Doping dependence of thermopower and thermoelectricity in strongly correlated systems

The search for semiconductors with high thermoelectric figure of merit has been greatly aided by theoretical modeling of electron and phonon transport, both in bulk materials and in nanocomposites. Recent experiments have studied thermoelectric transport in ``strongly correlated'' materials derived by doping Mott insulators, whose insulating behavior without doping results from electron-electron repulsion, rather than from band structure as in semiconductors. Here a unified theory of electrical and thermal transport in the atomic and ``Heikes'' limit is applied to understand recent transport experiments on sodium cobaltate and other doped Mott insulators at room temperature and above. For optimal electron filling, a broad class of narrow-bandwidth correlated materials are shown to have power factors (the electronic portion of the thermoelectric figure of merit) as high at and above room temperature as in the best semiconductors.Comment: 4 pages, 4 figure

Optimal thermoelectric figure of merit of a molecular junction

We show that a molecular junction can give large values of the thermoelectric figure of merit $ZT$, and so could be used as a solid state energy conversion device that operates close to the Carnot efficiency. The mechanism is similar to the Mahan-Sofo model for bulk thermoelectrics -- the Lorenz number goes to zero violating the Wiedemann-Franz law while the thermopower remains non-zero. The molecular state through which charge is transported must be weakly coupled to the leads, and the energy level of the state must be of order $k_B T$ away from the Fermi energy of the leads. In practice, the figure of merit is limited by the phonon thermal conductance; we show that the largest possible $ZT\sim(\tilde{G}_{th}^{ph})^{-1/2}$, where $\tilde{G}_{th}^{ph}$ is the phonon thermal conductance divided by the thermal conductance quantum.Comment: 4 pages, 2 figure

Signatures of integrability in charge and thermal transport in 1D quantum systems

Integrable and non-integrable systems have very different transport properties. In this work, we highlight these differences for specific one dimensional models of interacting lattice fermions using numerical exact diagonalization. We calculate the finite temperature adiabatic stiffness (or Drude weight) and isothermal stiffness (or ``Meissner'' stiffness) in electrical and thermal transport and also compute the complete momentum and frequency dependent dynamical conductivities $\sigma(q,\omega)$ and $\kappa(q,\omega)$. The Meissner stiffness goes to zero rapidly with system size for both integrable and non-integrable systems. The Drude weight shows signs of diffusion in the non-integrable system and ballistic behavior in the integrable system. The dynamical conductivities are also consistent with ballistic and diffusive behavior in the integrable and non-integrable systems respectively.Comment: 4 pages, 4 figure

Interactions of unconjugated bilirubin with vesicles, cyclodextrins and micelles: New modeling and the role of high pKa values

<p>Abstract</p> <p>Background</p> <p>Unconjugated bilirubin (UCB) is an unstable substance with very low aqueous solubility. Its aqueous pKa values affect many of its interactions, particularly their pH-dependence. A companion paper shows that only our prior solvent partition studies, leading to pKa values of 8.12 and 8.44, met all essential requirements for valid pKa determinations. Other published values, generally lower, some below 5.0, were shown to be invalid. The present work was designed to derive suitable models for interpreting published data on the pH-dependent binding of UCB with four agents, mentioned below, chosen because they are not, themselves, sensitive to changes in the pH range 4-10, and the data, mainly spectrometric, were of reasonable quality.</p> <p>Results</p> <p>These analyses indicated that the high pKa values, dianion dimerization constant and solubilities of UCB at various pH values, derived from our partition studies, along with literature-derived pH- and time-dependent supersaturation effects, were essential for constructing useful models that showed good qualitative, and sometimes quantitative, fits with the data. In contrast, published pKa values below 5.0 were highly incompatible with the data for all systems considered. The primary species of bound UCB in our models were: undissociated diacid for phosphatidylcholine, dianion for dodecyl maltoside micelles and cyclodextrins, and both monoanions and dianion for sodium taurocholate. The resulting binding versus pH profiles differed strikingly from each other.</p> <p>Conclusions</p> <p>The insights derived from these analyses should be helpful to explore and interpret UCB binding to more complex, pH-sensitive, physiological moieties, such as proteins or membranes, in order to understand its functions.</p

Revalidation and rationale for high pKa values of unconjugated bilirubin

<p>Abstract</p> <p>Background</p> <p>Our prior solvent partition analysis, published in 1992, yielded pKa values for unconjugated bilirubin of about 8.1 and 8.4, but these results have been challenged and studies by other methods have suggested pKa values below 5.0.</p> <p>Methods</p> <p>We repeated our published solvent partition studies, using ¹⁴C-unconjugated bilirubin highly purified by extraction of residual labeled impurities from CHCl₃into an aqueous buffer, pH 7.0. Partition ratios at six pH values from 5.0 to 9.0 were determined by radioassay and compared with our prior values obtained by diazo assay.</p> <p>Results</p> <p>At pH values ranging from 4.8 to 9.2, stable aqueous/chloroform ¹⁴C-partition ratios did not differ significantly from our published partition ratios based on diazo assay.</p> <p>Conclusion</p> <p>These results support the high pKa values of unconjugated bilirubin, above 8.0, derived from our earlier solvent partition study. In both studies, our measurements were based on the rapid analysis of clearly under-saturated solutions of highly-purified bilirubin over a wide pH range, using properly purified and preserved solvents. No previous direct estimate of the aqueous pKa values of unconjugated bilirubin meets all these preconditions. Three theoretical factors acting in combination, each related to the unique, extensive internal H-bonding of the -COOH groups, are proposed to support high pKa values of unconjugated bilirubin in water: a) donation of an H-bond from the -OH moiety of the -COOH group, which is broken on ionization; b) hindered solvation of the -COO^-group after ionization; and c) restricted rotation of the -COO^-and -COOH groups. Our findings and rationale rebut methodological and theoretical criticisms leveled against our prior work. High pKa values for unconjugated bilirubin dictate that: a) bilirubin diacid, which readily diffuses across membranes and can cause neurotoxicity, is the dominant unbound bilirubin species of unconjugated bilirubin in plasma at physiological pH; b) at the near-neutral pH range of gallbladder bile, the monoanion is the major unconjugated bilirubin anion present, concordant with the finding that the calcium bilirubinate precipitated in gallstones is the monoanion salt. Our conclusions are thus relevant to understanding bilirubin-induced neurological disease in severely jaundiced neonates and the precipitation of calcium bilirubinate salts in gallstones.</p

Review: Bilirubin pKa studies; new models and theories indicate high pKa values in water, dimethylformamide and DMSO

<p>Abstract</p> <p>Background</p> <p>Correct aqueous pKa values of unconjugated bilirubin (UCB), a poorly-soluble, unstable substance, are essential for understanding its functions. Our prior solvent partition studies, of unlabeled and [¹⁴C] UCB, indicated pKa values above 8.0. These high values were attributed to effects of internal H-bonding in UCB. Many earlier and subsequent studies have reported lower pKa values, some even below 5.0, which are often used to describe the behavior of UCB. We here review 18 published studies that assessed aqueous pKa values of UCB, critically evaluating their methodologies in relation to essential preconditions for valid pKa measurements (short-duration experiments with purified UCB below saturation and accounting for self-association of UCB).</p> <p>Results</p> <p>These re-assessments identified major deficiencies that invalidate the results of all but our partition studies. New theoretical modeling of UCB titrations shows remarkable, unexpected effects of self-association, yielding falsely low pKa estimates, and provides some rationalization of the titration anomalies. The titration behavior reported for a soluble thioether conjugate of UCB at high aqueous concentrations is shown to be highly anomalous. Theoretical re-interpretations of data in DMSO and dimethylformamide show that those indirectly-derived aqueous pKa values are unacceptable, and indicate new, high average pKa values for UCB in non-aqueous media (>11 in DMSO and, probably, >10 in dimethylformamide).</p> <p>Conclusions</p> <p>No reliable aqueous pKa values of UCB are available for comparison with our partition-derived results. A companion paper shows that only the high pKa values can explain the pH-dependence of UCB binding to phospholipids, cyclodextrins, and alkyl-glycoside and bile salt micelles.</p

Many-body localization in incommensurate models with a mobility edge

We review the physics of many-body localization in models with incommensurate potentials. In particular, we consider one-dimensional quasiperiodic models with single-particle mobility edges. Although a conventional perspective suggests that delocalized states act as a thermalizing bath for the localized states in the presence of of interactions, there is evidence that such systems can display non-ergodicity. This is in part due to the fact that the delocalized states do not have any kind of protection due to symmetry or topology and are thus susceptible to localization. A study of non-interacting incommensurate models shows that they admit extended, partially extended, and fully localized many-body states. These models cannot thermalize dynamically and remain localized upon the introduction of interactions. In particular, for a certain range of energy, the system can host a non-ergodic extended (i.e. metallic) phase in which the energy eigenstates violate the eigenstate thermalization hypothesis (ETH) but the entanglement entropy obeys volume-law scaling. The level statistics and entanglement growth also indicate the lack of ergodicity in these models. The phenomenon of localization and non-ergodicity in a system with interactions despite the presence of single-particle delocalized states is closely related to the so-called "many-body proximity effect" and can also be observed in models with disorder coupled to systems with delocalized degrees of freedom. Many-body localization in systems with incommensurate potentials (without single-particle mobility edges) have been realized experimentally, and we show how this can be modified to study the the effects of such mobility edges. Demonstrating the failure of thermalization in the presence of a single-particle mobility edge in the thermodynamic limit would indicate a more robust violation of the ETH.Comment: 17 pages, 14 figures, Review articl

Studies of orbital parameters and pulse profile of the accreting millisecond pulsar XTE J1807-294

The accreting millisecond pulsar XTE J1807-294 was observed by XMM-Newton on March 22, 2003 after its discovery on February 21, 2003 by RXTE. The source was detected in its bright phase with an observed average count rate of 33.3 cts/s in the EPIC-pn camera in the 0.5-10 keV energy band (3.7 mCrab). Using the earlier established best-fit orbital period of 40.0741+/-0.0005 minutes from RXTE observations and considering a circular binary orbit as first approximation, we derived a value of 4.8+/-0.1 lt-ms for the projected orbital radius of the binary system and an epoch of the orbital phase of MJD 52720.67415(16). The barycentric mean spin period of the pulsar was derived as 5.2459427+/-0.0000004 ms. The pulsar's spin-pulse profile showed a prominent (1.5 ms FWHM) pulse, with energy and orbital phase dependence in the amplitude and shape. The measured pulsed fraction in four energy bands was found to be 3.1+/-0.2 % (0.5-3.0 keV), 5.4+/-0.4 % (3.0-6.0 keV), 5.1+/-0.7 % (6.0-10.0 keV) and 3.7+/-0.2 % (0.5-10.0 keV), respectively. Studies of spin-profiles with orbital phase and energy showed significant increase in its pulsed fraction during the second observed orbit of the neutron star, gradually declining in the subsequent two orbits, which was associated with sudden but marginal increase in mass accretion. From our investigations of orbital parameters and estimation of other properties of this compact binary system, we conclude that XTE J1807-294 is very likely a candidate for a millisecond radio pulsar.Comment: 4 pages, 4 figures, Accepted for publication in Astronomy and Astrophysics letter

Understanding the nature of electronic effective mass in double-doped SrTiO3_{3}

We present an approach to tune the effective mass in an oxide semiconductor by a double doping mechanism. We demonstrate this in a model oxide system Sr$_{1-x}$La$_x$TiO$_{3-\delta}$, where we can tune the effective mass ranging from 6--20$\mathrm{m_e}$ as a function of filling or carrier concentration and the scattering mechanism, which are dependent on the chosen lanthanum and oxygen vacancy concentrations. The effective mass values were calculated from the Boltzmann transport equation using the measured transport properties of thin films of Sr$_{1-x}$La$_x$TiO$_{3-\delta}$. Our method, which shows that the effective mass decreases with carrier concentration, provides a means for understanding the nature of transport processes in oxides, which typically have large effective mass and low electron mobility, contrary to the tradional high mobility semiconductors.Comment: 5 pages with 4 figure