Development of Novel Density Functionals for Thermochemical Kinetics

A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for transition state barriers but, unlike previous attempts at such a functional, this improved accuracy does not come at the expense of equilibrium properties. This makes it a general-purpose functional whose domain of applicability has been extended to transition states, rather than a specialized functional for kinetics. The improvement in BMK rests on the inclusion of the kinetic energy density together with a large value of the exact exchange mixing coefficient. For this functional, the kinetic energy density appears to correct `back' the excess exact exchange mixing for ground-state properties, possibly simulating variable exchange.Comment: J. Chem. Phys., in press (303431JCP, scheduled for August 15, 2004 issue); supplementary data available at http://theochem.weizmann.ac.il/web/papers/BMK.htm

From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia

The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liquid ammonia to judge its performance in describing the associated liquid. Both the HCTH/407+ and BLYP functionals describe the properties of the liquid well as judged by analysis of radial distribution functions, hydrogen bonding structure and dynamics, translational diffusion, and orientational relaxation processes. It is demonstrated that the solvation shell of the ammonia molecule in the liquid phase is dominated by steric packing effects and not so much by directional hydrogen bonding interactions. In addition, the propensity of ammonia molecules to form bifurcated and multifurcated hydrogen bonds in the liquid phase is found to be negligibly small.Comment: Journal of Chemical Physics, in press (305335JCP

Finite-size effects in tunneling between parallel quantum wires

We present theoretical calculations and experimental measurements which reveal finite-size effects in the tunneling between two parallel quantum wires, fabricated at the cleaved edge of a GaAs/AlGaAs bilayer heterostructure. Observed oscillations in the differential conductance, as a function of bias voltage and applied magnetic field, provide direct information on the shape of the confining potential. Superimposed modulations indicate the existence of two distinct excitation velocities, as expected from spin-charge separation.Comment: Accepted to Phys. Rev. Lett. 7/200

Influence of nano-mechanical properties on single electron tunneling: A vibrating Single-Electron Transistor

We describe single electron tunneling through molecular structures under the influence of nano-mechanical excitations. We develop a full quantum mechanical model, which includes charging effects and dissipation, and apply it to the vibrating C$_{60}$ single electron transistor experiment by Park {\em et al.} {[Nature {\bf 407}, 57 (2000)].} We find good agreement and argue vibrations to be essential to molecular electronic systems. We propose a mechanism to realize negative differential conductance using local bosonic excitations.Comment: 7 pages, 6 figure

Mechanical Cooper pair transportation as a source of long distance superconducting phase coherence

Transportation of Cooper-pairs by a movable single Cooper-pair-box placed between two remote superconductors is shown to establish coherent coupling between them. This coupling is due to entanglement of the movable box with the leads and is manifested in the supression of quantum fluctuations of the relative phase of the order parameters of the leads. It can be probed by attaching a high resistance Josephson junction between the leads and measuring the current through this junction. The current is suppressed with increasing temperature.Comment: 4 pages, 4 figures, RevTeX; Updated version, typos correcte

Carbon–water flux coupling under progressive drought

Water-use efficiency, defined as the ratio of carbon assimilation over evapotranspiration (ET), is a key metric to assess ecosystem functioning in response to environmental conditions. It remains unclear which factors control this ratio during periods of extended water-limitation, and current semi-empirical water-use efficiency models fail to reproduce observed ET dynamics for these periods. Here, we use dry-down events occurring at eddy-covariance flux tower sites in the FLUXNET database as natural experiments to assess if and how decreasing soil-water availability modifies water-use efficiency on ecosystem scale. We demonstrate that an attenuating soil-water availability factor in junction with a previously discovered additive radiation term is necessary to accurately predict ET flux magnitudes and dry-down lengths of these water-limited periods. In an analysis of the attenuation, 20–33% of the observed decline in ET was due to the previously unconsidered soil-water availability effect. We conclude by noting the rates of ET decline differ significantly between FLUXNET sites with tall and short vegetation types and discuss the dependency of this rate on the variability of seasonal dryness

Phonon distributions of a single bath mode coupled to a quantum dot

The properties of an unconventional, single mode phonon bath coupled to a quantum dot, are investigated within the rotating wave approximation. The electron current through the dot induces an out of equilibrium bath, with a phonon distribution qualitatively different from the thermal one. In selected transport regimes, such a distribution is characterized by a peculiar selective population of few phonon modes and can exhibit a sub-Poissonian behavior. It is shown that such a sub-Poissonian behavior is favored by a double occupancy of the dot. The crossover from a unequilibrated to a conventional thermal bath is explored, and the limitations of the rotating wave approximation are discussed.Comment: 21 Pages, 7 figures, to appear in New Journal of Physics - Focus on Quantum Dissipation in Unconventional Environment

Thermoelectric effects in Kondo correlated quantum dots

In this Letter we study thermoelectric effects in ultra small quantum dots. We study the behaviour of the thermopower, Peltier coefficient and thermal conductance both in the sequencial tunneling regime and in the regime where Kondo correlations develope. Both cases of linear response and non-equilibrium induced by strong temperature gradients are considered. The thermopower is a very sensitive tool to detect Kondo correlations. It changes sign both as a function of temperature and temperature gradient. We also discuss violations of the Wiedemann-Franz law.Comment: 7 pages; 5 figure