High-temperature X-ray powder diffraction study of the tetragonal-cubic phase transition in nanocrystalline, compositionally homogeneous ZrO2-CeO2 solid solutions

Crystal structure of compositionally homogeneous, nanocrystalline ZrO2-CeO2 solutions was investigated by X-ray powder diffraction as a function of temperature for compositions between 50 and 65 mol % CeO2 center dot ZrO2-50 and 60 mol % CeO2 solid solutions, which exhibit the t'-form of the tetragonal phase at room temperature, transform into the cubic phase in two steps: t'-to-t '' followed by t ''-to-cubic. But the ZrO2-65 mol % CeO2, which exhibits the t ''-form, transforms directly to the cubic phase. The results suggest that t'-to-t '' transition is of first order, but t ''-to-cubic seems to be of second order. (C) 2008 International Centre for Diffraction Data.

Synchrotron X-ray powder diffraction study of the tetragonal-cubic phase transition in nanostructured ZrO2-Sc2O3 solid solutions

The transition between tetragonal and cubic phases in nanostructured ZrO2-Sc2O3 solid solutions by high-temperature X-ray powder diffraction using synchrotron radiation is presented. ZrO2-8 and 11 mol% Sc2O3 nanopowders that exhibit the t'- and t ''-forms of the tetragonal phase, respectively, were synthesized by a stoichiometric nitrate-lysine gel-combustion route. The average crystallite size treated at 900 degrees C was about 25 nm for both compositions. Our results showed that t'-t '' and t ''-cubic transitions take place for the 8 and 11 mol% Sc2O3 samples, respectively. (C) 2008 International Centre for Diffraction Data.

Study of the influence of indium segregation on the optical properties of InGaAs/GaAs quantum wells via split-operator method

In the case of quantum wells, the indium segregation leads to complex potential profiles that are hardly considered in the majority of the theoretical models. The authors demonstrated that the split-operator method is useful tool for obtaining the electronic properties in these cases. Particularly, they studied the influence of the indium surface segregation in optical properties of InGaAs/GaAs quantum wells. Photoluminescence measurements were carried out for a set of InGaAs/GaAs quantum wells and compared to the results obtained theoretically via split-operator method, showing a good agreement.

Detailed study of the K(L)->pi(0)pi(0)pi(0) Dalitz plot

Using a sample of 68.3x10(6) K(L)->pi(0)pi(0)pi(0) decays collected in 1996-1999 by the KTeV (E832) experiment at Fermilab, we present a detailed study of the K(L)->pi(0)pi(0)pi(0) Dalitz plot density. We report the first observation of interference from K(L)->pi(+)pi(-)pi(0) decays in which pi(+)pi(-) rescatters to pi(0)pi(0) in a final-state interaction. This rescattering effect is described by the Cabibbo-Isidori model, and it depends on the difference in pion scattering lengths between the isospin I=0 and I=2 states, a(0)-a(2). Using the Cabibbo-Isidori model, and fixing (a(0)-a(2))m(pi)(+)=0.268 +/- 0.017 as measured by the CERN-NA48 collaboration, we present the first measurement of the K(L)->pi(0)pi(0)pi(0) quadratic slope parameter that accounts for the rescattering effect: h(000)=(+0.59 +/- 0.20(stat)+/- 0.48(syst)+/- 1.06(ext))x10(-3), where the uncertainties are from data statistics, KTeV systematic errors, and external systematic errors. Fitting for both h(000) and a(0)-a(2), we find h(000)=(-2.09 +/- 0.62(stat)+/- 0.72(syst)+/- 0.28(ext))x10(-3), and m(pi)(+)(a(0)-a(2))=0.215 +/- 0.014(stat)+/- 0.025(syst)+/- 0.006(ext); our value for a(0)-a(2) is consistent with that from NA48.

The Importance of Protein-Protein Interactions on the pH-Induced Conformational Changes of Bovine Serum Albumin: A Small-Angle X-Ray Scattering Study

The combined effects of concentration and pH on the conformational states of bovine serum albumin (BSA) are investigated by small-angle x-ray scattering. Serum albumins, at physiological conditions, are found at concentrations of similar to 35-45 mg/mL (42 mg/mL in the case of humans). In this work, BSA at three different concentrations (10, 25, and 50 mg/mL) and pH values (2.0-9.0) have been studied. Data were analyzed by means of the Global Fitting procedure, with the protein form factor calculated from human serum albumin (HSA) crystallographic structure and the interference function described, considering repulsive and attractive interaction potentials within a random phase approximation. Small-angle x-ray scattering data show that BSA maintains its native state from pH 4.0 up to 9.0 at all investigated concentrations. A pH-dependence of the absolute net protein charge is shown and the charge number per BSA is quantified to 10(2), 8(l), 13(2), 20(2), and 26(2) for pH values 4.0, 5.4, 7.0, 8.0, and 9.0, respectively. The attractive potential diminishes as BSA concentration increases. The coexistence of monomers and dimers is observed at 50 mg/mL and pH 5.4, near the BSA isoelectric point. Samples at pH 2.0 show a different behavior, because BSA overall shape changes as a function of concentration. At 10 mg/mL, BSA is partially unfolded and a strong repulsive protein-protein interaction occurs due to the high amount of exposed charge. At 25 and 50 mg/mL, BSA undergoes some refolding, which likely results in a molten-globule state. This work concludes by confirming that the protein concentration plays an important role on the pH-unfolded BSA state, due to a delicate compromise between interaction forces and crowding effects.

Study of the optical and magnetic properties of pyrimidine in water combining PCM and QM/MM methodologies

The solvent effects on the low-lying absorption spectrum and on the (15)N chemical shielding of pyrimidine in water are calculated using the combined and sequential Monte Carlo simulation and quantum mechanical calculations. Special attention is devoted to the solute polarization. This is included by an iterative procedure previously developed where the solute is electrostatically equilibrated with the solvent. In addition, we verify the simple yet unexplored alternative of combining the polarizable continuum model (PCM) and the hybrid QM/MM method. We use PCM to obtain the average solute polarization and include this in the MM part of the sequential QM/MM methodology, PCM-MM/QM. These procedures are compared and further used in the discrete and the explicit solvent models. The use of the PCM polarization implemented in the MM part seems to generate a very good description of the average solute polarization leading to very good results for the n-pi* excitation energy and the (15)N nuclear chemical shield of pyrimidine in aqueous environment. The best results obtained here using the solute pyrimidine surrounded by 28 explicit water molecules embedded in the electrostatic field of the remaining 472 molecules give the statistically converged values for the low lying n-pi* absorption transition in water of 36 900 +/- 100 (PCM polarization) and 36 950 +/- 100 cm(-1) (iterative polarization), in excellent agreement among one another and with the experimental value observed with a band maximum at 36 900 cm(-1). For the nuclear shielding (15)N the corresponding gas-water chemical shift obtained using the solute pyrimidine surrounded by 9 explicit water molecules embedded in the electrostatic field of the remaining 491 molecules give the statistically converged values of 24.4 +/- 0.8 and 28.5 +/- 0.8 ppm, compared with the inferred experimental value of 19 +/- 2 ppm. Considering the simplicity of the PCM over the iterative polarization this is an important aspect and the computational savings point to the possibility of dealing with larger solute molecules. This PCM-MM/QM approach reconciles the simplicity of the PCM model with the reliability of the combined QM/MM approaches.

Liquid polymorphism, order-disorder transitions and anomalous behavior: A Monte Carlo study of the Bell-Lavis model for water

The Bell-Lavis model for liquid water is investigated through numerical simulations. The lattice-gas model on a triangular lattice presents orientational states and is known to present a highly bonded low density phase and a loosely bonded high density phase. We show that the model liquid-liquid transition is continuous, in contradiction with mean-field results on the Husimi cactus and from the cluster variational method. We define an order parameter which allows interpretation of the transition as an order-disorder transition of the bond network. Our results indicate that the order-disorder transition is in the Ising universality class. Previous proposal of an Ehrenfest second order transition is discarded. A detailed investigation of anomalous properties has also been undertaken. The line of density maxima in the HDL phase is stabilized by fluctuations, absent in the mean-field solution. (C) 2009 American Institute of Physics. [doi:10.1063/1.3253297]

Combined Monte Carlo and quantum mechanics study of the solvatochromism of phenol in water. The origin of the blue shift of the lowest pi-pi* transition

A combined and sequential use of Monte Carlo simulations and quantum mechanical calculations is made to analyze the spectral shift of the lowest pi-pi* transition of phenol in water. The solute polarization is included using electrostatic embedded calculations at the MP2/aug-cc-pVDZ level giving a dipole moment of 2.25 D, corresponding to an increase of 76% compared to the calculated gas-phase value. Using statistically uncorrelated configurations sampled from the MC simulation,first-principle size-extensive calculations are performed to obtain the solvatochromic shift. Analysis is then made of the origin of the blue shift. Results both at the optimized geometry and in room-temperature liquid water show that hydrogen bonds of water with phenol promote a red shift when phenol is the proton-donor and a blue shift when phenol is the proton-acceptor. In the case of the optimized clusters the calculated shifts are in very good agreement with results obtained from mass-selected free jet expansion experiments. In the liquid case the contribution of the solute-solvent hydrogen bonds partially cancels and the total shift obtained is dominated by the contribution of the outer solvent water molecules. Our best result, including both inner and outer water molecules, is 570 +/- 35 cm(-1), in very good agreement with the small experimental shift of 460 cm(-1) for the absorption maximum.

The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7 +/- 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm. (C) 2008 American Institute of Physics.

Numerical study of a model for nonequilibrium wetting

We revisit the scaling properties of a model for nonequilibrium wetting [Phys. Rev. Lett. 79, 2710 (1997)], correcting previous estimates of the critical exponents and providing a complete scaling scheme. Moreover, we investigate a special point in the phase diagram, where the model exhibits a roughening transition related to directed percolation. We argue that in the vicinity of this point evaporation from the middle of plateaus can be interpreted as an external field in the language of directed percolation. This analogy allows us to compute the crossover exponent and to predict the form of the phase transition line close to its terminal point.

Mn dimers on graphene nanoribbons: An ab initio study

We show, using ab initio density functional theory calculations, that Mn dimers adsorbed on graphene nanoribbons (Mn(2)/GNRs) present a magnetic bistability, as does the isolated Mn dimer. Our total energy results indicate that Mn dimers lying along the edge sites of zigzag GNRs represent the most likely configuration. We find that similar to the isolated Mn(2) molecule, the antiferromagnetic coupling represents the ground state for Mn(2)/GNR, and the spin density configuration of the GNR does not play an important role on the net magnetic moment of Mn(2), which makes GNRs an ideal substrate for adsorption of these molecules. The ground state and the excited state configuration of the Mn dimer, viz., low-spin (LS) and high-spin (HS), are maintained in the face of changes in the spin density configuration of the substrate. Here we find that the Mn(2)/GNR systems exhibit a LS <-> HS binary behavior, which can be considered as a useful property in the development of nanomemories based upon metallic clusters. (C) 2011 American Institute of Physics. [doi:10.1063/1.3553849]

Mn-doped cubic BN as an atomiclike memory device: A density functional study

We investigate the electronic properties of Mn(B) substitutional doping in cubic boron nitride (BN), for different charge states, using density functional theory (DFT) calculations. We show that the neutral Mn has a nonmagnetic ground state (S=0). Upon charge injection, it is unambiguously shown that the Mn(B)(-) has a high-spin configuration with a strong, localized magnetic moment of 5 mu(Bohr). We developed a simple model, parameterized by the DFT results, that allows us to interpret the rules played by the crystal-field and exchange-correlation splitting in the magnetization process.

Anelastic spectroscopy study of the metal-insulator transition of Nd(1-x)Eu(x)NiO(3)

Measurements are presented of the complex dynamic Young's modulus of NdNiO(3) and Nd(0.65)Eu(0.35)NiO(3) through the metal-insulator transition (MIT). Upon cooling, the modulus presents a narrow dip at the MIT followed by an abrupt stiffening of similar to 6%. The anomaly is reproducible between cooling and heating in Nd(0.65)Eu(0.35)NiO(3) but appears only as a slow stiffening during cooling in undoped NdNiO(3), in conformance with the fact that the MIT in RNiO(3) changes from strongly first order to second order when the mean R size is decreased. The elastic anomaly seems not to be associated with the antiferromagnetic transition, which is distinct from the MIT in Nd(0.65)Eu(0.35)NiO(3). It is concluded that the steplike stiffening is due to the disappearance or freezing of dynamic Jahn-Teller (JT) distortions through the MIT, where the JT active Ni(3+) is disproportionated into alternating Ni(3+delta) and Ni(3-delta). The fluctuating octahedral JT distortion necessary to justify the observed jump in the elastic modulus is estimated as similar to 3% but does not have a role in determining the MIT, since the otherwise-expected precursor softening is not observed.

Resistively detected NMR of the nu=1 quantum Hall state: A tilted magnetic field study

Previous resistively detected NMR (RDNMR) studies on the nu approximate to 1 quantum Hall state have reported a ""dispersionlike"" line shape and extremely short nuclear-spin-lattice relaxation times, observations which have been attributed to the formation of a skyrme lattice. Here we examine the evolution of the RDNMR line shape and nuclear-spin relaxation for Zeeman: Coulomb energy ratios ranging from 0.012 to 0.036. According to theory, suppression of the skyrme crystal, along with the associated Goldstone mode nuclear-spin-relaxation mechanism, is expected at the upper end of this range. However, we find that the anomalous line shape persists at high Zeeman energy, and only a modest decrease in the RDNMR-detected nuclear-spin-relaxation rate is observed.

In-field Mossbauer study of disordered surface spins in core/shell ferrite nanoparticles

Magnetization and Mossbauer spectroscopy measurements are performed at low temperature under high field, on nanoparticles with a nickel ferrite core and a maghemite shell. These nanoparticles present finite size and surface effects, together with exchange anisotropy. High field magnetization brings the evidences of a monodomain ordered core and surface spins freezing in disorder at low temperature. Mossbauer spectra at 4.2 K present an extra contribution from the disordered surface which is field dependent. Field and size dependences of this latter show a progressive spin alignment along the ferrite core which is size dependent. The weak surface pinning condition of the nanoparticles confirms that the spin disorder is localized in the external shell. The underfield decrease in the mean canting angle in the superficial shell is then directly related to the unidirectional exchange anisotropy through the interface between the ordered core and the disordered shell. The obtained anisotropy field H(Ea) scales as the inverse of the nanoparticle diameter, validating its interfacial origin. The associated anisotropy constant K(Ea) equals 2.5 x 10(-4) J/m(2). (C) 2009 American Institute qf Physics. [doi: 10.1063/1.3245326]