Coriolis perturbations in the infrared spectrum of diborane

High‐resolution infrared spectra of B2H6 vapor are reported. The sample was prepared from the naturally occurring 11B☒10B isotopic mixture. The rotational structure of the infrared bands has been analysed for Coriolis perturbations due to rotation about the axis of least moment of inertia (the B⋅⋅⋅B axis). The following results have been obtained: (a) interaction between the Type A fundamental ν18 and the inactive fundamental ν5 has been observed, thus confirming the assignment of ν5 at 833 cm—1, giving ∣ ζ5,18Z ∣=0.55±0.05; (b) interaction observed between the Type A combination band (ν10+ν12) at 1283 cm—1 and the inactive combination (ν10+ν7) gives an estimate of the unobserved fundamental ν7 as 850±30 cm—1, and an estimate of ∣ ζ7,12Z ∣=0.6±0.1; (c) the absence of any observed perturbation of the Type C fundamental ν14 at 973 cm—1, suggests, by negative arguments, that either the unobserved fundamental ν9 does not lie in the frequency range 900 to 1100 cm—1, or ∣ ζ9,14Z ∣<0.2. The assignment of the unobserved fundamental vibrations of diborane is discussed in the light of this evidence.

Anharmonicity and local mode effects in the vibrational spectrum of NiCO4 and Co(CO)3NO

Previously published data on the vibrational fundamentals and overtones of the carbonyl stretching modes of Ni(CO)4 and Co(CO)3NO are reinterpreted using the recent model of Mills and Robiette, including Darling-Dennison resonances and local mode effects. The harmonic wavenumber θm and anharmonicity constant xm associated with the carbonyl and nitrosyl stretching modes are derived, and the 13C and 18O isotopic shifts are discussed in relation to the harmonic and anharmonic force field.

Perturbations in the infrared spectrum of monofluoroacetylene, and their relationship to intramolecular vibrational energy redistribution

Several high-order vibration-rotation perturbations in the high-resolution infrared spectrum of monofluoroacetylene, HCCF, are assigned and analyzed in detail. They result in avoided crossings in the rotational structure of several bands, and precise values for the effective high-order terms in the Hamiltonian have been determined. The significance of these results for intramolecular vibrational redistribution is discussed.

Calculating the exclusion probability and paternity index for X-chromosomal loci in the presence of substructure

There has been recent interest in the use of X-chromosomal loci for forensic and relatedness testing casework, with many authors developing new X-linked short tandem repeat (STR) loci suitable for forensic use. Here we present formulae for two key quantities in paternity testing, the average probability of exclusion and the paternity index, which are suitable for Xchromosomal loci in the presence of population substructure.

Wave-driven wind jets in the marine atmospheric boundary layer

The interaction between ocean surface waves and the overlying wind leads to a transfer of momentum across the air–sea interface. Atmospheric and oceanic models typically allow for momentum transfer to be directed only downward, from the atmosphere to the ocean. Recent observations have suggested that momentum can also be transferred upward when long wavelength waves, characteristic of remotely generated swell, propagate faster than the wind speed. The effect of upward momentum transfer on the marine atmospheric boundary layer is investigated here using idealized models that solve the momentum budget above the ocean surface. A variant of the classical Ekman model that accounts for the wave-induced stress demonstrates that, although the momentum flux due to the waves penetrates only a small fraction of the depth of the boundary layer, the wind profile is profoundly changed through its whole depth. When the upward momentum transfer from surface waves sufficiently exceeds the downward turbulent momentum flux, then the near-surface wind accelerates, resulting in a low-level wave-driven wind jet. This increases the Coriolis force in the boundary layer, and so the wind turns in the opposite direction to the classical Ekman layer. Calculations of the wave-induced stress due to a wave spectrum representative of fast-moving swell demonstrate upward momentum transfer that is dominated by contributions from waves in the vicinity of the peak in the swell spectrum. This is in contrast to wind-driven waves whose wave-induced stress is dominated by very short wavelength waves. Hence the role of swell can be characterized by the inverse wave age based on the wave phase speed corresponding to the peak in the spectrum. For a spectrum of waves, the total momentum flux is found to reverse sign and become upward, from waves to wind, when the inverse wave age drops below the range 0.15–0.2, which agrees reasonably well with previously published oceanic observations.

GIS in the cloud: implementing a web map service on Google App Engine

Many producers of geographic information are now disseminating their data using open web service protocols, notably those published by the Open Geospatial Consortium. There are many challenges inherent in running robust and reliable services at reasonable cost. Cloud computing provides a new kind of scalable infrastructure that could address many of these challenges. In this study we implement a Web Map Service for raster imagery within the Google App Engine environment. We discuss the challenges of developing GIS applications within this framework and the performance characteristics of the implementation. Results show that the application scales well to multiple simultaneous users and performance will be adequate for many applications, although concerns remain over issues such as latency spikes. We discuss the feasibility of implementing services within the free usage quotas of Google App Engine and the possibility of extending the approaches in this paper to other GIS applications.

Spectral analysis of the elliptic sine-Gordon equation in the quarter plane

We study the elliptic sine-Gordon equation in the quarter plane using a spectral transform approach. We determine the Riemann-Hilbert problem associated with well-posed boundary value problems in this domain and use it to derive a formal representation of the solution. Our analysis is based on a generalization of the usual inverse scattering transform recently introduced by Fokas for studying linear elliptic problems.

Puckering structure in the infrared spectrum of cyclobutane

The theory of rotational-pucker-vibrational transitions in the vibrational spectrum of cyclobutane is reviewed. Puckering sideband structure on the 1453 cm-1v14 infra-red fundamental of C4H8 has been observed and analysed, in terms of two slightly different puckering potential functions for the ground and the excited vibrational states. The results have been fitted to quartic-quadratic potential functions in the puckering coordinate, with a barrier to inversion of 503 cm-1 (1•44 kcal mole-1 = 6•02 kJ mole-1) in the ground state and 491 cm-1 in the excited state ν14 = 1. For reasonable assumptions about the reduced mass, the equilibrium dihedral angle of the C4 ring is determined to be about 35°, in agreement with previous estimates. Ueda and Shimanouchi's observations on the 2878 cm-1 C4H8 band have been re-analysed, and puckering sidebands have also been observed and analysed for the 1083 cm-1v14 infra-red fundamental of C4D8. Pure puckering transitions have been observed in the Raman spectrum of C4H8 vapour. All of these observations are shown to be consistent with the same ground state puckering potential function.

Vibrational Renner-Teller effects in the infrared spectrum of carbonsuboxide

The infrared spectrum of carbon suboxide has been recorded with a resolution of 0•01cm-1 from 400 to 700 cm-1. The region from 530 to 570 cm-1 shows intense absorption due to the v6(Πu) band system, of which the fundamental band only has been assigned and analysed, giving v6=540•221 cm-1. The region 590 to 660 cm-1 shows weaker absorption due to the v5(Πg) band system appearing in combination with odd quanta of the v7(Πu) fundamental at 18 cm-1. The v5 + v7 band and several hot bands have been assigned and analysed, and the effective v7 bending potential in the v5 state has been deduced. This potential shows a splitting as the large amplitude bending coordinate q7 is displaced due to interaction between v5 and v7 analogous to the Renner-Teller effect in electronic spectroscopy. This splitting is about 4 cm-1 for the classical turning points in q7 and the mean q7 bending potential is closely similar to that in the ground state.

Intensities in the v7, v8 and v9 bands of CH2NH, and the harmonic force field of methyleneimine

A high resolution Fourier transform infrared spectrum of methyleneimine, HN=CH2, has been obtained in the gas phase in the region 700 to 1300 cm−1. The rovibrational line intensities of the three lowest fundamentals ν7 (A′), ν8 (A″), and ν9 (A″) have been simulated including all Coriolis interactions between the three bands, and by fitting the observed spectrum the relative signs and magnitudes of the vibrational transition moments have been determined. All of the available spectroscopic data have been used to determine the harmonic force field of methyleneimine.

The calculation of force constants and normal co-ordinates--VII Normal co-ordinates in the E species of allene

Force constant and normal co-ordinate calculations are reported for the E species vibrations of the allene molecule. Data on the fundamental vibration frequencies of allene-h4, allene-d4 and allene-1.1-d2 and on the five experimentally determined Coriolis zeta constants of C3H4 and C3D4, were used in a force constant refinement procedure. Allowing for product and sum rules this gives 21 independent data which were used to refine to the most general harmonic force field (10 parameters) with one constraint (in the absence of any constraints the refinement was not satisfactory). The results have been used to calculate the complete ζz Coriolis interaction matrix for the allene-1.1-d2 molecule, and hence to calculate the expected rotational structure of the perpendicular bending vibrations of this molecule; the good agreement obtained with the observed spectra is a check on our results.

Calibration and use of a cesium-iodide prism in the infrared

With a cesium-iodide prism the long wavelength range of an infrared spectrometer may be extended to 55µ The use of such a prism, the choice of optical system, and the problems of stray radiation are all discussed. Accurate data are assembled for calibration in this region, and sample calibration traces are shown. A simple gas absorption cell is described for use at long wavelengths.