Pressure-induced H2 opacity in the 5-μm region

The H₂ opacity arising from the pure-rotational hexadecapole-induced U₀(J) transitions occurring during H₂H₂ and H₂He collisions, and from the hexadecapole-induced U₀(J) + S₀(J′) and the quadrupole-induced S₀(J) + S₀(J′) transitions in H₂He collisions, has been calculated. The U₀(J) and S₀(J) + S₀(J′) contributions from H₂H₂ collisions are important H₂ opacities in the frequency range from 700–3000 cm^?1 for temperatures appropriate to the outer planets. It is concluded that this opacity is needed in addition to the opacity from the extrapolation of the 0-0 and 1-0 H₂H₂ collisionally induced bands to interpret the spectrum at 5 μm for the outer planets.     

Temperature dependence of pressure broadening of NH3 perturbed by H2 and N2

The temperature dependence of pressure broadening of 134 rovibrational transitions of several branches in the ν₄ and 2ν₂ bands of ammonia perturbed by H₂ and N₂ has been measured using a high-resolution Fourier transform spectrometer. The temperature range covered during the experiments was between 235 and 296 K. The pressure-broadening linewidths were obtained using the method of multipressure fitting to the measured shapes of the lines. These broadenings were also calculated using a semiclassical model leading to a reasonable agreement with the observations and reproduces well the strong systematic experimental J and K quantum number dependencies. The retrieved values of the linewidths, along with those previously determined from the spectra at room temperature, were used to derive the temperature dependence of both H₂ and N₂ broadening of NH₃ lines. The broadening coefficients were shown to fit closely the well-known exponential law. For both experimental and theoretical results, the temperature exponent n has been obtained. Careful inspection of the experimental values shows that, contrary to the linewidths, the coefficient n is nearly K independent within each J multiplet. Also for a given J it does not seem to exhibit any noticeable variation with the type of rotational transition. On the other hand, the calculated n values exhibit a strong J and K systematic dependencies. n increases with K for a given J, decreases with J for a given K and are independent of the type of rotational transition.     

The temperature dependence of the angular variation of,and the critical point exponent for the EPR linewidth in the two-dimensional canted antiferromagnetic (C2H5NH3)2MnBr4: Evidence for a structural phase transition

The angular variation of the EPR linewidths in single crystals of (C₂H₅NH₃)₂MnBr₄ has been measured as a function of temperature. The angular dependence is well characterized by δH(θ) = a + b(3 cos²θ ? 1) + c(3 cos²θ ? 1)². The temperature dependence of the expansion coefficients is reported, and the effect of critical point fluctuations near the Néel temperature as well as a linear temperature dependence at high temperature are observed. A sharp decrease in linewidths at 160°K is attributed to a structural phase transition. The Néel temperature is determined to be 46°K (± 1°) from linewidth measurements of a powder sample. The linewidths diverge exponentially near the Néel temperature with a critical point exponent of 1.5.     

Microwave linewidths of C2H4O perturbed by H2, N2, O2 and CO2

Microwave linewidths of C₂H₄O (κ = -0.41) broadened by H₂, N₂, O₂, and CO₂ and considering dipole-quadrupole interactions have been calculated using the Mehrotra-Boggs theory (1977). This theory accounts satisfactorily for observed linewidths     

On the validity and properties of the atom-atom potential as a function of intermolecular separation,configuration, and partial wave order

The intermolecular partial wave expansion of the atom-atom potential U is reviewed briefly and developed, by using results due to Sack, so that the radial components of the expansion can be evaluated to arbitrary accuracy for all relevant partial wave orders and values of the intermolecular distance r. These results are used to study the convergence of the partial wave expansion of U as a function of partial wave order, r, intermolecular orientation, and the anisotropy of the interacting molecules. In marked contrast to previous work it is found that many of the higher order partial wave components of U are important relative to the isotropic term even for the interaction of relatively spherical molecules and that the results obtained from a truncated partial wave expansion depend significantly upon the method of summation due to the generally poor convergence of the expansion. The validity of the atom-atom potential as a representation of the correct attractive intermolecular potential is also discussed in some detail. There are basic problems associated with the representations furnished by both the isotropic and the anisotropic parts of the atom-atom potential at intermediate and large r. The different convergence properties of the r ^-1 expansions of the partial wave expansions of U and of the correct potential for these values of r is illustrated by using model interactions. While it appears that it may be possible to obtain a qualitatively reasonable representation of the attractive part of an intermolecular potential over a useful range of r from atom-atom results, this apparently cannot be achieved for wider ranges of r or for the purely anisotropic part of the potential.     

Pressure Lineshift and Broadening Coefficients in the 2ν3 Band of OCS

In this study we report the first measurements of the pressure-induced lineshift coefficients due to Ar, He, O₂, and N₂ for 22 rovibrational lines from P(53) to R(53), belonging to the 2ν₃ band of ¹⁶O¹²C³²S at 4100 cm⁻¹. The lineshift results were obtained from the simultaneous record of the pressure-broadened and pure low-pressure OCS lines, using a tunable difference-frequency laser spectrometer. For four lines of the 2ν₃ band we also report Ar-, He-, O₂-, and N₂-broadening coefficients by fitting Voigt and Rautian profiles to the measured shapes of these lines. The broadening and shift coefficients are compared to the results of theoretical calculations based on the semiclassical Robert–Bonamy formalism and two different isotropic and anisotropic intermolecular potentials. For OCS–Ar we also consider the Smith–Giraud–Cooper model including all orders of the interaction within the peaking approximation. In all cases, the calculated broadening coefficients are in reasonable agreement with the experimental data. By considering adjustable parameters for the vibrational dependence of the isotropic potential, the general trends of the lineshifts with J can be roughly predicted, except at low J values where an asymmetry behavior for P and R branches is generally observed.     

The structure of H2CSe from microwave spectroscopy

The microwave spectra of six isotopic species of selenoformaldehyde, H₂¹³C^78,80Se, D₂C^78,80Se, and DHC^78,80Se have been assigned. The resultant rotational constants, together with those of previous work yield the following substitution structure: r(C=Se) = 175.31 pm, HCH = 117.93°, and r(C---H) = 109.04 pm. This structure is compared with the equilibrium structure derived from ab initio calculations. The fundamental vibrational frequencies and centrifugal distortion constants of H₂C⁸⁰Se have been calculated.     

Effect of sorbic acid doping on flux pinning in bulk MgB2 with the percolation model

In this paper, we study the doping effect of sorbic acid (C₆H₈O₂), from 0 to 20 wt.% of the total MgB₂, on critical temperature (T_c), critical current density (J_c), irreversibility field (H_irr) and crystalline structure. The XRD patterns of samples show a slightly decrease in a-axis lattice parameter for doped samples, due to the partial substitution of carbon at boron site. On the other hand, we investigate the influence of doping on the behavior of flux pinning and J_c(B) in the framework of percolation theory and it is found that the J_c(B) behavior could be well fitted in high field region. The two key parameters, anisotropy and percolation threshold, play very important roles. It is believed that the enhancement of J_c is due to the reduction of anisotropy in high field region.     

Stereodynamics of the reactions Ne+H2+/Ne+D2+/Ne+T2

The vector correlations between products and reagents for the reactions Ne+H + 2 , Ne+D + 2 , and Ne+T + 2 are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lü et al. [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections (2π/σ)(dσ 00 /dω t ), (2π/σ)(dσ 20 /dω t ), (2π/σ)(dσ 22+ /dω t ), and (2π/σ)(dσ 21 /dω t ), and the distributions of P (θ r ), P (φ r ), and P (θ r ,φ r ) are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Translational and rotational motions of a diatomic molecule enclosed in a solid matrix

The hamiltonian for a molecule enclosed in a cavity may be written H = H ^R(θ) + H ^T(r) + U ^RT(θ, r), where θ and r denote the molecular orientation and the displacement of the centre of mass. The crystalline potential seen by the guest molecule can be explicitly calculated on the basis of atom-atom and electrostatic multipolar interactions, by using an nth-order gradient formula in the spherical representation. We take a N ₂ molecule encaged in β-quinol clathrate as our model system, and solve variationally the Schrödinger equation for H to clarify the translation-rotation coupling. Energy levels of H are obtained as a function of the height of the hindering potential for rotation, by modifying the strength of the electrostatic multipolar interaction. Three limiting cases of H ^R are important: (a) libration around the Z-axis, (b) free rotation, and (c) an oscillational rotation whose equilibrium orientation is perpendicular to the Z-axis. The constrained translation under consideration is an anharmonic and almost spherically symmetric oscillation. The Pauli principle must be applied to the eigenstate of H. Excepting the case (a), translational states of H are different for different nuclear spin species, and higher-order effects of U ^RT on these states are significant. For p-N₂, some modes of motion interchange if the rotational motion changes from case (a) to case (c). If the constraining potential for translation is steeper, the effect of U ^RT will become smaller. The anharmonicity involved in H ^T is not negligible in discussing this effect.     

Rotational and hyperfine spectra for a sandwich titanium complex, C5H5TiC7H7

Microwave spectroscopy measurements and density functional theory calculations are reported for the cyclopentadienyl cycloheptatrienyl titanium complex, C₅H₅TiC₇H₇. Rotational transition frequencies for this symmetric-top complex were measured in the 4-13 GHz range using a Flygare-Balle-type pulsed beam spectrometer. The spectroscopic constants obtained for the normal C₅H₅⁴⁸TiC₇H₇ isotopomer are B = 771.78907(38), D_J = 0.0000295(41), and D_JK = 0.001584(73) MHz. The quadrupole hyperfine splittings for C₅H₅⁴⁷TiC₇H₇ were clearly observed and the measured constants are B = 771.79024(32) MHz, D_J = 0.0000395(33), D_JK = 0.001646(24), and eQq_aa = 8.193(40) MHz. Analysis of the experimental and theoretical rotational constants indicates that the η⁷-C₇H₇Ti and η⁵-C₅H₅Ti bond lengths in the gas phase are about 0.02 Å longer than those reported for the solid-state X-ray structure. The calculated Ti-C bond lengths are shorter for the C₇H₇ ligand (r(Ti-C) = 2.21 Å) than for the C₅H₅ ligand (r(Ti-C) = 2.34 Å), and the C₇H₇ H atoms are displaced 0.15 Å out of the C₇ plane, toward the Ti atom.     

q-Fuzzy Spheres and Quantum Differentials on Bq[SU2] and Uq(su2)

We provide a new unified construction of the two-parameter Podleś two-spheres as characterised by a projector e with trace _q (e) = 1 + λ. In our formulation the limit in which q → 1 with λ fixed is the fuzzy sphere, while the limit λ → 0 with q fixed is the standard q-deformed sphere. We show further that the non-standard Podleś spheres arise geometrically as ‘constant time slices’ of the unit hyperboloid in q-Minkowski space viewed as the braided group B _q [SU ₂]. Their localisations are then isomorphic to quotients of U _q (su ₂) at fixed values of the q-Casimir precisely q-deforming the fuzzy case. We also use transmutation and twisting theory to introduce a C_q[G_\mathbb C]{C_q[G_\mathbb {C}]} -covariant differential calculus on general B _q [G] and U _q (g), with Ω(B _q [SU ₂]) and Ω(U _q (su ₂) given in detail. To complete the picture, we show how the covariant calculus on the 3D bicrossproduct spacetime arises from Ω(C _q [SU ₂]) prior to twisting.     

Conformational Equilibria in Polypeptides. I. Determination of AccurateJHCCoupling Constants in Antamanide by 2D NMR Multiplet Simulation

High-precision heteronuclear three-bond coupling constants including³J(H^N, C′),³J(H^N, C^β),³J(H^α,C^γ), and³J(H^β, C′) are determined for the nonproline residues in uniformly¹³C-enrichedantamanide,cyclo-(-Val¹-Pro²-Pro³-Ala⁴-Phe⁵-Phe⁶-Pro⁷-Pro⁸-Phe⁹- Phe¹⁰-), using quantitative numerical 2D NMR spectrum evaluation based on the product-operator formalism. The experimental basis comprises two-dimensional¹H,¹³C-heteronuclear relayed E.COSY spectra [J. M. Schmidt, R. R. Ernst, S. Aimoto, and M. Kainosho,J. Biomol. NMR6,95 (1995)], the multiplet patterns of which are subjected to iterative least-squares 2D multiplet-simulation procedures. Accuracy and precision of the spectrum fit are assessed byFstatistics and analysis of variances (ANOVA) leading to confidence intervals for the optimized spin-system parameters. The long-range J coupling constants obtained and their standard deviations provide the experimental foundation for a later detailed analysis of φ and χ₁dihedral-angle equilibrium conformations contributing to the flexible peptide structure.     

Mechanisms of direct microwave absorption in Y1Ba2Cu3O7−x

Direct microwave absorption was studied as a function of magnetic field up to 8 kG and in a temperature range between 10 K and 150 K in Y₁Ba₂Cu₃O_7−x. Large microwave absorption was observed below T_c over a wide magnetic field range. The microwave power absorption is approximately described by I=A(T) H+C(T), where A(T) and C(T) are temperature dependent constants. A(T) is proportional to the square root of the microwave power, while C(T) shows a different behaviour. We propose different origins for A(T) and C(T), namely fluxons in grains and weak Josephson links. Moreover, also flux trapping was observed in the superconducting state. Possible mechanisms for the absorption are discussed.     

Microstructural and superconducting properties of C6H6 added bulk MgB2 superconductor

The effect of aromatic hydrocarbon (benzene, C₆H₆) addition on lattice parameters, microstructure, critical temperature (T_c), critical current density (J_c) of bulk MgB₂ has been studied. In this work only 2 mol% C₆H₆ addition was found to be very effective in increasing the J_c values, while resulting in slight reduction of the T_c. J_c values of 2 mol% C₆H₆ added MgB₂ bulks reached to 1.83×10⁶ A/cm² at 15 K and 0 T. Microstructural analyses suggest that J_c enhancement is associated with the substitution of carbon with boron and which also results in the smaller MgB₂ grain size. The change in the lattice parameters or the lattice disorder is claimed as a cause of the slight reduction in the T_c by carbon addition. We note that our results show the advantages of C₆H₆ addition include homogeneous mixing of precursor powders, avoidance of expansive nanoadditives, production of highly reactive C, and significant enhancement in J_c of MgB₂, compared to un-doped samples.     

BeH,H2和BeH2的分子结构和势能函数

用二次组态相关(QCISD)和密度泛函(B3LYP)方法, 选用6-311++g(d,p), 6-311++g(3df,3pd)和D95(3df,3pd)基组对H₂, BeH和BeH₂分子的结构进行优化. 得到它们的基态电子态分别为H₂(¹Σ_g), BeH(²Σ)和BeH₂(¹Σ_{g 关键词： BeH 2}')" href="#">BeH₂ 2')" href="#">H₂ 二次组态相关(QCISD) 势能函数     

Hydrogen line broadening in the ν2 and ν4 bands of phosphine at low temperature

Using a tunable diode-laser spectrometer, we have measured H₂-broadening coefficients of PH₃ at low temperature (173.2 K) for 27 lines in the ^QR branch of the ν₂ band and in the ^PP and ^RP branches of the ν₄ band. The recorded lines with J values ranging from 2 to 11 and K from 0 to 9 are located between 1016 and 1093 cm⁻¹. The collisional widths are determined by fitting each spectral line with a Voigt profile and a speed-dependent Rautian profile which provides slightly larger broadening coefficients than the Voigt model. These coefficients have also been calculated on the basis of a semiclassical model of interacting linear molecules by considering an atom-atom Lennard-Jones potential in addition to the weak electrostatic contributions. Except for three ^QR(J,K) lines, where K = J, the calculated broadening coefficients are in good agreement with the experimental data. By comparing the results obtained at room and low temperatures, the temperature dependence of linewidths has been determined both theoretically and experimentally.     

采用Lennard-Jones原子间势研究(C60)N分子团簇的结构演化行为

采用描述原子间相互作用的Lennard-Jones势来描述C₆₀分子间的相互作用,考虑了每个C₆₀分子的一定位置取向,并采用最速下降法计算了IH,fcc,hcp,DH及SC五种典型结构满壳层(C₆₀)_N团簇(N<2000)的能量.结果显示:当尺寸较小(N<20)时,IH结构最稳定;当尺寸处于中等(50<N<300)时,HCP结构最稳定;当尺寸较大(300<N 关键词： 60团簇')" href="#">C₆₀团簇 取向 最速下降法 结构演化     

Zero field splittings of Gd3+IN Nd2(SO4)3 · 8H2O and Sm2(SO4)3 · 8H2O crystals at 273 K

The electron paramagnetic resonance (EPR) of Nd₂(SO₄)₃ · 8H₂O and Sm₂(SO₄)₃ · 8H₂O doped with Gd³⁺ has been carried out at 273 K and the spin-Hamiltonian parameters are deduced. The zero field splittings have been computed and compared with those observed directly by Bogle and Symmons. It is found that the discrepancy in the zero field splittings. between computed and directly observed values falls within the range of linewidths of directly observed values.     

Pinning mechanism in carbon nanotube doping of MgB2 superconductor

MgB_1.9C_0.1 samples are synthesized under the ambient pressure (AP) and high pressure (HP), respectively. The further studies demonstrate different field-dependence of the critical current density J_c(H) in each sample. In the view of two-gap superconductivity in these samples, δT_c pinning (resulting from the spatial fluctuations of the transition temperature) is dominant in the AP sample, while in the HP sample, both δT_c and δl pinning (due to the mean-free-path fluctuations) act together and their contributions vary with temperature. Besides the improvement of H_c2(0), due to the different pinning mechanism, J_c(H) of the HP sample shows a slower decay with the increasing fields than that of the AP sample in high fields, which suggests a possible method of retarding the rapid decay of J_c(H) under elevated fields.