Investigating the role of carbon doping on the structural and energetic properties of small aluminum clusters using quantum Monte Carlo.

In this study, we investigate the energetics of small aluminum clusters doped with a carbon atom using several computational methods, including diffusion quantum Monte Carlo, Hartree-Fock (HF), and density functional theory. We calculate the lowest energy structure, total ground-state energy, electron population distribution, binding energy, and dissociation energy as a function of the cluster size of the carbon-doped aluminum clusters compared with the undoped ones. The obtained results show that carbon doping enhances the stability of the clusters mainly due to the electrostatic and exchange interactions from the HF contribution gain. The calculations also indicate that the dissociation energy required to remove the doped carbon atom is much larger than that required to remove an aluminum atom from the doped clusters. In general, our results are consistent with available theoretical and experimental data.

Electron correlation effects in boron clusters BQn (for Q = -1, 0, 1 and n ≤ 13) based on quantum Monte Carlo simulations.

We present all-electron quantum Monte Carlo simulations on the anionic, neutral, and cationic boron clusters BQn with up to 13 atoms (Q = -1, 0, +1 and n ≤ 13). Accurate total energies of these clusters are obtained and an excellent agreement is reached with available experimental results for adiabatic and vertical detachment energies. We also perform very accurate Hartree-Fock calculations in the complete-basis-set limit where electron correlation is absent. In combination with the FN-DMC and HF-CBS results, we quantify the correlation effects and present the first attempt for a systematic investigation on the electron correlation effects in boron clusters. The obtained results show that, in general, electron correlation may contribute significantly to both the atomic and electronic structures of the boron clusters, manifested in the quantities such as the average binding energies of the clusters, atomic dissociation energies, detachment energies, and ionization potentials. For instance, the calculations indicate that the electron correlation maintains the bound state of cationic cluster B2+ and it also contributes 99% of the detachment energy of the anionic cluster B5-.

Quantifying electron-correlation effects in small coinage-metal clusters via ab initio calculations.

We investigate many-electron correlation effects in neutral and charged coinage-metal clusters Cun, Agn, and Aun (n = 1-4) via ab initio calculations using fixed-node diffusion Monte Carlo (FN-DMC) simulations, density functional theory (DFT), and the Hartree-Fock (HF) method. From very accurate FN-DMC total energies of the clusters and the HF results in the infinity large complete-basis-set limit, we obtain correlation energies in these strongly correlated many-electron clusters involving d orbitals. The obtained bond lengths of the clusters, atomic binding and dissociation energies, ionization potentials, and electron affinities are in satisfactory agreement with the available experiments. In the analysis, the electron correlation effects on these observable physical quantities are quantified by relative correlation contributions determined by the difference between the calculated FN-DMC and HF results. We show that the correlation contribution is not only significant for the quantities related to electronic structures of the coinage-metal clusters, such as electron affinity, but it is also essential for the stability of the atomic structures of these clusters. For example, the electron correlation contribution is responsible for more than 90% of the atomic binding energies of the small neutral copper clusters. We also demonstrate the orbital-occupation dependence of the correlation energy and electron pairing of the valence electrons in these coinage-metal clusters from the electron correlation-energy gain and spin-multiplicity change in the electron addition processes, which are reflected in their ionization potentials and electron affinities.

Quantum Monte Carlo simulation for the many-body decomposition of the interaction energy and electron correlation of small superalkali lithium clusters.

Using the fixed-node diffusion Monte Carlo (FN-DMC) method, we calculate the total energy of small lithium clusters Lin (n = 2-6) to obtain the many-body decomposition of the interaction energy of 2- up to 6-body interactions. The obtained many-body decomposition of the interaction energy shows an alternating series with even and odd terms of attractive and repulsive contributions, respectively. The two-body attractive interactions guarantee the stability of the Li2, Li3, and Li4 clusters. For larger clusters Li5 and Li6, the 4-body attractive interactions are required for their stabilization once the strength of the 3-body repulsive interactions overwhelms that of the 2-body attractive ones. With increasing the cluster size, the additive and nonadditive contributions to the interaction energy increase linearly in magnitude but with different slopes for the two-dimensional (2D) planar and three-dimensional (3D) cagelike clusters. The significant increment in nonadditive effects from the 4-atom to the 5-atom cluster has driven the structural transition from 2D to 3D. Combining the FN-DMC calculations with the Hartree-Fock many-body decomposition of the interaction energy, we extract the correlation effects, showing that an odd-even competition pattern in the many-body repulsive and attractive interactions is crucial for the stabilization of the clusters.

Quantum Monte Carlo study of the electron binding energies and aromaticity of small neutral and charged boron clusters.

The valence electron binding energies and the aromaticity of neutral and charged small boron clusters with three and four atoms are investigated using a combination of the fixed-node diffusion quantum Monte Carlo (FN-DMC) method, the density functional theory, and the Hartree-Fock approximation. The obtained electron binding energies such as the adiabatic detachment energy, vertical detachment energy, adiabatic ionization potential, and the vertical ionization potential are in excellent agreement with available experimental measurements. Their decomposition into three physical components such as the electrostatic potential and exchange interaction, the relaxation energy, and the electronic correlation effects has allowed us to determine that the neutral boron clusters are stabilized by the electrostatic and exchange interactions, while the anionic ones are stabilized by the relaxation and correlation effects. The aromaticity is studied based on electronic structure principles descriptor and on the resonance energy. The FN-DMC results from the electronic structure principles of the energy, hardness, and eletrophilicity have supported the aromaticity of B 3 - , B 4 - , and B4 and partially supported the aromaticity of the clusters B3, B 3 + , and B 4 + . The obtained values for the resonance energy of the clusters B 3 - , B3, B 3 + , B4, B 4 + , and B 4 - are 55.1(7), 54.2(8), 33.9(7), 84(1), 67(1), and 58(1) kcal/mol, respectively. Therefore, the order of decreasing stability of the trimer is B 3 - > B 3 > B 3 + , while for the tetramer it is B 4 > B 4 + > B 4 - , which is in agreement with the results from the molecular orbital analysis.

Cutaneous papillomavirus infection in patients with rheumatoid arthritis or systemic lupus erythematosus. A case-control study.

Previous studies informed an increased prevalence of cutaneous papillomavirus (cHPV) infection in patients with systemic lupus erythematosus (SLE). The main objective of our study was to evaluate factors associated with cHPV infection in patients with either rheumatoid arthritis (RA) or SLE, and to determine whether SLE itself is an independent risk factor for cHPV infection. We included 670 patients (in consecutive selection) in this cross-sectional study (550 with RA and 120 with SLE). All patients were evaluated by a dermatologist; patients with cHPV infection were selected as cases (63) and the other 607 patients were selected as controls. The prevalence of cHPV infection was increased 2.8-fold in SLE patients (20%) compared with RA patients (7.1%). When comparing cases with controls, bivariate analysis showed statistically significant differences for: age, having SLE, and treatment with mycophenolate mofetil (MMF). When all of the potential risk factors identified using bivariate analysis (age, having SLE, and MMF) were included into a multivariate model, independent risk factors for cHPV infection were: having SLE (odds ratio: 2.16, 95% confidence interval: 1.04-4.48) and MMF therapy (odds ratio: 2.91, 95% confidence interval: 1.18-7.14).

Adaptability and genotypic stability of Coffea arabica genotypes based on REML/BLUP analysis in Rio de Janeiro State, Brazil.

Biannuality in coffee culture causes temporal variability in plant productivity. Consequently, it is essential to evaluate genotypes during various crop years to ensure selection of productive and stable genotypes. We evaluated the effectiveness of simultaneous selection of coffee genotypes along harvests, based on productivity, stability, and adaptability, via mixed models, for indication of varieties suitable for Rio de Janeiro State. We evaluated 25 genotypes during 4 crop seasons (2009-2012), in a randomized block design with 5 replications. The ranking of genotypes was obtained on the basis of the adaptability and temporal stability methods (harmonic average of genetic values, relative performance of genetic values, and harmonic mean of the relative performance of the genetic values), obtained via restricted maximum likelihood/best linear unbiased procedure analysis. The selection accuracy (0.8717), associated with the high magnitude of mean heritability, indicate good reliability and prospects for success in the indication of agronomically superior genotypes. There was little variation in the ordering of genotypes among the environments, indicating low influence of harvests in the performance of the genotypes. Five of the 25 genotypes were superior and could be recommended for planting in the northwestern region of Rio de Janeiro State, due to high predicted productivity and stability. We recommend that these methodologies for evaluation of productivity, stability, and adaptability be included in the selection criteria for recommendation of genotypes for commercial plantings.

Genetic progress in the UNB-2U population of popcorn under recurrent selection in Rio de Janeiro, Brazil.

As part of the Universidade Estadual do Norte Fluminense recurrent selection program of popcorn, we evaluated full-sib families of the sixth cycle of recurrent selection and estimated genetic progress for grain yield and expansion capacity. We assessed 200 full-sib families for 10 agronomic traits, in a randomized block design, with two replications within sets in two environments: Campos dos Goytacazes and Itaocara, in the State of Rio de Janeiro, Brazil. There were significant differences for families/"sets" for all traits, indicating genetic variability that could be exploited in future cycles. In the selection of superior progenies, the Mulamba and Mock index gave the best gains for popping expansion (PE) and grain yield (GY), with values of 10.97 and 15.30%, respectively, using random economic weights. By comparing the evolution of the means obtained for PE and GY in the cycles C(0), C(1), C(2), C(3), C(4), C(5), and predicted for C(6), a steady increase was observed for both PE and GY, with the addition of 1.71 mL/g (R(2) = 0.93) and 192.87 kg/ha (R(2) = 0.88), respectively, in each cycle. Given the good performance of this popcorn population in successive cycles of intrapopulation recurrent selection, we expect that a productive variety with high expansion capacity will soon be available for producers in the north and northwest regions of Rio de Janeiro State, Brazil.

Stability and adaptability of popcorn genotypes in the State of Rio de Janeiro, Brazil.

This study aimed to obtain estimates of stability and adaptability of phase launched materials and materials recommended in the country, for the northern and northwestern regions of Rio de Janeiro State, Brazil, and made a comparative analysis of different methods to evaluate stability and adaptability of grain yield and popping expansion. To this end, 10 genotypes were evaluated (UNB2U-C3, UNB2U-C4, BRS Angela, Viçosa, Beija-Flor, IAC 112, IAC 125, Zélia, Jade, and UFVM2 Barão de Viçosa) in five environments. The Yates and Cochran method revealed that genotypes UFV2M Barão de Viçosa, BRS Angela and UNB2U-C3 were the most stable for grain yield. This method also indicated superiority of genotypes UNB2U-C3, UNB2U-C4, BRS Angela, Viçosa, IAC 125, and Zélia for popping expansion. The Plaisted and Peterson and Wricke methods demonstrated that genotypes Zélia and UNB2U-C4 were the most productive and stable. These methods indicated genotypes UNB2U-C3 and BRS Angela as the most stable for popping expansion. The Kang and Phan ranking system uses methods based on analysis of variance and classified population UNB2U-C4 as the genotype with the highest stability of grain production and confirmed cultivar BRS Angela as the most stable for popping expansion. Genotypes IAC 112 and UNB2U-C4 were the most stable and adapted for grain yield, according to the Lin and Binns method. The P(i) statistics also ranked UNB2U-C3 and UNB2U-C4 as the genotypes with the best predictability and capacity for popping expansion.

Expression and function of Cbl-b in T cells from patients with systemic lupus erythematosus, and detection of the 2126 A/G Cblb gene polymorphism in the Mexican mestizo population.

Systemic lupus erythematosus (SLE) is characterized by abnormalities in the function of T and B lymphocytes and in the signaling pathways induced through their receptors. Cbl-b is an intracellular adaptor protein that plays a key role in the negative regulation of lymphocyte activity. We explored the expression and function of Cbl-b in T lymphocytes from SLE patients. In addition, the possible association of SLE and a single nucleotide polymorphism (SNP) of the Cblb gene was determined. We studied 150 SLE patients, 163 healthy individuals, and 14 patients with rheumatoid arthritis (RA). The expression of Cbl-b was analyzed in the peripheral blood mononuclear cells, and the negative regulatory function of Cbl-b was assessed by analyzing actin polymerization and the phosphorylation of JNK and c-Jun induced through CD3. Furthermore, the 2126(A/G) SNP of the Cblb gene was detected by real-time polymerase chain reaction. We found a significant small reduction in the expression of Cbl-b as well as increased levels of activation of c-Jun and actin polymerization in T lymphocytes from patients with SLE compared with healthy controls or RA patients. In addition, a significant association between the 2126(A/G) SNP and SLE was detected. Our data suggest that Cbl-b may contribute to the deregulated activation of T lymphocytes observed in SLE.

Probing the ground-state structural transition in small lithium clusters by quantum Monte Carlo simulations.

The ground-state structural transition in small lithium clusters Lin (n = 4 - 6) is analyzed based on the many-body expansion of the interaction energy using the total energy calculated by the fixed-node diffusion Monte Carlo (FN-DMC) simulations. The results show that the transition from 2D to 3D structure occurs through an intricate competition of attractive and repulsive interaction energies. As the structure dimensionality increases from 2D to 3D, the electron-correlation contribution to the interaction energy in the isomer of the ground-state structure is always the largest.

Combining ability of tropical and temperate inbred lines of popcorn.

In Brazil, using combining ability of popcorn genotypes to achieve superior hybrids has been unsuccessful because the local genotypes are all members of the same heterotic group. To overcome this constraint, 10 lines (P(1) to P(10)) with different adaptations to tropical or temperate edaphoclimatic environments were used to obtain 45 F(1) hybrids in a complete diallel. These hybrids and three controls were evaluated in two environments in Rio de Janeiro State. Grain yield (GY), popping expansion (PE), plant height (PH), ear height (EH), and days to silking (FL) were evaluated in randomized complete blocks with three replications. Significant differences between genotypes (P

Does Diamond Stone Grinding Change the Surface Characteristics and Flexural Strength of Monolithic Zirconia?

PURPOSE: The present study evaluated the effect of grinding on the surface morphology, mean roughness, crystalline phase, flexural strength, and Weibull modulus of monolithic (MZ) and conventional (CZ) zirconias. METHODS AND MATERIALS: CZ and MZ bars and square-shaped specimens were distributed into three subgroups, combining grinding (G) and irrigation (W) with distilled water: Ctrl (Control: no grinding, 20 × 4 × 1.2 mm and 12 × 1.2 mm), DG (dry grinding, 20 × 4 × 1.5 mm and 12 × 1.5 mm), and WG (grinding with irrigation, 20 × 4 × 1.5 mm and 12 × 1.5 mm). The grinding (0.3 mm) was performed on a standardized device using a low-rotation wheel-shaped diamond stone. The four-point flexural strength test was performed on the EMIC 2000 machine (5 KN, 0.5 mm/min). Scanning electron microscopy (SEM) was used to evaluate the surface morphology. An X-ray diffractometer (XRD) was used to obtain the crystalline structures that were analyzed by the Rietveld method. Flexural strength (FS) values were subjected to the Shapiro-Wilk test and two-way analysis of variance followed by the Tukey's test (for all tests, α=0.05). RESULTS: Grinding, either with or without irrigation, did not change the FS of the MZ but increased the FS of the CZ. Both MZ and CZ showed similar morphologic patterns after grinding, and in the WG groups, the grinding was more aggressive. The MZ had greater monoclinic content in all groups; grinding without irrigation caused the smallest t→m transformation. CONCLUSION: The grinding, when necessary, should be carried out without irrigation for conventional and monolithic zirconias.

Mechanical and Surface Properties of Monolithic Zirconia.

PURPOSE: This study compared monolithic zirconia with conventional ones based on mean roughness (Ra), Vickers hardness (VHN), topography, transmittance, grain size, flexural strength (FS), Weibull modulus, and fractographic behavior. METHODS AND MATERIALS: One monolithic (Prettau Zircon [PR group]) and two conventional (ICE Zirkon Transluzent [IZ group] and BloomZir [BL group]) zirconias were used. Specimens were tested using a profilometer, a microhardness tester, a scanning electron microscope, a spectrophotometer, and a Universal Testing Machine (EMIC DL 2000). Ra, VHN, grain size, and transmittance were analyzed using the Kruskal-Wallis test associated with Dunn test (α=0.05). FS was analyzed using one-way analysis of variance with the Tukey honestly significant difference test (α=0.05). RESULTS: Means and standard deviations of roughness, after sintering (Ra, in µm) and VHN, were, respectively, 0.11 ± 0.01, 1452.16 ± 79.49, for the PR group; 0.12 ± 0.02, 1466.72 ± 91.76, for the IZ group; and 0.21 ± 0.08, 1516.06 ± 104.02, for the BL group. BL was statistically rougher ( p<0.01) than PR and IZ. Hardness was statistically similar ( p=0.30) for all groups. Means and standard deviations of FS (in MPa) were 846.65 ± 81.97 for the PR group, 808.88 ± 117.99 for the IZ group, and 771.81 ± 114.43 for the BL group, with no statistical difference ( p>0.05). Weibull moduli were 12.47 for the PR group, 7.24 for the IZ group, and 6.31 for the BL group, with no statistical differences. The PR and BL groups had higher transmittance values and grain sizes than the IZ group ( p<0.05). Although the BL group had some fractures that originated in the center of the tensile surface, fractographic analyses showed the same fracture pattern. CONCLUSIONS: All tested zirconia showed similar VHN, and the monolithic zirconia had similar roughness compared to one of the conventional zirconias. In addition, the monolithic zirconia showed similar flexural strength and Weibull modulus compared to the others even though its mean grain size was larger. The total transmittance of monolithic zirconia was higher than only one of the conventional zirconias tested.

Characterization of a Diamond Ground Y-TZP and Reversion of the Tetragonal to Monoclinic Transformation.

PURPOSE: To characterize the surface of an yttria-stabilized zirconia (Y-TZP) ceramic after diamond grinding in terms of its crystalline phase, morphology, mean roughness (Ra), and wettability as well as to determine a thermal treatment to reverse the resulting tetragonal to monoclinic (t-m) transformation. METHODS AND MATERIALS: Y-TZP specimens were distributed into different groups according to the actions (or no action) of grinding and irrigation. Grinding was accomplished using a diamond stone at a low speed. The samples were characterized by x-ray diffraction (XRD), scanning electron microscopy, goniometry, and profilometry. In situ high-temperature XRD was used to determine an annealing temperature to reverse the t-m transformation. Ra was submitted to the Kruskal-Wallis test, followed by the Dunn test (α=0.05). The volume fraction of the monoclinic phase and contact angle were submitted to one-way analysis of variance, followed by the Tukey test (α=0.05). RESULTS: Monoclinic zirconia was observed on the surface of samples after dry and wet grinding with a diamond stone. The volume fraction of the monoclinic phase was smaller on the dry ground samples (3.6%±0.3%) than on the wet ground samples (5.6%±0.3%). High-temperature XRD showed reversion of the t-m phase transformation, which started at 700°C and completed at 800°C in a conventional oven. CONCLUSIONS: Grinding with a diamond stone partially transformed the crystalline phase on the surface of a Y-TZP ceramic from tetragonal to monoclinic zirconia while simultaneously increasing the surface roughness and wettability. The t-m transformation could be reversed by heat treatment at 800°C or 900°C for 60 minutes or 1000°C for 30 minutes.

Two-dimensional electron states bound to an off-plane donor in a magnetic field.

The states of an electron confined in a two-dimensional (2D) plane and bound to an off-plane donor impurity center, in the presence of a magnetic field, are investigated. The energy levels of the ground state and the first three excited states are calculated variationally. The binding energy and the mean orbital radius of these states are obtained as a function of the donor center position and the magnetic field strength. The limiting cases are discussed for an in-plane donor impurity (i.e. a 2D hydrogen atom) as well as for the donor center far away from the 2D plane in strong magnetic fields, which corresponds to a 2D harmonic oscillator.

Single and paired point defects in a 2D Wigner crystal.

Using the path-integral Monte Carlo method, we calculate the energy to form single and pair vacancies and interstitials in a two-dimensional Wigner crystal of electrons. We confirm that the lowest energy point defects of a 2D electron Wigner crystal are interstitials, with a creation energy roughly 2/3 that of a vacancy. The formation energy of the defects goes to zero at melting, suggesting that point defects may be the melting mechanism and that the melting could be a continuous transition. In addition, we find that the interaction between defects is strongly attractive, so that most defects will exist as bound pairs.

Exchange frequencies in the 2D Wigner crystal.

Using path integral Monte Carlo we have calculated exchange frequencies as electrons undergo ring exchanges in a "clean" 2D Wigner crystal as a function of density. The results show agreement with WKB calculations at very low density, but show a more rapid increase with density near melting. Remarkably, the exchange Hamiltonian closely resembles the measured exchanges in 2D (3)He. Using the resulting multispin exchange model we find the spin Hamiltonian for r(s) < or = 175 +/- 10 is a frustrated antiferromagnetic; its likely ground state is a spin liquid. For lower density the ground state will be ferromagnetic.