coupling.

We consider the interaction between electrons and molecular vibrations in the context of electronic transport in nanoscale devices. We present a method based on nonequilibrium Green's functions to calculate both equilibrium and nonequilibrium electronic properties of a single-molecule junction in the presence of electron-vibron interactions. We apply our method to a model system consisting of a single electronic level coupled to a single vibration mode in the molecule, which is in contact with two electron reservoirs. Higher-order diagrams beyond the usual self-consistent Born approximation (SCBA) are included in the calculations. In this paper we consider the effects of the double-exchange diagram and the diagram in which the vibron propagator is renormalized by one electron-hole bubble. We study in detail the effects of the first- and second-order diagrams on the spectral functions for a large set of parameters and for different transport regimes (resonant and off-resonant cases), both at equilibrium and in the presence of a finite applied bias. We also study the linear response (linear conductance) of the nanojunction for all the different regimes. We find that it is indeed necessary to go beyond the SCBA in order to obtain correct results for a wide range of parameters.

First-principles conductance of nanoscale junctions from the polarizability of finite systems.

A method for the calculation of the conductance of nanoscale electrical junctions is extended to ab initio electronic structure methods that make use of the periodic supercell technique and applied to realistic models of metallic wires and break junctions of sodium and gold. The method is systematically controllable and convergeable and can be straightforwardly extended to include more complex processes and interactions. Important issues, about the order in which the thermodynamic and static (small field) limits are taken, are clarified, and characterized further through comparisons to model systems.

Electron localisation in static and time-dependent one-dimensional model systems.

The most direct signature of electron localisation is the tendency of an electron in a many-body system to exclude other same-spin electrons from its vicinity. By applying this concept directly to the exact many-body wavefunction, we find that localisation can vary considerably between different ground-state systems, and can also be strongly disrupted, as a function of time, when a system is driven by an applied electric field. We use this measure to assess the well-known electron localisation function (ELF), both in its approximate single-particle form (often applied within density-functional theory) and its full many-particle form. The full ELF always gives an excellent description of localisation, but the approximate ELF fails in time-dependent situations, even when the exact Kohn-Sham orbitals are employed.

Stroboscopic wave-packet description of nonequilibrium many-electron problems.

We introduce the construction of an orthogonal wave-packet basis set, using the concept of stroboscopic time propagation, tailored to the efficient description of nonequilibrium extended electronic systems. Thanks to three desirable properties of this basis, significant insight is provided into nonequilibrium processes (both time-dependent and steady-state), and reliable physical estimates of various many-electron quantities such as density, current, and spin polarization can be obtained. Use of the wave-packet basis provides new results for time-dependent switching-on of the bias in quantum transport, and for current-induced spin accumulation at the edge of a 2D doped semiconductor caused by edge-induced spin-orbit interaction.

Efficient total energy calculations from self-energy models.

We propose a new method for calculating total energies of systems of interacting electrons, which requires little more computational resources than standard density-functional theories. The total energy is calculated within the framework of many-body perturbation theory by using an efficient model of the self-energy, that nevertheless retains the main features of the exact operator. The method shows promising performance when tested against quantum Monte Carlo results for the linear response of the homogeneous electron gas and structural properties of bulk silicon.

Many-body GW calculations of ground-state properties: quasi-2D electron systems and van der Waals forces.

We present GW many-body results for ground-state properties of two simple but very distinct families of inhomogeneous systems in which traditional implementations of density-functional theory (DFT) fail drastically. The GW approach gives notably better results than the well-known random-phase approximation, at a similar computational cost. These results establish GW as a superior alternative to standard DFT schemes without the expensive numerical effort required by quantum Monte Carlo simulations.