Dramatic effects of excess oxygen on physical properties and crystal structure of La0.95Sr0.05MnOy single crystal

We have examined the effects of excess oxygen on the magnetization, electrical transport properties and crystal structure of La_0.95Sr_0.05MnO_y. An antiferromagnetic insulator phase confirmed in the as-grown crystal at low temperatures changed to a ferromagnetic insulator phase after the introduction of excess oxygen. The ferromagnetic transition temperature, T_C, systematically increased with increasing oxygen content, y, due to an increase in the mean valence of manganese. However, the T_C of crystals with excess oxygen was lower than that of the La_1−xSr_xMnO_3.00 having identical manganese valence. This is considered to be a result of the competition among the mean valence of manganese, the concentration of cation vacancies, and the mean ionic radius of cations at the A-site.     

Theoretical analysis on changes in thermodynamic quantities upon protein folding: essential role of hydration

The free energy change associated with the coil-to-native structural transition of protein G in aqueous solution is calculated by using the molecular theory of solvation, also known as the three-dimensional reference interaction site model theory, to uncover the molecular mechanism of protein folding. The free energy is decomposed into the protein intramolecular energy, the hydration energy, and the hydration entropy. The folding is accompanied with a large gain in the protein intramolecular energy. However, it is almost canceled by the correspondingly large loss in the hydration energy due to the dehydration, resulting in the total energy gain about an order of magnitude smaller than might occur in vacuum. The hydration entropy gain is found to be a substantial driving force in protein folding. It is comparable with or even larger than the total energy gain. The total energy gain coupled with the hydration entropy gain is capable of suppressing the conformational entropy loss in the folding. Based on careful analysis of the theoretical results, the authors present a challenging physical picture of protein folding where the overall folding process is driven by the water entropy effect.     

Second- and third-order triples and quadruples corrections to coupled-cluster singles and doubles in the ground and excited states

Second- and third-order perturbation corrections to equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) incorporating excited configurations in the space of triples [EOM-CCSD(2)T and (3)T] or in the space of triples and quadruples [EOM-CCSD(2)TQ] have been implemented. Their ground-state counterparts--third-order corrections to coupled-cluster singles and doubles (CCSD) in the space of triples [CCSD(3)T] or in the space of triples and quadruples [CCSD(3)TQ]--have also been implemented and assessed. It has been shown that a straightforward application of the Rayleigh-Schrodinger perturbation theory leads to perturbation corrections to total energies of excited states that lack the correct size dependence. Approximations have been introduced to the perturbation corrections to arrive at EOM-CCSD(2)T, (3)T, and (2)TQ that provide size-intensive excitation energies at a noniterative O(n(7)), O(n(8)), and O(n(9)) cost (n is the number of orbitals) and CCSD(3)T and (3)TQ size-extensive total energies at a noniterative O(n(8)) and O(n(10)) cost. All the implementations are parallel executable, applicable to open and closed shells, and take into account spin and real Abelian point-group symmetries. For excited states, they form a systematically more accurate series, CCSD1 eV) and the ground-state wave function has single-determinant character. In other cases, however, the corrections tend to overestimate the triples and quadruples effects, the origin of which is discussed. For ground states, the third-order corrections lead to a rather small improvement over the highly effective second-order corrections [CCSD(2)T and (2)TQ], which is a manifestation of the staircase convergence of perturbation series.     

Synthesis and phosphate uptake behavior of Zr4+ incorporated MgAl-layered double hydroxides

We synthesized Zr(4+) incorporated MgAl-layered double hydroxides, Mg(AlZr)-LDH(A) (where A denotes a counteranion in the interlayer space and is expressed as CO(3) for carbonate and Cl for chloride ions), with different molar ratios of Mg/(Al+Zr). Then we characterized their uptake behavior toward phosphate ions. CO(3)-type tertiary LDH materials synthesized at room temperature show low crystallinity, whereas the highly crystalline Cl-type tertiary LDH, [Mg(0.68)Al(0.17)Zr(0.14)(OH)(2)][Cl(0.26)(CO(3))(0.04)1.24H(2)O], was synthesized for the first time using a hydrothermal treatment at 120 degrees C. The distribution coefficients (K(d)) of oxo-anions were measured with a mixed solution containing trace amounts of the anions. The selectivity sequences were Cl(-), NO(-)(3)相似文献   

Characterization of nanoscale mechanical heterogeneity in a metallic glass by dynamic force microscopy

We report nanoscale mechanical heterogeneity of a metallic glass characterized by dynamic force microscopy. Apparent energy dissipation with a variation of ~12%, originating from nonuniform distribution of local viscoelasticity, was observed. The correlation length of the heterogeneity was measured to be ~2.5 nm, consistent with the dimension of shear transformation zones for plastic flow. This study provides the first experimental evidence on the nanoscale viscoelastic heterogeneity in metallic glasses and may fill the gap between atomic models and macroscopic glass properties.     

Thermodynamic limit and size-consistent design

This article aims to dispel confusions about the definition of size consistency as well as some incompatibility that exists between different criteria for judging whether an electronic structure theory is size consistent and thus yields energies and other quantities having correct asymptotic size dependence. It introduces extensive and intensive diagram theorems, which provide unambiguous sufficient conditions for size consistency for extensive and intensive quantities, respectively, stipulated in terms of diagrammatic topology and vertex makeup. The underlying algebraic size-consistency criterion is described, which relies on the polynomial dependence of terms in the formalism on the number of wave vector sampling points in Brillouin-zone integrations. The physical meanings of two types of normalization of excitation amplitudes in electron-correlation theories, namely, the intermediate and standard normalization, are revealed. The amplitudes of the operator that describes an extensive quantity (the extensive operator) are subject to the intermediate normalization, while those of the operator that corresponds to an intensive quantity (the intensive operator) must be normalized. The article also introduces the extensive-intensive consistency theorem which specifies the relationship between the spaces of determinants reached by the extensive and intensive operators in a size-consistent method for intensive quantities. Furthermore, a more fundamental question is addressed as to what makes energies extensive and thus an application of thermodynamics to chemistry valid. It is shown that the energy of an electrically neutral, periodic, non-metallic solid is extensive. On this basis, a strictly size-consistent redefinition of the Hartree--Fock theory is proposed.     

Squarefree P-modules and the cd-index

In this paper, we introduce a new algebraic concept, which we call squarefree P-modules. This concept is inspired from Karu's proof of the non-negativity of the cd-indices of Gorenstein* posets, and supplies a way to study cd-indices from the viewpoint of commutative algebra. Indeed, by using the theory of squarefree P-modules, we give several new algebraic and combinatorial results on CW-posets. First, we define an analogue of the cd-index for any CW-poset and prove its non-negativity when a CW-poset is Cohen–Macaulay. This result proves that the h-vector of the barycentric subdivision of a Cohen–Macaulay regular CW-complex is unimodal. Second, we prove that the Stanley–Reisner ring of the barycentric subdivision of an odd dimensional Cohen–Macaulay polyhedral complex has the weak Lefschetz property. Third, we obtain sharp upper bounds of the cd-indices of Gorenstein* posets for a fixed rank generating function.     

Ring Opening Three-Carbon Extension of 2-Carboethoxycyclo-Alkanones with 3-Bromo-1-(p-Tolylsulfonyl)Propene

Reaction with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) of 2-[3-(p-tolylsulfonyl)-2-propenyl]-2-carboethoxycycloalkanones, derived from 2-carboethoxy-2-sodiocycloalkanones and 3-bromo-l-(p-tolylsulfonyl)propene, caused ring opening three-carbon extension in ethanol and three-carbon ring expansion in benzene to produce terminal dienes and cyclic dienes, respectively.