Benchmarking Nonequilibrium Green's Functions against Configuration Interaction for time-dependent Auger decay processes

We have recently proposed a Nonequilibrium Green's Function (NEGF) approach to include Auger decay processes in the ultrafast charge dynamics of photoionized molecules. Within the so called Generalized Kadanoff-Baym Ansatz the fundamental unknowns of the NEGF equations are the reduced one-particle density matrix of bound electrons and the occupations of the continuum states. Both unknowns are one-time functions like the density in Time-Dependent Functional Theory (TDDFT). In this work we assess the accuracy of the approach against Configuration Interaction (CI) calculations in one-dimensional model systems. Our results show that NEGF correctly captures qualitative and quantitative features of the relaxation dynamics provided that the energy of the Auger electron is much larger than the Coulomb repulsion between two holes in the valence shells. For the accuracy of the results dynamical electron-electron correlations or, equivalently, memory effects play a pivotal role. The combination of our NEGF approach with the Sham-Schl\"uter equation may provide useful insights for the development of TDDFT exchange-correlation potentials with a history dependence.Comment: 7 pages, 3 figure

Optical absorption in small BN and C nanotubes

We present a theoretical study of the optical absorption spectrum of small boron-nitride and carbon nanotubes using time-dependent density-functional theory and the random phase approximation. Both for C and BN tubes, the absorption of light polarized perpendicular to the tube-axis is strongly suppressed due to local field effects. Since BN-tubes are wide band-gap insulators, they only absorb in the ultra-violet energy regime, independently of chirality and diameter. In comparison with the spectra of the single C and BN-sheets, the tubes display additional fine-structure which stems from the (quasi-) one-dimensionality of the tubes and sensitively depends on the chirality and tube diameter. This fine structure can provide additional information for the assignment of tube indices in high resolution optical absorption spectroscopy.Comment: 5 pages, 3 figure

Transient charge and energy flow in the wide-band limit

The wide-band limit is a commonly used approximation to analyze transport through nanoscale devices. In this work we investigate its applicability to the study of charge and heat transport through molecular break junctions exposed to voltage biases and temperature gradients. We find that while this approximation faithfully describes the long-time charge and heat transport, it fails to characterize the short-time behavior of the junction. In particular, we find that the charge current flowing through the device shows a discontinuity when a temperature gradient is applied, while the energy flow is discontinuous when a voltage bias is switched on and even diverges when the junction is exposed to both a temperature gradient and a voltage bias. We provide an explanation for this pathological behavior and propose two possible solutions to this problem.Comment: 11 pages, 9 figure

Time-dependent density functional theory on a lattice

A time-dependent density functional theory (TDDFT) for a quantum many-body system on a lattice is formulated rigorously. We prove the uniqueness of the density-to-potential mapping and demonstrate that a given density is $v$-representable if the initial many-body state and the density satisfy certain well defined conditions. In particular, we show that for a system evolving from its ground state any density with a continuous second time derivative is $v$-representable and therefore the lattice TDDFT is guaranteed to exist. The TDDFT existence and uniqueness theorem is valid for any connected lattice, independently of its size, geometry and/or spatial dimensionality. The general statements of the existence theorem are illustrated on a pedagogical exactly solvable example which displays all details and subtleties of the proof in a transparent form. In conclusion we briefly discuss remaining open problems and directions for a future research.Comment: 12 pages, 1 figur

Direct estimation of electron density in the Orion Bar PDR from mm-wave carbon recombination lines

A significant fraction of the molecular gas in star-forming regions is irradiated by stellar UV photons. In these environments, the electron density (n_e) plays a critical role in the gas dynamics, chemistry, and collisional excitation of certain molecules. We determine n_e in the prototypical strongly irradiated photodissociation region (PDR), the Orion Bar, from the detection of new millimeter-wave carbon recombination lines (mmCRLs) and existing far-IR [13CII] hyperfine line observations. We detect 12 mmCRLs (including alpha, beta, and gamma transitions) observed with the IRAM 30m telescope, at ~25'' angular resolution, toward the H/H2 dissociation front (DF) of the Bar. We also present a mmCRL emission cut across the PDR. These lines trace the C+/C/CO gas transition layer. As the much lower frequency carbon radio recombination lines, mmCRLs arise from neutral PDR gas and not from ionized gas in the adjacent HII region. This is readily seen from their narrow line profiles (dv=2.6+/-0.4 km/s) and line peak LSR velocities (v_LSR=+10.7+/-0.2 km/s). Optically thin [13CII] hyperfine lines and molecular lines - emitted close to the DF by trace species such as reactive ions CO+ and HOC+ - show the same line profiles. We use non-LTE excitation models of [13CII] and mmCRLs and derive n_e = 60-100 cm^-3 and T_e = 500-600 K toward the DF. The inferred electron densities are high, up to an order of magnitude higher than previously thought. They provide a lower limit to the gas thermal pressure at the PDR edge without using molecular tracers. We obtain P_th > (2-4)x10^8 cm^-3 K assuming that the electron abundance is equal or lower than the gas-phase elemental abundance of carbon. Such elevated thermal pressures leave little room for magnetic pressure support and agree with a scenario in which the PDR photoevaporates.Comment: Accepted for publication in A&A Letters (includes language editor corrections