arXiv subjects
Publications and source records attributed to B. J. Powell.
We discuss the emergence of symmetry-breaking {\it via} the Pomeranchuk instability from interactions that respect the underlying point-group symmetry. We use a variational mean-field theory to consider a 2D continuum and a square lattice. We describe two experimental signatures: a symmetry-breaking pattern of Friedel oscillations around an impurity; and a structural transition.
We give a quantitative analysis of the previously published nuclear magnetic resonance (NMR) experiments in the k-(ET)2X family of organic charge transfer salts by using the phenomenological spin fluctuation model of Moriya, and Millis, Monien and Pines (M-MMP). For temperatures above T_nmr ~ 50 K, the model gives a good quantitative description of the data in the metallic phases of several k-(ET)2X materials. These materials display antiferromagnetic correlation lengths which increase with decreasing temperature and grow to several lattice constants by T_nmr. It is shown that the fact that the dimensionless Korringa ratio is much larger than unity is inconsistent with a broad class of theoretical models (such as dynamical mean-field theory) which neglects spatial correlations and/or vertex corrections. For materials close to the Mott insulating phase the nuclear spin relaxation rate, the Knight shift and the Korringa ratio all decrease significantly with decreasing temperature below T_nmr. This cannot be described by the M-MMP model and the most natural explanation is that a pseudogap, similar to that observed in the underdoped cuprate superconductors, opens up in the density of states below T_nmr. Such a pseudogap has recently been predicted to occur in the dimerised organic charge transfer salts materials by the resonating valence bond (RVB) theory. We propose specific new experiments on organic superconductors to elucidate these issues. For example, measurements to see if high magnetic fields or high pressures can be used to close the pseudogap would be extremely valuable.
We study the resonating valence bond (RVB) theory of the Hubbard-Heisenberg model on the half-filled anisotropic triangular lattice. Varying the frustration changes the wavevector of maximum spin correlation in the Mott insulating phase. This, in turn, changes the symmetry of the superconducting state, that occurs at the boundary of the Mott insulating phase. We propose that this physics is realised in several families of quasi-two-dimensional organic superconductors.
We review the role of strong electronic correlations in quasi--two-dimensional organic charge transfer salts such as (BEDT-TTF)$_2X$, (BETS)$_2Y$ and $β'$-[Pd(dmit)$_2$]$_2Z$. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerised and is described by a half-filled Hubbard model; the second class is not strongly dimerised and is described by a quarter filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi--two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and `bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental situation, focusing on the key experimental results that may distinguish between rival theories of superconductivity, particularly probes of the pairing symmetry and measurements of the superfluid stiffness. We then discuss some strongly correlated theories of superconductivity, in particular, the resonating valence bond (RVB) theory of superconductivity. We conclude by discussing some of the major challenges currently facing the field.
We present a group theoretical analysis of the superconducting state of the Bechgaard salts, e.g., (TMTSF)_2PF_6 or (TMTSF)_2ClO_6. We show that there are eight symmetry distinct superconducting states. Of these only the (fully gapped, even frequency, p-wave, triplet) 'polar state' is consistent with the full range of the experiments on the Bechgaard salts. The gap of the polar state is d(k) (psi_uk,0,0), where psi_uk may be any odd parity function that is translationally invariant.
Motivated by the unconventional properties and rich phase diagram of NaxCoO2 we consider the electronic and magnetic properties of a two-dimensional Hubbard model on an isotropic triangular lattice doped with electrons away from half-filling. Dynamical mean-field theory (DMFT) calculations predict that for negative inter-site hopping amplitudes (t<0) and an on-site Coulomb repulsion, U, comparable to the bandwidth, the system displays properties typical of a weakly correlated metal. In contrast, for t>0 a large enhancement of the effective mass, ferromagnetism and a Curie-Weiss magnetic susceptibility are found in a broad electron doping range. Our observation of Nagaoka ferromagnetism is consistent with the A-type antiferromagnetism (i.e. ferromagnetic layers stacked antiferromagnetically) observed in neutron scattering experiments on NaxCoO2. We propose that `Curie-Weiss metal' phase observed in NaxCoO2 is a consequence of the crossover from ``bad metal'' with incoherent quasiparticles at temperatures T>T* and Fermi liquid behavior with enhanced parameters below T*, where T* is a low energy coherence scale induced by strong local Coulomb electron correlations. We propose a model which contains the charge ordering phenomena observed in the system which, we propose, drives the system close to the Mott insulating phase even at large dopings.
Ion-implantation of normally insulating polymers offers an alternative to depositing conjugated organics onto plastic films to make electronic circuits. We used a 50 keV nitrogen ion beam to mix a thin 10 nm Sn/Sb alloy film into the sub-surface of polyetheretherketone (PEEK) and report the low temperature properties of this material. We observed metallic behavior, and the onset of superconductivity below 3 K. There are strong indications that the superconductivity does not result from a residual thin-film of alloy, but instead from a network of alloy grains coupled via a weakly conducting, ion-beam carbonized polymer matrix.
We present a group theoretic analysis of several classes of organic superconductors. We argue that highly frustrated half-filled layered organic superconductors, such as kappa-(ET)_2Cu2(CN)_3 (where ET is BEDT-TTF) and beta'-[Pd(dmit)_2]_2X, undergo two superconducting phase transitions, the first from the normal state to a d-wave superconductor and the second to a d+id state. We show that the monoclinic distortion of kappa-(ET)_2Cu(NCS)_2 means that the symmetry of its superconducting order parameter is different from that of orthorhombic kappa-(ET)_2Cu[N(CN)_2]Br. We propose that quarter filled layered organic superconductors, e.g., theta-(ET)_2I_3, have d_{xy}+s order parameters.
We report the results of an experimental and theoretical study of the electronic and structural properties of a key eumelanin precursor - 5,6,-dihydroxyindole-2-carboxylic acid (DHICA) and its dimeric forms. We have used optical spectroscopy to follow the oxidative polymerization of DHICA to eumelanin, and observe red shifting and broadening of the absorption spectrum as the reaction proceeds. First principles density functional theory calculations indicate that DHICA oligomers (possible reaction products of oxidative polymerization) have red shifted HOMO-LUMO gaps with respect to the monomer. Furthermore, different bonding configurations (leading to oligomers with different structures) produce a range of gaps. These experimental and theoretical results lend support to the chemical disorder model where the broad band monotonic absorption characteristic of all melanins is a consequence of the superposition of a large number of inhomogeneously broadened Gaussian transitions associated with each of the components of a melanin ensemble. These results suggest that the traditional model of eumelanin as an amorphous organic semiconductor is not required to explain its optical properties, and should be thoroughly re-examined. These results have significant implications for our understanding of the physics, chemistry and biological function of these important biological macromolecules. Indeed, one may speculate that the robust functionality of melanins in vitro is a direct consequence of its heterogeneity, i.e. chemical disorder is a "low cost" natural resource in these systems.
The coupling between electrons and phonons plays important roles in physics, chemistry and biology. However, the accurate calculation of the electron-phonon coupling constants is computationally expensive as it involves solving the Schrodinger equation for O(N) nuclear configurations, where N is the number of nuclei. Herein we show that by considering the forces on the nuclei caused by the addition or subtraction of an arbitrarily small electronic charge one may calculate the electron-phonon coupling constants from O(1) solutions of the Schrodinger equation. We show that Janak's theorem means that this procedure is exact within the density functional formalism. We demonstrate that the O(1) approach produces numerically accurate results by calculating the electron-phonon coupling constants for a series of molecules ranging in size from H_2 to C_60. We use our approach to introduce a computationally fast approximation for the adiabatic ionisation potentials and electron affinities which is shown to be accurate for large molecules. We also show that our approach allows for the calculation isotope effects in O(0) time and discuss the deuteration driven Mott transition in kappa-(BEDT-TTF)_2Cu[N(CN)_2]Br.
We discuss recent progress towards the establishment of important structure-property-function relationships in eumelanins - key functional bio-macromolecular systems responsible for photo-protection and immune response in humans, and implicated in the development of melanoma skin cancer. We focus on the link between eumelanin's secondary structure and optical properties such as broad band UV-visible absorption and strong non-radiative relaxation; both key features of the photo-protective function. We emphasise the insights gained through a holistic approach combining optical spectroscopy with first principles quantum chemical calculations, and advance the hypothesis that the robust functionality characteristic of eumelanin is related to extreme chemical and structural disorder at the secondary level. This inherent disorder is a low cost natural resource, and it is interesting to speculate as to whether it may play a role in other functional bio-macromolecular systems.
We present an resonating valence bond (RVB) theory of superconductivity for the Hubbard--Heisenberg model on an anisotropic triangular lattice. We show that these calculations are consistent with the observed phase diagram of the half-filled layered organic superconductors, such as the beta, beta', kappa and lambda phases of (BEDT-TTF)_2X [bis(ethylenedithio)tetrathiafulvalene] and (BETS)_2X [bis(ethylenedithio)tetraselenafulvalene]. We find a first order transition from a Mott insulator to a d_{x^2-y^2} superconductor with a small superfluid stiffness and a pseudogap with d_{x^2-y^2} symmetry. The Mott--Hubbard transition can be driven either by increasing the on-site Coulomb repulsion, U, or by changing the anisotropy of the two hopping integrals, t'/t. Our results suggest that the ratio t'/t plays an important role in determining the phase diagram of the organic superconductors.
We report first principles density functional calculations for 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and several reduced forms. DHICA and 5,6-dihydroxyindole (DHI) are believed to be the basic building blocks of the eumelanins. Our results show that carboxylation has a significant effect on the physical properties of the molecules. In particular, the relative stabilities and the HOMO-LUMO gaps (calculated with the $Δ$SCF method) of the various redox forms are strongly affected. We predict that, in contrast to DHI, the density of unpaired electrons, and hence the ESR signal, in DHICA is negligibly small.
We present an analysis of previously published measurements of the London penetration depth of layered organic superconductors. The predictions of the BCS theory of superconductivity are shown to disagree with the measured zero temperature, in plane, London penetration depth by up to two orders of magnitude. We find that fluctuations in the phase of the superconducting order parameter do not determine the superconducting critical temperature as the critical temperature predicted for a Kosterlitz--Thouless transition is more than an order of magnitude greater than is found experimentally for some materials. This places constraints on theories of superconductivity in these materials.
We discuss the key principles of artificial photosynthesis for photovoltaic energy conversion. We demonstrate these principles by examining the operation of the so-called "dye sensitized solar cell" (DSSC) - a photoelectrochemical device which simulates the charge separation process across a nano-structured membrane that is characteristic of natural systems. These type of devices have great potential to challenge silicon semiconductor technology in the low cost, medium efficiency segment of the PV market. Ruthenium charge transfer complexes are currently used as the photon harvesting components in DSSCs. They produce a relatively broad band UV and visible response, but have long term stability problems and are expensive to manufacture. We suggest that a class of biological macromolecules called the melanins may be suitable replacements for the ruthenium complexes. They have strong, broad band absorption, are chemically and photochemically very stable, can be cheaply and easily synthesized, and are also bio-available and bio-compatible. We demonstrate a melanin-based regenerative solar cell, and discuss the key properties that are necessary for an effective broad band photon harvesting system.
We report first principles density functional calculations for hydroquinone (HQ), indolequinone (IQ) and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of bio-macromolecules with important biological functions (including photoprotection) and with potential for certain bioengineering applications. We have used the DeltaSCF (difference of self consistent fields) method to study the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), Delta_HL. We show that Delta_HL is similar in IQ and SQ but approximately twice as large in HQ. This may have important implications for our understanding of the observed broad band optical absorption of the eumelanins. The possibility of using this difference in Delta_HL to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to non-destructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behaviour of the eumelanins.
We give a theoretical analysis of published experimental studies of the effects of impurities and disorder on the superconducting transition temperature, T_c, of the organic molecular crystals kappa-ET_2X and beta-ET_2X (where ET is bis(ethylenedithio)tetrathiafulvalene and X is an anion eg I_3). The Abrikosov-Gorkov (AG) formula describes the suppression of T_c both by magnetic impurities in singlet superconductors, including s-wave superconductors and by non-magnetic impurities in a non-s-wave superconductor. We show that various sources of disorder lead to the suppression of T_c as described by the AG formula. This is confirmed by the excellent fit to the data, the fact that these materials are in the clean limit and the excellent agreement between the value of the interlayer hopping integral, t_perp, calculated from this fit and the value of t_perp found from angular-dependant magnetoresistance and quantum oscillation experiments. If the disorder is, as seems most likely, non-magnetic then the pairing state cannot be s-wave. We show that the cooling rate dependence of the magnetisation is inconsistent with paramagnetic impurities. Triplet pairing is ruled out by several experiments. If the disorder is non-magnetic then this implies that l>=2, in which case Occam's razor suggests that d-wave pairing is realised. Given the proximity of these materials to an antiferromagnetic Mott transition, it is possible that the disorder leads to the formation of local magnetic moments via some novel mechanism. Thus we conclude that either kappa-ET_2X and beta-ET_2X are d-wave superconductors or else they display a novel mechanism for the formation of localised moments. We suggest systematic experiments to differentiate between these scenarios.
We present a first-principles density-functional calculation for the Raman spectra of a neutral BEDT-TTF molecule. Our results are in excellent agreement with experimental results. We show that a planar structure is not a stable state of a neutral BEDT-TTF molecule. We consider three possible conformations and discuss their relation to disorder in these systems.