A new torsion-rotation fitting program for molecules with a sixfold barrier: Application to the microwave spectrum of toluene

A new program is described for fitting rotation-torsion energy levels in molecules like toluene, in which the frame (C₆H₅) has C_2v symmetry and the methyl top has C_3v symmetry, i.e., for molecules where the internal rotation barrier is expanded in cos6nα, where α is the internal rotation angle and n = 1,2,…. The program is based on the theoretical framework developed by Sørensen and Pedersen in their application of the Longuet-Higgins permutation-inversion group G₁₂ to the microwave spectrum of CH₃NO₂. It is specifically designed for sixfold barrier molecules, and allows the user to select almost any symmetry-allowed torsion-rotation term for inclusion in the fitting Hamiltonian. This program leads to a very successful fit of transitions in the microwave spectrum of toluene characterized by J ? 30, K_a ? 12, and by the free-rotor quantum number ∣m∣ ? 3. In these fits we included both published and rather extensive unpublished new measurements, for which fits using other torsion-rotation programs have not been very successful. The fit presented here uses 28 parameters to give an overall standard deviation of 7.4 kHz for 372 line frequencies, and results in a much improved value for the sixfold barrier for toluene, V₆ = 13.832068(3) cal mol⁻¹.     

Zur Methodik der Messung der Aktivität von umschlossenen γ-Strahlungsquellen mittels Ionisationskammern

In der Arbeit wird über eine Empfehlung zur Methodik der Weitergabe der Aktivitätseinheit für umschlossene γ-Strahlungsquellen von den Normalen der metrologischen Slaatsämter der UdSSR (WNIIM) und der DDR (ASMW) an Normale niederer Ordnung berichtet. Die Weitergabe der Aktivitätseinheit geschieht durch Vergleich mittels Ionisationskammern. Die Empfehlung bezieht sich auch auf solche Fälle, in denen neben dem Hauptnuklid ein Verunreinigungsnuklid in der Quelle enthalten ist, sowie auf solche, bei denen unterschiedlicher Aufbau der zu vergleichenden Quellen vorliegt. Auβerdem umfaβt die Empfehlung die Methode der Fehlerrechnung.     

A revisit of photoluminescence property for vanadate oxides AVO3 (A:K, Rb and Cs) and M3V2O8 (M:Mg and Zn)

We revisited the vanadium oxide phosphors, AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg and Zn) for a revaluation of possibility of these compounds for lighting applications, and the internal quantum efficiency (η) and luminescent colour properties for AVO₃ (A:K, Rb, and Cs) and M₃V₂O₈ (A:Mg, and Zn) have been presented. The AVO₃ showed the broadband emission from 380 to 800 nm, and the η for the KVO₃, RbVO₃ and CsVO₃ were 4%, 79% and 87%, respectively. The CIE colour coordinates are located at white region on the chromaticity diagram. The M₃V₂O₈ (A:Mg and Zn) also exhibited a quite broadband emission between 410 and 900 nm, indicating yellow luminescent colour. The Zn₃V₂O₈ showed high η value, 52%, compared to that of the Mg₃V₂O₈ (η=6%). This enhancement of η in the Zn₃V₂O₈ could be due to the increasing exciton diffusion assisted by the hybridizations of Zn 3d and O 2p orbitals for the valence band, and Zn 4s and Ti 3d orbitals for the conduction band.     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

Steady light diffusion application to rheology: a new tool for the characterization of concentrated suspensions

We present new developments of steady light diffusion applied to rheology. Though many techniques allow the structural investigation of diluted or transparent media, very few give direct information on optically dense systems. The technique proposed here is based on the diffusion approximation and is thus valid for sheared, time-dependent flows.After recalling important theoretical results, we show the techniques ability to determine typical sizes and orientation of structures in shear flows for various concentrated suspensions (emulsions, and an industrial softener). In particular, it is able to demonstrate the effect of shear on the orientation of anisotropic objects. Moreover, the use of simple structural models incorporating the measured anisotropy allows good predictions of experimental rheological measurements. This new technique, applicable to a wide range of colloidal systems, is very helpful to characterize the shear induced structural organization of optically dense materials.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

A rotation-torsion-vibration treatment with three-dimensional internal coordinate approach and additional FTIR spectral assignments for the CH3-bending fundamentals of methanol

A theoretical model has been developed to account for certain features of both newly observed and previously reported CH₃-bending subbands between 1450 and 1570 cm⁻¹ in the high-resolution Fourier transform infrared spectrum of CH₃OH [Can. J. Phys. 79 (2001) 435]. The features include (i) an apparent inversion of the rotationless E-A torsional splitting with respect to the ground state, i.e., the A state located above the E state, (ii) a pronounced upward slope in the K-reduced torsion-vibration energy pattern for the subband origins, and (iii) unexpected A₁/A₂ inversion of the K=2A and K=3AJ-rotational levels that led to ambiguity in identifying the vibrational mode as or . The model is an effective internal coordinate Hamiltonian constructed in G₆ molecular symmetry with the CH₃-bends coupled to each other and to torsion and including a- and γ-type Coriolis coupling. With this model, 33 out of 36 experimental upper-state K-term values for newly assigned , and ν₁₀ subbands plus previous ν₄ subbands have together been fitted successfully, employing 9 adjustable parameters and 17 fixed parameters to give a standard deviation of 0.14 cm⁻¹. The P_γ Coriolis term appears to be the leading cause of the upward shift in the K-reduced energies. When J-dependence is introduced via a rotational Hamiltonian including b- and c-type Coriolis terms in addition to molecular asymmetry, the observed A₁/A₂ inversion of the K=2A and 3A rotational levels can also be reproduced. Predictions using the fitted K-rotation-torsion-vibration Hamiltonian show an interesting Coriolis-induced crossover and mixing of the ν₅ and ν₁₀ torsion-vibration energy patterns. These predictions played a role in identifying two of the new ν₅ subbands in the crossing region, thereby helping to validate the model.     

Numerical analysis of buoyant flow in a hemispherical enclosure at high Rayleigh numbers

A numerical analysis is presented for buoyancy driven flow of a Newtonian fluid contained in a two dimensional (R, ) hemispherical enclosure for high Rayleigh (Ra) numbers. It is assumed that the flow is driven by the uniformly distributed internal heat sources within the enclosure. All walls of the cavity are maintained at a constant temperature. Finite volume based SIMPLER algorithm has been used for the present analysis. Discretised governing equations, in primitive variables, are solved by a combination of Three Diagonal Matrix Algorithm (TDMA) and Point Successive Overrelaxation (PSOR) method. A benchmark solution prepared for a Ra number range of 10⁷ to 10¹² and Prandtl (Pr) number 7.0, shows an excellent agreement with the experimental results obtained from the open literature.     

量子频标中的原子物理

频率是自然界中测量得最准的物理量.量子频标是频率的测量标准,它是利用原子跃迁谱线的稳定而准确的频率作为参考频率.频标研究中存在几乎所有的原子物理问题,如原子结构与光谱、原子与电磁场的相互作用以及原子碰撞等问题值得深入研究.本文就量子频标的基本原理和应用,量子频标中存在的原子物理问题做以简要评述.     

The internal strain of three-dimensional braided composites with co-braided FBG sensors

The performance analysis of three-dimensional (3-D) braided composites is made difficult by their complex and interlacing structure, and is still under development. To get complete first-hand data on the material parameters of these composites, co-braided optical fiber sensors (OFS) can be used to measure the internal strain. This information is helpful for subsequent stiffness predictions and failure analysis. This paper introduces a method of incorporating OFS into braided composites, and establishes a constitutive theoretical model for the hybrid material. Experiments are conducted to measure the internal strain of specimens under tension, and the results are compared to theoretical predictions.     

The millimeter wave rotational spectrum of pyruvic acid

The rotational spectrum of pyruvic acid has been investigated for the first time in the millimeter-wave region, at 160-314 GHz, and also in supersonic expansion, at 10-17.4 GHz. The analysis of the broadband spectra recorded in this work was carried out with the newly developed AABS software package for Assignment and Analysis of Broadband Spectra, and precise spectroscopic constants are reported for the ground state, the first excited state of the low-frequency skeletal torsional mode ν₂₄, and the first excited state of the methyl torsional mode ν₂₃. Limited results have also been obtained for several higher excited states. The dataset for the ground state currently exceeds 1500 lines and for both the A and E internal rotor sublevels spans the complete range of values of K_a at the mid values of J for the measured transitions. The results were analysed with three freely available computer programs employing different strategies for dealing with internal rotation and a comparative discussion of their merits is made.