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191.
We present a general, rigorous theory of Lee-Yang zeros for models with first-order phase transitions that admit convergent contour expansions. We derive formulas for the positions and the density of the zeros. In particular, we show that, for models without symmetry, the curves on which the zeros lie are generically not circles, and can have topologically nontrivial features, such as bifurcation. Our results are illustrated in three models in a complex field: the low-temperature Ising and Blume-Capel models, and the q-state Potts model for large q. 相似文献
192.
Vocal vibrato is regarded as one of the essential characteristics of voice quality in classical singing. Professional singers seem to develop vibrato automatically, without actively striving to acquire it. In this longitudinal investigation, the vocal vibrato of 22 singing students was examined at the beginning of and after 3 years of professional singing education. Subjects sang an ascending-descending triad pattern in slow tempo on vowel [a:] at a comfortable pitch level twice at soft (piano) and twice at medium (mezzoforte) loudness. The top note of the triad pattern was sustained for approximately 5s. The mean and the standard deviation (SD) of the vibrato rate were measured for this note. Results revealed that after 3 years of training, voices with vibrato slower than 5.2 Hz were found to have a faster vibrato, and voices with vibrato faster than 5.8 Hz were found to have a slower vibrato. Standard deviation of vibrato rate was higher in soft than in medium loudness, particularly before the education. Also high values of SD of vibrato rate, exceeding 0.65 Hz, had decreased after the education. These findings confirm that vibrato characteristics can be affected by singing education. 相似文献
193.
194.
Dr. Saravanan Gowrisankar Dr. Helfried Neumann Dirk Gördes Kerstin Thurow Dr. Haijun Jiao Prof. Dr. Matthias Beller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):15979-15984
An efficient procedure for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, with molecular oxygen under ambient conditions has been achieved. By applying catalytic amounts of Pd(OAc)2 in the presence of tertiary phosphine oxides (O?PR3) as ligands, a variety of substrates are selectively oxidized without formation of ester byproducts. Spectroscopic investigations and DFT calculations suggest stabilization of the active palladium(II) catalyst by phosphine oxide ligands. 相似文献
195.
3D porous and non-porous structures are designed and prepared by stereolithography using resins based on PTMC macromers. Tough, flexible network films prepared in this manner show E moduli of ≈3.8 MPa and high elongations at break >900%; tensile strengths are ≈4.2 MPa. These values increase with increasing PTMC macromer molecular weight. To reach suitable viscosities for processing, up to 45 wt% propylene carbonate is added as non-reactive diluent. The solid specimens have compression moduli of 3.1-4.2 MPa, similar to the values determined in tensile testing. The built porous structures show porosities of 53-66% and average pore sizes of 309-407 μm. The compression moduli of the porous structures are significantly lower than those of the solid structures. 相似文献
196.
We used a combination of theoretical and experimental methods to derive the spectroscopic properties of imidazolium-based ionic liquids. Vibrational frequencies, NMR chemical shifts, and quadrupole coupling constants react in comparable manner to changes in the chemical environment. This suggests that both the IR and the NMR spectroscopic properties reflect a similar type of electronic perturbation caused by hydrogen bonding. These relationships of the spectroscopic properties provide detailed information about structural complexes and may thus serve as good indicators of ion-pair formation. They also help to decide which spectroscopic tool is the most sensitive for investigating molecular interactions. The measurement of only one spectroscopic property allows the prediction of other properties that cannot be so easily measured. In some cases, this is the only way to obtain reliable coupling constants for deriving molecular correlation times from macroscopic NMR relaxation times, thus opening a new path for studying structure-dynamics relations in ionic liquids. 相似文献
197.
The orange cerium‐niobium‐oxysulfide Ce3NbO4S3 was synthesized by the solid state reaction of CeO2, Ce‐metal, Nb2O5 and sulfur at 1100 °C. The crystal structure has orthorhombic symmetry (space group Pbam, a = 7.055(1), b = 14.571(3), c = 7.627(2) Å, Z = 4) and contains isolated [Nb2S4O6]10− ions consisting of two strongly distorted, edge sharing NbO3SS2/2 octahedra. Niobium is connected to three oxygen and three sulfur atoms. The cerium atoms are eightfold coordinated by oxygen and sulfur atoms. Certain oxygen and sulfur atoms are not connected to niobium, but exclusively surrounded by cerium. By connecting these cation polyhedra, one recognizes layers of polycations perpendicular to the c‐axis. The magnetic susceptibility shows Curie‐Weiss behavior with an effective magnetic moment μeff = 2.63(1) μB/Ce in agreement with Ce3+. A Weiss‐constant θp = –12(1) K indicates weak antiferromagnetic coupling. No magnetic ordering was detected above 2 K. 相似文献
198.
Dirk Walther 《Journal of organometallic chemistry》1980,190(4):393-401
Nickel(O) complex moieties with a high electron density at the central atom are able to yield stable complexes with many aromatic aldehydes. 1H NMR spectroscopic data give evidence about olefin-like bonding of the aldehyde group and indicate a high charge transfer. Chelate ligands like tetramethylethylenediamine yield stable complexes of the composition (TME)NiL (L = aldehyde, benzil, ,β-unsaturated carbonyl compounds). Some reactions and properties of typical mixed ligand complexes are described. 相似文献
199.
Metal ion coordination in metallo-supramolecular assemblies offers the opportunity to fabricate and study devices and materials that are equally important for fundamental research and new technologies. Metal ions embedded in a specific ligand field offer diverse thermodynamic, kinetic, chemical, physical and structural properties that make these systems promising candidates for active components in functional materials. In particular, dynamic coordination polymers offer exciting opportunities to provide materials with responsive properties. In addition, this approach allows to incorporate the well known properties of metal complexes in polymeric architectures. This review highlights the improvements and the possible applications based on metallo-supramolecular systems with an emphasis on materials science. Examples for new materials such as molecular magnets, coordination polymers as carrier package as well as molecular electronics are featured in this article. 相似文献
200.
The predictive capabilities of the shear-modified Gurson model [Nielsen and Tvergaard, Eng. Fract. Mech. 77, 2010] and the Modified Mohr-Coulomb (MMC) fracture model [Bai and Wierzbicki, Int. J. Fract. 161, 2010] are evaluated. Both phenomenological fracture models are physics-inspired and take the effect of the first and third stress tensor invariants into account in predicting the onset of ductile fracture. The MMC model is based on the assumption that the initiation of fracture is determined by a critical stress state, while the shear-modified Gurson model assumes void growth as the governing mechanism. Fracture experiments on TRIP-assisted steel sheets covering a wide range of stress states (from shear to equibiaxial tension) are used to calibrate and validate these models. The model accuracy is quantified based on the predictions of the displacement to fracture for experiments which have not been used for calibration. It is found that the MMC model predictions agree well with all experiments (less than 4% error), while less accurate predictions are observed for the shear-modified Gurson model. A comparison of plots of the strain to fracture as a function of the stress triaxiality and the normalized third invariant reveals significant differences between the two models except within the vicinity of stress states that have been used for calibration. 相似文献