Density-matrix renormalization-group study of low-lying excitations of polyacene within a Pariser-Parr-Pople model

We have carried out symmetrized density-matrix renormalization-group calculations to study the nature of excited states of long polyacene oligomers within a Pariser-Parr-Pople Hamiltonian. We have used the C-2 symmetry, the electron-hole symmetry, and the spin parity of the system in our calculations. We find that there is a crossover in the lowest dipole forbidden two-photon state and the lowest dipole allowed excited state with size of the oligomer. In the long system limit, the two-photon state lies below the lowest dipole allowed excited state. The triplet state lies well below the two-photon state and energetically does not correspond to its description as being made up of two triplets. These results are in agreement with the general trends in linear conjugated polymers. However, unlike in linear polyenes wherein the two-photon state is a localized excitation, we find that in polyacenes, the two-photon excitation is spread out over the system. We have doped the systems with a hole and an electron and have calculated the charge excitation gap. Using the charge gap and the optical gap, we estimate the binding energy of the 1(1)B(-) exciton to be 2.09 eV. We have also studied doubly doped polyacenes and find that the bipolaron in these systems, to be composed of two separated polarons, as indicated by the calculated charge-density profile and charge-charge correlation function. We have studied bond orders in various states in order to get an idea of the excited state geometry of the system. We find that the ground state, the triplet state, the dipole allowed state, and the polaron excitations correspond to lengthening of the rung bonds in the interior of the oligomer while the two-photon excitation corresponds to the rung bond lengths having two maxima in the system.

Precise measurement of hyperfine intervals using avoided crossing of dressed states

We demonstrate a technique for precisely measuring hyperfine intervals in alkali atoms. The atoms form a three-level system in the presence of a strong control laser and a weak probe laser. The dressed states created by the control laser show significant linewidth reduction. We have developed a technique for Doppler-free spectroscopy that enables the separation between the dressed states to be measured with high accuracy even in room temperature atoms. The states go through an avoided crossing as the detuning of the control laser is changed from positive to negative. By studying the separation as a function of detuning, the center of the level-crossing diagram is determined with high precision, which yields the hyperfine interval. Using room temperature Rb vapor, we obtain a precision of 44 kHz. This is a significant improvement over the current precision of similar to1 MHz.

Quantum spin models with exact dimer ground states

Inspired by the exact solution of the Majumdar-Ghosh model, a family of one-dimensional, translationally invariant spin Hamiltonians is constructed. The exchange coupling in these models is antiferromagnetic, and decreases linearly with the separation between the spins. The coupling becomes identically zero beyond a certain distance. It is rigorously proved that the dimer configuration is an exact, superstable ground-state configuration of all the members of the family on a periodic chain. The ground state is twofold degenerate, and there exists an energy gap above the ground state. The Majumdar-Ghosh Hamiltonian with a twofold degenerate dimer ground state is just the first member of the family. The scheme of construction is generalized to two and three dimensions, and illustrated with the help of some concrete examples. The first member in two dimensions is the Shastry-Sutherland model. Many of these models have exponentially degenerate, exact dimer ground states.

Symmetry-breaking transitions in equilibrium shapes of coherent precipitates: Effect of elastic anisotropy and inhomogeneity

We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components epsilon(xx)*. and epsilon(yy)*. For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t = epsilon(yy)*/epsilon(xx)*. We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t = 1) and those with pure shear misfit (t = -1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (-1 < t < 1; t not equal 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0 < t < 1. For systems which allow an invariant line (-1 less than or equal to t < 0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0 < t less than or equal to 1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.

An XPS study on oxidation states of Pt and its alloys with Co and Cr and its relevance to electroreduction of oxygen

Cathodic reduction of oxygen in fuel cells is known to be enhanced on platinum alloys in relation to the platinum metal. The higher performance of the platinum alloys is as a result of the improved oxygen-reduction kinetics on the alloys but there is hardly any increase in the electrode platinum-surface-areas for the platinum alloys as compared to the platinum metal, and thus the higher performance is solely due to the enhanced electrocatalytic activity of the alloys as compared to the platinum metal. The present X-ray photoelectron spectroscopic (XPS) study on carbon-supported Pt, Pt–Co and Pt–Co–Cr electrocatalysts suggests the presence of a relatively lower Pt-oxide content on the alloys. The X-ray powder diffraction patterns for these electrocatalysts show that while the carbon-supported platinum electrocatalyst has a face-centered cubic (fcc) phase, carbon-supported Pt–Co and Pt–Co–Cr electrocatalysts exhibit a face-centered tetragonal (fct) phase. But, Pt electrocatalyst has a lower particle-size and, hence, a higher dispersion. Previous studies have shown higher activities on the Pt-alloys than on Pt, and have attributed it to changes in the electronic and structural characteristics of Pt. These changes can be correlated with the lower oxidation-state of Pt sites, as found in this study.

Denaturant mediated unfolding of both native and molten globule states of maltose binding protein are accompanied by large [Delta]Cp's

Maltose binding protein (MBP) is a large, monomeric two domain protein containing 370 amino acids. In the absence of denaturant at neutral pH, the protein is in the native state, while at pH 3.0 it forms a molten globule. The molten globule lacks a tertiary circular dichroism signal but has secondary structure similar to that of the native state. The molten globule binds 8-anilino-1-naphthalene sulfonate (ANS). The unfolding thermodynamics of MBP at both pHs were measured by carrying out a series of isothermal urea melts at temperatures ranging from 274–329 K. At 298 K, values of [Delta]G°, [Delta]Cp, and Cm were 3.1 ± 0.2 kcal mol−1, 5.9 ± 0.8 kcal mol−1 K−1 (15.9 cal (mol-residue)−1 K−1), and 0.8 M, respectively, at pH 3.0 and 14.5 ± 0.4 kcal mol−1, 8.3 ± 0.7 kcal mol−1 K−1 (22.4 kcal (mol-residue)−1 K−1), and 3.3 M, respectively, at pH 7.1. Guanidine hydrochloride denaturation at pH 7.1 gave values of [Delta]G° and [Delta]Cp similar to those obtained with urea. The m values for denaturation are strongly temperature dependent, in contrast to what has been previously observed for small globular proteins. The value of [Delta]Cp per mol-residue for the molten globule is comparable to corresponding values of [Delta]Cp for the unfolding of typical globular proteins and suggests that it is a highly ordered structure, unlike molten globules of many small proteins. The value of [Delta]Cp per mol-residue for the unfolding of the native state is among the highest currently known for any protein.

Photoluminescence of Sr(2-x)Ln(x)CeO(4+x/2) (Ln = Eu, Sm or Yb) prepared by a wet chemical method

A wet chemical route is developed for the preparation of Sr2CeO4 denoted the carbonate-gel composite technique. This involves the coprecipitation of strontium as fine particles of carbonates within hydrated gels of ceria (CeO2.xH(2)O, 40states in oxides. Efficient energy transfer occurs from Ce4+-O2- CT state to trivalent lanthanide ions (Ln(3+)) if the latter has CT excited states, leading to sensitizer-activator relation, through non-resonance process involving exchange interaction. Yb3+-substituted Sr2CeO4 does not show any line emission because the energy of Yb3+-O2- CT level is higher than that of the Ce4+-O2- CT level. Sr2-xEuxCeO4+x/2 shows white emission at xless than or equal to0.02 because of the dominant intensities of D-5(2)-F-7(0-3) transitions in blue-green region whereas the intensities of D-5(0)-F-7(0-3) transitions in orange-red regions dominate at concentrations xgreater than or equal to0.03 and give red emission. The appearance of all the emissions from D-5(2), D-5(1) and D-5(0) excited states to the F-7(0-3) ground multiplets of Eu3+ is explained on the basis of the shift from the hypersensitive electric-dipole to magnetic-dipole related transitions with the variation in site symmetry with increasing concentration of Eu3+. White emission of Sr2-x SmxCeO4+x/2 at xless than or equal to0.02 is due the co-existence of Ce4+-O2- CT emission and (4)G(4)(5/2)-H-6(J) Sm3+ transitions whereas only the Sm3+ red emission prevails for xgreater than or equal to0.03. The above unique changes in PL emission features are explained in terms of the changes in NNN environments of Ce4+. Quenching of Ce4+-O2- CT emission by other Ln(3+) is due to the ground state crossover arising out of the NNN interactions.

Role of interface states associated with transitional nanophase precipitates in the photoluminescence enhancement of SrTiO3 : Pr3+,Al3+

SrTiO3:Pr3+,Al3+ phosphor samples with varying ratios of Sr/Ti/Al were prepared by the gel-carbonate method and the mechanism of enhancement of the red photoluminescence intensity therein was investigated. The photoluminescence (PL) spectra of SrTiO3:Pr3+ show both D-1(2) --> H-3(4) and P-3(0) --> H-3(4) emission in the red and blue spectral regions, respectively, with comparable intensity. The emission intensity of D-1(2) --> H-3(4) is drastically enhanced by the incorporation of Al3+ and excess Ti4+ in the compositional range Sr(Ti,Al-y)(O3+3y/2):Pr3+ (0.2 less than or equal to y less than or equal to 0.4) and SrTi1+xAlyO3+z:Pr3+ (0.2 less than or equal to x less than or equal to 0.5; 0.05 less than or equal to y less than or equal to 0.1; z = 2x + 3y/2) with the complete disappearance of the blue band. This cannot be explained by the simple point defect model as the EPR studies do not show any evidence for the presence of electron or hole centers. TEM investigations show the presence of exsolved nanophases of SrAl12O19 and/or TiO2 in the grain boundary region as well as grain interiors as lamellae which, in turn, form the solid-state defects, namely, dislocation networks, stacking faults and crystallographic shear planes whereby the framework of corner shared TiO6 octehedra changes over to edge-sharing TiO5-AlO5 strands as indicated from the Al-27 MAS NMR studies. The presence of transitional nanophases and the associated defects modify the excitation-emission processes by way of formation of electronic sub-levels at 3.40 and 4.43 eV, leading to magnetic-dipole related red emission with enhanced intensity. This is evidenced by the fact that SrAl12O19:Pr3+,Ti4+ shows bright red emission whereas SrAl12O19:Pr3+ does not show red photoluminescence.

The effect of host glass on optical absorption and fluorescence of Nd3+ in xNa(2)O-(30-x)K2O-70B(2)O(3) glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Nd3+ has been studied in mixed alkali borate glasses of the type xNa(2)O-(30-x)K2O-69.5B(2)O(3)-0.5Nd(2)O(3) (X = 5,10,15,20 and 25). Various spectroscopic parameters such as Racah (E-1, E-2 and E-3), spin-orbit (xi(4f)) and configuration interaction (alpha, beta) parameters have been calculated. The Judd-Ofelt intensity parameters (Omega(lambda)) have been calculated and the radiative transition probabilities (A(rad)), radiative lifetimes (tau(r)), branching ratios (beta) and integrated absorption cross sections (Sigma) have been obtained for certain excited states of the Nd3+, ion and are discussed with respect to x. From the fluorescence spectra, the effective fluorescence line widths (Deltalambda(eff)) and stimulated emission cross sections (sigma(p)) have been obtained for the three transitions F-4(3/2) --> I-4(9/2), F-4(3/2) --> I-4(11/2) and F-4(3/2) --> I-4(13/2) of Nd3+. The stimulated emission cross section (sigma(p)) values are found to be in the range (2.0-4.8) x 10(-2)0 cm(2) and they are large enough to indicate that the mixed alkali borate glasses could be potential laser host materials.

Effect of Te addition on the optical properties of As(2)S(3) thin film

Bilayer thin films of Te/As(2)S(3) were prepared from Te and As(2)S(3) by thermal technique under high vacuum. Optical constants were calculated by analysing the transmission spectrum in the spectral range 400-1100 nm. The optical band gap decreases with the addition of Te to As(2)S(3). The decrease of optical band gap has been explained on the basis of density of states and the increase in disorder in the system. We have irradiated the as-deposited films using a diode pumped solid state laser of 532 nm wavelength to study photo-diffusion of Te into As(2)S(3). The changes were characterised by Fourier Transform Infrared and X-ray Photoelectron Spectroscopy (XPS). The optical band gap is found to be decreased with the light irradiation which is proposed due to homopolar bond formation. The core level peaks in XPS spectra give information about different bond formation. (C) 2011 Elsevier B.V. All rights reserved.

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

Direct evidence of redox interaction between metal ion and support oxide in Ce(0.98)Pd(0.02)O(2-delta) by a combined electrochemical and XPS study

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd(2+)/CeO(2) interaction in Ce(1-x)Pd(x)O(2-delta) (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce(0.98)Pd(0.02)O(2-delta) working electrode which causes Ce(4+) to reduce to Ce(3+) to the extent of similar to 35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0-1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce(4+) to Ce(3+) state. CeO(2) electrode with no metal component reduces to CeO(2-y) (y similar to 0.4) after applying 1.2 V which is not reversible and the original composition of CeO(2) cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce(0.98)Pd(0.02)O(2-delta) reaches a steady state composition with Pd in the +2 states and Ce(4+) : Ce(3+) in the ratio of 0.65 : 0.35. This composition can be denoted as Ce(0.63)(4+)Ce(0.35)(4+)Pd(0.02)O(2-delta-y) (y similar to 0.17). When pure CeO(2) is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce(0.98)Pd(0.02)O(2-delta) forms a stable electrode for the electro-oxidation of H(2)O to O(2) unlike CeO(2) due to the metal support interaction.

Structure and Photocatalytic Activity of Ti 1- x M x O 2±δ (M = W, V, Ce, Zr, Fe, and Cu) Synthesized by Solution Combustion Method

The W, V, Ce, Zr, Fe, and Cu metal ion substituted nanocrystalline anatase TiO2 was prepared by solution combustion method and characterized by XRD, Raman, BET, EPR, XPS, IR TGA, UV absorption, and photoluminescence measurements. The structural studies indicate that the solid solution formation was limited to a narrow range of concentrations of the dopant ions. The photocatalytic degradation of 4-nitrophenol under UV and solar exposure was investigated with Ti1-xMxO2±δ. The degradation rates of 4-nitrophenol with these catalysts were lesser than the degradation rates of 4-nitrophenol with undoped TiO2 both with UV exposure and solar radiation. However, the photocatalytic activities of most metal ion doped TiO2 are higher than the activity of the commercial TiO2, Degussa P25. The decrease in photocatalytic activity is correlated with decrease in photoluminescence due to electron states of metal ions within the band gap of TiO2.

Density matrix renormalization group algorithm for Bethe lattices of spin-1/2 or spin-1 sites with Heisenberg antiferromagnetic exchange

A density matrix renormalization group (DMRG) algorithm is presented for the Bethe lattice with connectivity Z = 3 and antiferromagnetic exchange between nearest-neighbor spins s = 1/2 or 1 sites in successive generations g. The algorithm is accurate for s = 1 sites. The ground states are magnetic with spin S(g) = 2(g)s, staggered magnetization that persists for large g > 20, and short-range spin correlation functions that decrease exponentially. A finite energy gap to S > S(g) leads to a magnetization plateau in the extended lattice. Closely similar DMRG results for s = 1/2 and 1 are interpreted in terms of an analytical three-site model.

Feasibility study of the measurement of Higgs pair creation at a photon linear collider

We studied the feasibility of the measurement of Higgs pair creation at a photon linear collider. From the sensitivity to the anomalous self-coupling of the Higgs boson, the optimum gamma gamma collision energy was found to be around 270 GeV for a Higgs mass of 120 GeV/c(2). We found that large backgrounds such as gamma gamma -> W+W-, ZZ, and b (b) over barb (b) over bar can be suppressed if correct assignment of tracks to parent partons is achieved and Higgs pair events can be observed with a statistical significance of similar to 5 sigma by operating the photon linear collider for 5 years.