Increasing thermoelectric performance using coherent transport

We show that coherent electron transport through zero-dimensional systems can be used to tailor the shape of the system's transmission function. This quantum-engineering approach can be used to enhance the performance of quantum dots or molecules in thermal-to-electric power conversion. Specifically, we show that electron interference in a two-level system can substantially improve the maximum thermoelectric power and the efficiency at maximum power by suppressing parasitic charge flow near the Fermi energy, and by reducing electronic heat conduction. We discuss possible realizations of this approach in molecular junctions or quantum dots.Comment: 4+ pages, 4 figure

Correlation-induced conductance suppression at level degeneracy in a quantum dot

The large, level-dependent g-factors in an InSb nanowire quantum dot allow for the occurrence of a variety of level crossings in the dot. While we observe the standard conductance enhancement in the Coulomb blockade region for aligned levels with different spins due to the Kondo effect, a vanishing of the conductance is found at the alignment of levels with equal spins. This conductance suppression appears as a canyon cutting through the web of direct tunneling lines and an enclosed Coulomb blockade region. In the center of the Coulomb blockade region, we observe the predicted correlation-induced resonance, which now turns out to be part of a larger scenario. Our findings are supported by numerical and analytical calculations.Comment: 5 pages, 4 figure

Multi-Orbital Molecular Compound (TTM-TTP)I_3: Effective Model and Fragment Decomposition

The electronic structure of the molecular compound (TTM-TTP)I_3, which exhibits a peculiar intra-molecular charge ordering, has been studied using multi-configuration ab initio calculations. First we derive an effective Hubbard-type model based on the molecular orbitals (MOs) of TTM-TTP; we set up a two-orbital Hamiltonian for the two MOs near the Fermi energy and determine its full parameters: the transfer integrals, the Coulomb and exchange interactions. The tight-binding band structure obtained from these transfer integrals is consistent with the result of the direct band calculation based on density functional theory. Then, by decomposing the frontier MOs into two parts, i.e., fragments, we find that the stacked TTM-TTP molecules can be described by a two-leg ladder model, while the inter-fragment Coulomb energies are scaled to the inverse of their distances. This result indicates that the fragment picture that we proposed earlier [M.-L. Bonnet et al.: J. Chem. Phys. 132 (2010) 214705] successfully describes the low-energy properties of this compound.Comment: 5 pages, 4 figures, published versio

Yb2+-doped SrCl2: electronic structure of impurity states and impurity-trapped excitons

First-principles electronic structure calculations of the excited states of Yb2+-doped Sr Cl2 crystals up to 65 000 cm-1 reveal the existence of unexpected excited states with double-well potential energy surfaces and dual electronic structure lying above and very close in energy to the 4f 135d  manifold, with which they interact strongly through spin-orbit coupling. The double-well energy curves result from avoided crossings between Yb-trapped exciton states (more stable at short Yb–Cl distances) and 4f 136s impurity states (more stable at long Yb–Cl distances); the former are found to be preionization states in which the impurity holds the excited electron in close lying empty interstitials located outside the YbCl8 moiety. Spin-orbit coupling between the double-well states and the lower lying 4f 135d  impurity states spreads the dual electronic structure character to lower energies and, hence, the instability of the divalent oxidation state is also spread. To some extent, the dual electronic structure (impurity-trapped exciton–impurity state) of some excited states expresses and gives support to hypotheses of interaction between Yb2+ and Yb3+ pairs proposed to understand the complex spectroscopy of the material and conciliates these hypotheses with interpretations in terms of the existence of only one type of Yb2+ defect. The results presented confirm the presence of impurity states of the 4f 136s configuration among the 4f 135d manifolds, as proposed in literature, but their energies are very different from those assumed. The Yb-trapped excitons found in this chloride host can be seen as precursors of the luminescent Yb-trapped excitons characterized experimentally in the isomorphous SrF2 crystals

γ-Secretase modulators show selectivity for γ-secretase–mediated amyloid precursor protein intramembrane processing

The aggregation of β-amyloid peptide 42 results in the formation of toxic oligomers and plaques, which plays a pivotal role in Alzheimer's disease pathogenesis. Aβ42 is one of several Aβ peptides, all of Aβ30 to Aβ43 that are produced as a result of γ-secretase–mediated regulated intramembrane proteolysis of the amyloid precursor protein. γ-Secretase modulators (GSMs) represent a promising class of Aβ42-lowering anti-amyloidogenic compounds for the treatment of AD. Gamma-secretase modulators change the relative proportion of secreted Aβ peptides, while sparing the γ-secretase–mediated processing event resulting in the release of the cytoplasmic APP intracellular domain. In this study, we have characterized how GSMs affect the γ-secretase cleavage of three γ-secretase substrates, E-cadherin, ephrin type A receptor 4 (EphA4) and ephrin type B receptor 2 (EphB2), which all are implicated in important contexts of cell signalling. By using a reporter gene assay, we demonstrate that the γ-secretase–dependent generation of EphA4 and EphB2 intracellular domains is unaffected by GSMs. We also show that γ-secretase processing of EphA4 and EphB2 results in the release of several Aβ-like peptides, but that only the production of Aβ-like proteins from EphA4 is modulated by GSMs, but with an order of magnitude lower potency as compared to Aβ modulation. Collectively, these results suggest that GSMs are selective for γ-secretase–mediated Aβ production

On ordinal utility, cardinal utility, and random utility

Though the Random Utility Model (RUM) was conceived  entirely in terms of ordinal utility, the apparatus throughwhich it is widely practised exhibits properties of  cardinal utility.  The adoption of cardinal utility as a  working operation of ordinal is perfectly valid, provided  interpretations drawn from that operation remain faithful  to ordinal utility.  The paper considers whether the latterrequirement holds true for several measurements commonly  derived from RUM.  In particular it is found that  measurements of consumer surplus change may depart from  ordinal utility, and exploit the cardinality inherent in  the practical apparatus.

Heat dissipation in atomic-scale junctions

Atomic and single-molecule junctions represent the ultimate limit to the miniaturization of electrical circuits. They are also ideal platforms to test quantum transport theories that are required to describe charge and energy transfer in novel functional nanodevices. Recent work has successfully probed electric and thermoelectric phenomena in atomic-scale junctions. However, heat dissipation and transport in atomic-scale devices remain poorly characterized due to experimental challenges. Here, using custom-fabricated scanning probes with integrated nanoscale thermocouples, we show that heat dissipation in the electrodes of molecular junctions, whose transmission characteristics are strongly dependent on energy, is asymmetric, i.e. unequal and dependent on both the bias polarity and the identity of majority charge carriers (electrons vs. holes). In contrast, atomic junctions whose transmission characteristics show weak energy dependence do not exhibit appreciable asymmetry. Our results unambiguously relate the electronic transmission characteristics of atomic-scale junctions to their heat dissipation properties establishing a framework for understanding heat dissipation in a range of mesoscopic systems where transport is elastic. We anticipate that the techniques established here will enable the study of Peltier effects at the atomic scale, a field that has been barely explored experimentally despite interesting theoretical predictions. Furthermore, the experimental advances described here are also expected to enable the study of heat transport in atomic and molecular junctions, which is an important and challenging scientific and technological goal that has remained elusive.Comment: supporting information available in the journal web site or upon reques

A linear nonequilibrium thermodynamics approach to optimization of thermoelectric devices

Improvement of thermoelectric systems in terms of performance and range of applications relies on progress in materials science and optimization of device operation. In this chapter, we focuse on optimization by taking into account the interaction of the system with its environment. For this purpose, we consider the illustrative case of a thermoelectric generator coupled to two temperature baths via heat exchangers characterized by a thermal resistance, and we analyze its working conditions. Our main message is that both electrical and thermal impedance matching conditions must be met for optimal device performance. Our analysis is fundamentally based on linear nonequilibrium thermodynamics using the force-flux formalism. An outlook on mesoscopic systems is also given.Comment: Chapter 14 in "Thermoelectric Nanomaterials", Editors Kunihito Koumoto and Takao Mori, Springer Series in Materials Science Volume 182 (2013

On the possibility of magneto-structural correlations: detailed studies of di-nickel carboxylate complexes

A series of water-bridged dinickel complexes of the general formula [Ni<sub>2</sub>(μ<sub>2</sub>-OH<sub>2</sub>)(μ2- O<sub>2</sub>C<sup>t</sup>Bu)<sub>2</sub>(O<sub>2</sub>C<sup>t</sup>Bu)2(L)(L0)] (L = HO<sub>2</sub>C<sup>t</sup>Bu, L0 = HO<sub>2</sub>C<sup>t</sup>Bu (1), pyridine (2), 3-methylpyridine (4); L = L0 = pyridine (3), 3-methylpyridine (5)) has been synthesized and structurally characterized by X-ray crystallography. The magnetic properties have been probed by magnetometry and EPR spectroscopy, and detailed measurements show that the axial zero-field splitting, D, of the nickel(ii) ions is on the same order as the isotropic exchange interaction, J, between the nickel sites. The isotropic exchange interaction can be related to the angle between the nickel centers and the bridging water molecule, while the magnitude of D can be related to the coordination sphere at the nickel sites