Conformations and enthalpies of formation of methylenecyclohexane, 1,4‐dimethylenecyclohexane,cyclohexanone, 4‐methylenecyclohexanone, 1,4‐cyclohexanedione,and their mono‐ and dioxa derivatives by G3(MP2)//B3LYP calculations

A computational study of the stable conformations and gas‐phase enthalpies of formation at 25 °C of the title compounds has been carried out by G3(MP2)//B3LYP calculations. The work stems from our early observations on the thermodynamic and NMR spectroscopic properties of 2‐methylenetetrahydropyran and related compounds suggesting a dominating chair conformation, with poor p–π overlap in the ? O? C?C moiety, for these compounds. Besides computational verification of the chair conformation of 2‐methylenetetrahydropyran, the work was extended to find out the stable conformations of a number of other related compounds and to evaluate the relative stabilities of the various conformers. Another important goal of the work was the estimation of the gas‐phase enthalpies of formation of the present compounds, for which such literature data are scarce. A significant error in the literature value of the enthalpy of formation of methylenecyclohexane was found. Finally, the relative enthalpy levels of the isomeric compounds of this work are discussed. The high thermodynamic stability of the compounds containing an ester functional group, ? O? C?O, relative to the stability of isomeric compounds with an ? O? C?C moiety in place of the ester function, is demonstrated. Copyright © 2009 John Wiley & Sons, Ltd.     

Stress effects on the anisotropic thermal expansions of “martensitic” A15 compounds

Precision capacitance dilatometry provides a sensitive measure of the thermal strain developed in a sample undergoing a structural distortion with its varying temperature. The A15 structure compounds, V₃Si and Nb₃Sn, are well known to undergo distortion from their cubic structures at room temperature to tetragonal structures (c/a > 1 for V₃Si and c/a < 1 for Nb₃Sn) at low temperatures. In the past, highly anomalous thermal expansion behaviour recorded for these materials has been attributed to a strongly anharmonic lattice potential manifesting itself in unusually high, and strongly temperature-dependent, Grüneisen parameters. Further studies on polycrystalline material revealed this anomalous expansion to be highly anisotropic at temperatures for which, according to conventional diffraction data, the materials are cubic. This behaviour was linked to control of sample morphology by a residual stress field resulting from sample preparation.

More recent experiments, in which the transformation morphology has been controlled by the application of external stresses to single crystal V₃Si and polycrystalline samples of Nb₃Sn and Nb₃(Sn_1-x Sb _x ), have confirmed the occurrence of significant anisotropy in the thermal strain in the cubic phase, well above the structural transformation.

We link this departure from cubic symmetry with the well-known soft-mode character of these materials and the associated “central peak” scattering which is also observed well above the transformation temperature. We are led to propose that the “central peak” is the precursor to a Bragg reflection for the transformation structure. This coincidence between “central peak” scattering and the reciprocal lattice for the transformed phase in Ti-Ni has been termed a “ghost lattice”.     

Изотопные мишени для ядерных исследований

A non-contact measuring method on electrostatic potential by using α-ray ionization is proposed. In this method potential of a charged material is estimated from ionic current flowing through an ion collector attached with a small ²⁴¹Am source. As hade electrode surrounding the collector has a function of adjusting sensitivity and potential up to 50 kV was measured with precision of 1 kV.     

Absolutbestimmung der spezifischen Aktivität 35S-haltiger Substanzen

Als wesentlichste Vorausselzungen für eine präzise Absolutbestimmung der spezifischen Aktivität ³³S-haltiger Substanzen werden die Sorption von SO₂ an den Zählrohren und der Füllapparatur, die Beeinflussung des Gasentladungsmechanismus im beschränkten Proportionalbereich durch negativ geladene SO₂-Ionen und die kinetischen Isotopieeffekte bei nicht hundertprozentiger Überführung der Ausgangssubstanzen zu Meβgas untersucht. Speziell beschrieben werden die Umsetzung von Natriumsulfat bzw. Schwefelsäure in wäβriger Lösung und Thioharstoff zu Bariumsulfat und dessen Verbrennung zu Schwefeldioxid. Der Gesamtfehlre, mit dem die Angabe der spezifischen Aktivität für die genannten Ausgangssubstanzen behaftel ist, wird angegeben.     

Phonon density-of-states in the new superconductor MgB 2

We provide here experimental data on the phonon density-of-states of MgB₂ obtained by the inelastic neutron scattering technique. The measurements were performed for the natural boron-based magnesium diboride with use of a time-of-flight neutron spectrometer. Several phonon bands were observed in the phonon spectrum at energies of about 33, 55, 82 and 99 meV. We show that the cut-off energy of the density-of-states occurs at around 105 meV which is much higher than expected so far from heat-capacity data and partially explains the high T _c value observed for MgB₂. The characteristic phonon energies are indicative of an intermediate coupling regime in this compound. We conclude that a much needed neutron experiment aimed at the study of the isotopic effect in the phonon density-of-states of MgB₂ is conceivable. Received 19 March 2001     

几种叔丁墓酚化合物的核磁共振研究

研究了11种叔丁基酚化合物的化学位移和偶合常数,并讨论了影响因素.     

Vibrational Spectroscopy of Phenols and Phenolic Polymers. Theory,Experiment, and Applications

In the first part of this review, the authors give a survey on the literature of vibrational spectroscopy of phenol, phenol derivatives, and other phenolic componds from the last decade of the last century through today. The classical and modern methods of vibrational spectroscopy are also introduced and a glossary is included to aid comprehension. The second part deals with the literature regarding the importance of vibrational spectroscopy in the investigation and identification of phenolic compounds in natural substances, the application of vibrational spectroscopy in composite and synthetic polymer chemistry, and following of chemical processes and investigating their resulting products. Vibrational spectroscopy is a very good tool for determination of molecular structures and is important in chemical analysis and in the chemical industry.     

Antiferromagnetic Ordering in TmCu2

Intermetallic compound TmCu₂ crystalizes in the orthorhombic structure, orders antiferromagnetically (AF) and exhibits four different AF phases below T _N = 6.5 K. In all these phases the Tm magnetic moment is parallel to the b-axis. The ground-state AF1 (T < 3.4 K) corresponds to the squared-up AF structure with propagation vector ₀₁ = (5/8, 0, 0) and magnetic unit cell 8a × b × c. Narrow phases AF2 and AF3 (3.3 K < T < 3.7 K and 3.6 K < T < 4.6 K) are 'spin-slip'-derivatives from the AF1 structure, yielding propagation vectors ₀₂ = (0.633, 0, 0.02) and ₀₃ = (0.618, 0, 0), respectively. The phase AF4 (4.4 K < T < T _N) is then incommensurate transversal spin-wave with the propagation ₀₄ = (0.64, 0, 0). The co-existence of AF phases indicates the first-order transitions between them.     

Carbon-13 NMR Study of 2,4,6-Triaryl Pyridinium Salts

The carbon-13 chemical shift of seventeen N-substituted 2,4,6-triphenyl pyridinium salts (TPP) and N-substituted 2,4,6-triaryl pyridinium (TsPP) salts have been determined.