Time and energy-resolved two photon-photoemission of the Cu(100) and Cu(111) metal surfaces

We present calculations on energy- and time-resolved two-photon photoemission spectra of images states in Cu(100) and Cu(111) surfaces. The surface is modeled by a 1D effective potential and the states are propagated within a real-space, real-time method. To obtain the energy resolved spectra we employ a geometrical approach based on a subdivision of space into two regions. We treat electronic inelastic effects by taking into account the scattering rates calculated within a GW scheme. To get further insight into the decaying mechanism we have also studied the effect of the variation of the classical Hartree potential during the excitation. This effect turns out to be small.Comment: 11 pages, 7 figure

A TDDFT study of the excited states of DNA bases and their assemblies

We present a detailed study of the optical absorption spectra of DNA bases and base pairs, carried out by means of time dependent density functional theory. The spectra for the isolated bases are compared to available theoretical and experimental data and used to assess the accuracy of the method and the quality of the exchange-correlation functional: Our approach turns out to be a reliable tool to describe the response of the nucleobases. Furthermore, we analyze in detail the impact of hydrogen bonding and $\pi$-stacking in the calculated spectra for both Watson-Crick base pairs and Watson-Crick stacked assemblies. We show that the reduction of the UV absorption intensity (hypochromicity) for light polarized along the base-pair plane depends strongly on the type of interaction. For light polarized perpendicular to the basal plane, the hypochromicity effect is reduced, but another characteristic is found, namely a blue shift of the optical spectrum of the base-assembly compared to that of the isolated bases. The use of optical tools as fingerprints for the characterization of the structure (and type of interaction) is extensively discussed.Comment: 31 pages, 8 figure

A monolayer transition-metal dichalcogenide as a topological excitonic insulator

Monolayer transition-metal dichalcogenides in the T\u2032 phase could enable the realization of the quantum spin Hall effect1 at room temperature, because they exhibit a prominent spin\u2013orbit gap between inverted bands in the bulk2,3. Here we show that the binding energy of electron\u2013hole pairs excited through this gap is larger than the gap itself in the paradigmatic case of monolayer T\u2032 MoS2, which we investigate from first principles using many-body perturbation theory4. This paradoxical result hints at the instability of the T\u2032 phase in the presence of spontaneous generation of excitons, and we predict that it will give rise to a reconstructed \u2018excitonic insulator\u2019 ground state5\u20137. Importantly, we show that in this monolayer system, topological and excitonic order cooperatively enhance the bulk gap by breaking the crystal inversion symmetry, in contrast to the case of bilayers8\u201316 where the frustration between the two orders is relieved by breaking time reversal symmetry13,15,16. The excitonic topological insulator is distinct from the bare topological phase because it lifts the band spin degeneracy, which results in circular dichroism. A moderate biaxial strain applied to the system leads to two additional excitonic phases, different in their topological character but both ferroelectric17,18 as an effect of electron\u2013electron interaction

Spin-polarized stable phases of the 2-D electron fluid at finite temperatures

The Helmholtz free energy F of the interacting 2-D electron fluid is calculated nonperturbatively using a mapping of the quantum fluid to a classical Coulomb fluid [Phys. Rev. Letters, vol. 87, 206404 (2001)]. For density parameters rs such that rs<~25, the fluid is unpolarized at all temperatures t=T/EF where EF is the Fermi energy. For lower densities, the system becomes fully spin polarized for t<~0.35, and partially polarized for 0.35<t< 2, depending on the density. At rs ~25-30, and t ~0.35, an ''ambispin'' phase where F is almost independent of the spin polarization is found. These results support recent claims, based on quantum Monte Carlo results, for a stable, fully spin-polarized fluid phase at T = 0 for rs larger than about 25-26.Comment: Latex manuscript (4-5 pages) and two postscript figures; see also http://nrcphy1.phy.nrc.ca/ims/qp/chandre/chnc

Photo-excitation of a light-harvesting supra-molecular triad: a Time-Dependent DFT study

We present the first time-dependent density-functional theory (TDDFT) calculation on a light harvesting triad carotenoid-diaryl-porphyrin-C60. Besides the numerical challenge that the ab initio study of the electronic structure of such a large system presents, we show that TDDFT is able to provide an accurate description of the excited state properties of the system. In particular we calculate the photo-absorption spectrum of the supra-molecular assembly, and we provide an interpretation of the photo-excitation mechanism in terms of the properties of the component moieties. The spectrum is in good agreement with experimental data, and provides useful insight on the photo-induced charge transfer mechanism which characterizes the system.Comment: Accepted for publication on JPC, March 09th 200

Ab-initio angle and energy resolved photoelectron spectroscopy with time-dependent density-functional theory

We present a time-dependent density-functional method able to describe the photoelectron spectrum of atoms and molecules when excited by laser pulses. This computationally feasible scheme is based on a geometrical partitioning that efficiently gives access to photoelectron spectroscopy in time-dependent density-functional calculations. By using a geometrical approach, we provide a simple description of momentum-resolved photoe- mission including multi-photon effects. The approach is validated by comparison with results in the literature and exact calculations. Furthermore, we present numerical photoelectron angular distributions for randomly oriented nitrogen molecules in a short near infrared intense laser pulse and helium-(I) angular spectra for aligned carbon monoxide and benzene.Comment: Accepted for publication on Phys. Rev.

Spin-Polarization transition in the two dimensional electron gas

We present a numerical study of magnetic phases of the 2D electron gas near freezing. The calculations are performed by diffusion Monte Carlo in the fixed node approximation. At variance with the 3D case we find no evidence for the stability of a partially polarized phase. With plane wave nodes in the trial function, the polarization transition takes place at Rs=20, whereas the best available estimates locate Wigner crystallization around Rs=35. Using an improved nodal structure, featuring optimized backflow correlations, we confirm the existence of a stability range for the polarized phase, although somewhat shrunk, at densities achievable nowadays in 2 dimensional hole gases in semiconductor heterostructures . The spin susceptibility of the unpolarized phase at the magnetic transition is approximately 30 times the Pauli susceptibility.Comment: 7 pages, 4 figure

Spin-density functional approach to thermodynamic and structural consistence in the charge and spin response of an electron gas

We use spin-density functional theory to obtain novel expressions for the charge and spin local-field factors of an electron gas in terms of its electron-pair structure factors. These expressions (i) satisfy the compressibility and spin susceptibility sum rules; (ii) keep account of kinetic correlations by means of an integration over the coupling strength; and (iii) provide a practical self-consistent scheme for evaluating linear response and liquid structure. Numerical illustrations are given for the dielectric response of the paramagnetic electron gas in both three and two dimensions.Comment: 9 pages, 3 figures, submitted to Solid State Commu

Electronic and optical properties of doped TiO2 by many-body perturbation theory

Doping is one of the most common strategies for improving the photocatalytic and solar energy conversion properties of TiO2, hence an accurate theoretical description of the electronic and optical properties of doped TiO2 is of both scientific and practical interest. In this work we use many-body perturbation theory techniques to investigate two typical n-type dopants, niobium and hydrogen, in TiO2 rutile. Using the GW approximation to determine band edges and defect energy levels, and the Bethe-Salpeter equation for the calculation of the absorption spectra, we find that the defect energy levels form nondispersive bands lying 3c2.2 eV above the top of the corresponding valence bands ( 3c0.9 eV below the conduction bands of the pristine material). The defect states are also responsible for the appearance of low-energy absorption peaks that enhance the solar spectrum absorption of rutile. The spatial distributions of the excitonic wave functions associated with these low-energy excitations are very different for the two dopants, suggesting a larger mobility of photoexcited electrons in Nb-TiO2

Effective interactions between parallel-spin electrons in two-dimensional jellium approaching the magnetic phase transition

We evaluate the effective interactions in a fluid of electrons moving in a plane, on the approach to the quantum phase transition from the paramagnetic to the fully spin-polarized phase that has been reported from Quantum Monte Carlo runs. We use the approach of Kukkonen and Overhauser to treat exchange and correlations under close constraints imposed by sum rules. We show that, as the paramagnetic fluid approaches the phase transition, the effective interactions at low momenta develop an attractive region between parallel-spin electrons and a corresponding repulsive region for antiparallel-spin electron pairs. A connection with the Hubbard model is made and used to estimate the magnetic energy gap and hence the temperature at which the phase transition may become observable with varying electron density in a semiconductor quantum well.Comment: 11 pages, 3 figure