Electron Donor-Acceptor Complexes of the Fullerenes C60 and C70 with Amines

Based on electronic absorption spectroscopy, C60 is found to form complexes with aromatic amines with an enthalpy of association in the range 9-16 kJ mol-1. Interaction of C70 with the amines is negligible. Cyclic voltammetric measurements confirm these observations.

Phenomenological Ginzburg-Landau-like theory for superconductivity in the cuprates

We propose and develop here a phenomenological Ginzburg-Landau-like theory of cuprate high-temperature superconductivity. The free energy of a cuprate superconductor is expressed as a functional F of the complex spin-singlet pair amplitude psi(ij) equivalent to psi(m) = Delta(m) exp(i phi(m)), where i and j are nearest-neighbor sites of the square planar Cu lattice in which the superconductivity is believed to primarily reside, and m labels the site located at the center of the bond between i and j. The system is modeled as a weakly coupled stack of such planes. We hypothesize a simple form FDelta, phi] = Sigma(m)A Delta(2)(m) + (B/2)Delta(4)(m)] + C Sigma(< mn >) Delta(m) Delta(n) cos(phi(m) - phi(n)) for the functional, where m and n are nearest-neighbor sites on the bond-center lattice. This form is analogous to the original continuum Ginzburg-Landau free-energy functional; the coefficients A, B, and C are determined from comparison with experiments. A combination of analytic approximations, numerical minimization, and Monte Carlo simulations is used to work out a number of consequences of the proposed functional for specific choices of A, B, and C as functions of hole density x and temperature T. There can be a rapid crossover of from small to large values as A changes sign from positive to negative on lowering T; this crossover temperature T-ms(x) is identified with the observed pseudogap temperature T*(x). The thermodynamic superconducting phase-coherence transition occurs at a lower temperature T-c(x), and describes superconductivity with d-wave symmetry for positive C. The calculated T-c(x) curve has the observed parabolic shape. The results for the superfluid density rho(s)(x, T), the local gap magnitude , the specific heat C-v(x, T) (with and without a magnetic field), as well as vortex properties, all obtained using the proposed functional, are compared successfully with experiments. We also obtain the electron spectral density as influenced by the coupling between the electrons and the correlation function of the pair amplitude calculated from the functional, and compare the results successfully with the electronic spectrum measured through angle resolved photoemission spectroscopy (ARPES). For the specific heat, vortex structure, and electron spectral density, only some of the final results are reported here; the details are presented in subsequent papers.

Coherent phonons in pyrochlore titanates A(2)Ti(2)O(7) (A = Dy, Gd, Tb): A phase transition in Dy2Ti2O7 at 110 K

We study the generation of coherent optical phonons in spin-frustrated pyrochlore single crystals Dy2Ti2O7, Gd2Ti2O7, and Tb2Ti2O7 using femtosecond laser pulses (65 fs, 1.57 eV) in degenerate time-resolved transmission experiments as a function of temperature from 4 to 296 K. At 4 K, two coherent phonons are observed at similar to 5.3 THz (5.0 THz) and similar to 9.3 THz (9.4 THz) for Dy2Ti2O7 (Gd2Ti2O7), whereas three coherent phonons are generated at similar to 5.0, 8.6, and 9.7 THz for Tb2Ti2O7. In the case of spin-ice Dy2Ti2O7, a clear discontinuity is observed in the linewidths of both the coherent phonons as well as in the phase of lower-energy coherent phonon mode, indicating a subtle structural change at 110 K. Another important observation is a phase difference of pi between the modes in all the samples, thus suggesting that the driving forces behind the generation of these modes could be different in nature, unlike a purely impulsive or displacive mechanism.

Probing the structural changes in the phase transitions of a Bi2MoO6 catalyst: the nature of the intermediate-temperature phase

The nature of the phase transitions of Bi2MoO6 has been investigated by the combined use of X-ray diffraction and Xray absorption spectroscopy. The distorted MoO6 octahedra in the low-temperature form are shown to undergo further distortion in the intermediate-temperature form before transforming to MoO4 tetrahedra in the high-temperature phase. (C) 1995 Academic Press, Inc.

Spectroscopic, redox and photophysical properties of push-pull fluoroarylporphyrins

Novel fluoroarylporphyrins bearing electron donor dimethylamino groups in the meso-aryl positions and an electron acceptor nitro group on one of the pyrrole carbons exhibit significant solvent dependent fluorescence spectra and time-resolved emission properties. These effects are suggestive of intramolecular charge transfer (ICT) in the singlet excited state of these porphyrins. Electrochemical redox behaviour of these porphyrins showed the presence of substantial donor-acceptor interactions in the nitro-amino porphyrins.

Photophysical and electrochemical redox properties of fixed distance porphyrin-quinone systems

A few fixed distance covalently linked porphyrin-quinone molecules have been synthesized in which a benzoquinone is directly attached to a meso/beta-pyrrole position of tri(phenyl/pentafluorophenyl)/tetraphenylporphyrins. The choice of fluoroarylporphyrins permit modulation of Delta G(ET) values for photoinduced electron-transfer reactions in these systems. All short distance porphyrin-quinone molecules showed efficient quenching of the porphyrin singlet excited state. The electrochemical redox data coupled with the steady-state and time-resolved singlet emission data are analysed to evaluate the dependence of Delta G(ET) values on the rate of electron transfer (k(ET)) in these systems. The meso-trifluoroarylporphyrin-quinones are found to be sensitive probes of the surrounding dielectric environment. Varying solvent polarity on the mechanism of fluorescence quenching and k(ET) values revealed that short donor-acceptor distance and the solvent dielectric relaxation properties play a dominant role. (C) 1999 Elsevier Science S.A. All rights reserved.

Crystallization of SrCO3 on a self-assembled monolayer substrate: an in-situ synchrotron X-ray study

Self-assembled monolayers (SAMs) of alkanethiols on gold surfaces show great promise in controlling the nucleation and growth of inorganic minerals from solution. In doing so, they mimic the role of some biogenic macromolecules in natural biomineralisation processes. Crystallization on SAM surfaces is usually monitored ex-situ; by allowing the process to commence and to evolve for some time, removing the substrate from the mother solution, and then examining it using microscopy, diffraction etc. We present here for the first time, the use of high energy monochromatic synchrotron X-radiation in conjunction with a two dimensional detector to monitor in situ, in a time resolved fashion, the growth of SrCO3 (strontianite) crystals on a SAM substrate.

Dynamics of bound dyes in a nonpolymeric aqueous gel derived from a tripodal bile salt

Rotational dynamics of polarity sensitive fluorescent dyes (ANS and DPH) in a nonpolymertic aqueous gel derived from tripodal cholamide I was studied using ultrafast time-resolved fluorescence technique. Results were compared with that of naturally occurring di- and trihydroxy bile salts. ANS in the gel showed two rotational correlation time (phi) components, 13.2 ns (bound to the hydrophobic region of the gel) and 1.0 ns (free aqueous ANS), whereas DPH showed only one component (4.8 ns). In the sol state, faster rotational motion was observed, both for ANS and DPH. Our data revealed that dyes get encapsulated more tightly in the gel network when compared to the micellar aggregates. ANS has more restrained rotation compared to DPH. This was attributed to the interaction of the sulfonate group of ANS with water molecules and hydrophilic parts of the gelator molecule. No restricted rotation was observed for DPH in the gel state unlike when it is in the gel phase of lipid bilayer.

Crystal structure of quenched and in-field electroluminescent phosphors

Electroluminescent zinc sulfide doped with copper and chloride (ZnS:Cu, Cl) powder was heated to 400°C and rapidly quenched to room temperature. Comparison between the quenched and non-quenched phosphors using synchrotron radiation X-ray powder diffraction (XRPD) (λ = 0.828692 Å) and X-ray absorption spectroscopy (XAS) was made. XRPD shows that the expected highly faulted structure is observed with excellent resolution out to 150° 2θ (or to (12 2 2) of the sphalerite phase). The quenched sample compared to the unheated sample shows a large change in peak ratios between 46.7° and 46.9°, which is thought to correspond to the wurtzite (0 0 6), (0 3 2) and sphalerite (3 3 3)/(5 1 1) peaks. Hence, a large proportion of this sphalerite diffraction is lost from the material upon rapid quenching, but not when the material is allowed to cool slowly. The Zn K-edge XAS data indicate that the crystalline structures are indistinguishable using this technique, but do give an indication that the electronic structure has altered due to changing intensity of the white line. It is noted that the blue electroluminescence (EL) emission bands are lost upon quenching: however, a large amount of total EL emission intensity is also removed, which is consistent with our findings. We report the XRPD of a working alternating-current electroluminescence device in the synchrotron X-ray beam, which exhibits a new diffraction pattern when the device is powered in an AC field even though the phosphor is fixed in the binder. Significantly, only a few crystals are required to yield the diffraction data because of the high flux X-ray source. These in panel data show multiple sharp diffraction lines spread out under the region, where capillary data show broad diffraction intensity indicating that the phosphor powder is comprised of unique crystals, each having different structures.

Solution processed reduced graphene oxide ultraviolet detector

Electronic properties of graphene have been studied more extensively than its photonic applications, in spite of its exciting optical properties. Recent results on solar cells, light emitting diodes and photodetectors show its true potential in photonics and optoelectronics. Here, we have explored the use of reduced graphene oxide as a candidate for solution processed ultraviolet photodetectors. UV detection is demonstrated by reduced graphene oxide in terms of time resolved photocurrent as well as photoresponse. The responsivity of the detectors is found to be 0.12 A/W with an external quantum efficiency of 40%. (C) 2011 American Institute of Physics. [doi:10.1063/1.3640222]

Effect of pairing fluctuations on low-energy electronic spectra in cuprate superconductors

We describe here a minimal theory of tight-binding electrons moving on the square planar Cu lattice of the hole-doped cuprates and mixed quantum mechanically with their own Cooper pairs. The superconductivity occurring at the transition temperature T(c) is the long-range, d-wave symmetry phase coherence of these Cooper pairs. Fluctuations, necessarily associated with incipient long-range superconducting order, have a generic large-distance behavior near T(c). We calculate the spectral density of electrons coupled to such Cooper-pair fluctuations and show that features observed in angle resolved photoemission spectroscopy (ARPES) experiments on different cuprates above T(c) as a function of doping and temperature emerge naturally in this description. These include ``Fermi arcs'' with temperature-dependent length and an antinodal pseudogap, which fills up linearly as the temperature increases toward the pseudogap temperature. Our results agree quantitatively with experiment. Below T(c), the effects of nonzero superfluid density and thermal fluctuations are calculated and compared successfully with some recent ARPES experiments, especially the observed bending or deviation of the superconducting gap from the canonical d-wave form.

Electrochemical detection and removal of lead in water using poly(propylene imine) modified re-compressed exfoliated graphite electrodes

Modification of exfoliated graphite (EG) electrode with generation 2 poly(propylene imine) dendrimer by electrodeposition resulted in an electrochemical sensor which was used to detect lead ions in water to a limit of 1 ppb and a linear response between 2.5 and 40 ppb using square wave anodic stripping voltammetry (SW-ASV). Pb(II) was also removed from spiked water sample using a 40-mm diameter unmodified EG electrode with an applied potential of -1,000 mV for 180 min. A removal efficiency of 99% was calculated from a 150 mL sample. The results obtained in both cases using SW-ASV, correlated with atomic absorption spectroscopy.

Infrared Photodetectors Based on Reduced Graphene Oxide and Graphene Nanoribbons

The use of reduced graphene oxide (RGO) and graphene nanoribbons (GNRs) as infrared photodetectors is explored, based on recent results dealing with solar cells, light-emitting devices, photodetectors, and ultrafast lasers. IR detection is demonstrated by both RGO and GNRs (see image) in terms of the time-resolved photocurrent and photoresponse. The responsivity of the detectors and their functioning are presented.

The interaction of halogen molecules with SWNTs and graphene

The interaction of halogen molecules of varying electron affinity, such as iodine monochloride (ICl), bromine (Br(2)), iodine monobromide (IBr) and iodine (I(2)) with single-walled carbon nanotubes (SWNTs) and graphene has been investigated in detail. Halogen doping of the two nanocarbons has been examined using Raman spectroscopy in conjunction with electronic absorption spectroscopy and extensive theoretical calculations. The halogen molecules, being electron withdrawing in nature, induce distinct changes in the electronic states of both the SWNTs and graphene, which manifests with a change in the spectroscopic signatures. Stiffening of the Raman G-bands of the nanocarbons upon treatment with the different halogen molecules and the emergence of new bands in the electronic absorption spectra, both point to the fact that the halogen molecules are involved in molecular charge-transfer with the nanocarbons. The experimental findings have been explained through density functional theory (DFT) calculations, which suggest that the extent of charge-transfer depends on the electron affinities of the different halogens, which determines the overall spectroscopic properties. The magnitude of the molecular charge-transfer between the halogens and the nanocarbons generally varies in the order ICl > Br(2) > IBr > I(2), which is consistent with the expected order of electron affinities.

Tuning the Efficiency of Dendritic Nanocarriers using Conformational Constraints

A series of deoxycholic and cholic acid-derived oligomers were synthesized and their ability to extract hydrophilic dye molecules of different structure, size, and functional groups into nonpolar media was studied. The structure of the dye and dendritic effect in the extraction process was examined using absorption spectroscopy and dynamic light scattering (DLS). The efficiency of structurally preorganized oligomers in the aggregation process was evaluated by 1-anilinonaphthalene-8-sulfonic acid (ANS) fluorescence studies. The possible formation of globular structures for higher-generation molecules was investigated by molecular modeling studies and the results were correlated with the anomaly observed in the extraction process with this molecule. The ability of these molecules for selective extraction of specific dyes from blended colors is also reported.