Microwave spectrum of CF3CCH

Attempts to observe ΔK = ±1 transitions in the rotational spectrum of CF3CCH and CF3H in the first excited state of a degenerate vibration, by direct absorption in the Y band and K band regions of the microwave spectrum, have not been successful. In the course of this work the J = 3-2 and 4-3 rotational spectrum of CF3CCH has been observed with higher sensitivity than previously, and from the positions of the vibrational satellites several new rB values have been determined.

First CRDS-measurements of water vapour continuum in the 940nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw- CRDS) have been performed at around 10611.6 and 10685:2 cm1. The continuum absorption coefficients for N2- broadening have been determined for two temperatures and wavenumbers. These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.

A narrow band pulsed eddy current instrument for materials testing

The principles of operation of an experimental prototype instrument known as J-SCAN are described along with the derivation of formulae for the rapid calculation of normalized impedances; the structure of the instrument; relevant probe design parameters; digital quantization errors; and approaches for the optimization of single frequency operation. An eddy current probe is used As the inductance element of a passive tuned-circuit which is repeatedly excited with short impulses. Each impulse excites an oscillation which is subject to decay dependent upon the values of the tuned-circuit components: resistance, inductance and capacitance. Changing conditions under the probe that affect the resistance and inductance of this circuit will thus be detected through changes in the transient response. These changes in transient response, oscillation frequency and rate of decay, are digitized, and then normalized values for probe resistance and inductance changes are calculated immediately in a micro processor. This approach coupled with a minimum analogue processing and maximum of digital processing has advantages compared with the conventional approaches to eddy current instruments. In particular there are: the absence of an out of balance condition and the flexibility and stability of digital data processing.

Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

The full-spectrum correlated-k method for longwave atmospheric radiative transfer using an effective Planck function

The correlated k-distribution (CKD) method is widely used in the radiative transfer schemes of atmospheric models and involves dividing the spectrum into a number of bands and then reordering the gaseous absorption coefficients within each one. The fluxes and heating rates for each band may then be computed by discretizing the reordered spectrum into of order 10 quadrature points per major gas and performing a monochromatic radiation calculation for each point. In this presentation it is shown that for clear-sky longwave calculations, sufficient accuracy for most applications can be achieved without the need for bands: reordering may be performed on the entire longwave spectrum. The resulting full-spectrum correlated k (FSCK) method requires significantly fewer monochromatic calculations than standard CKD to achieve a given accuracy. The concept is first demonstrated by comparing with line-by-line calculations for an atmosphere containing only water vapor, in which it is shown that the accuracy of heating-rate calculations improves approximately in proportion to the square of the number of quadrature points. For more than around 20 points, the root-mean-squared error flattens out at around 0.015 K/day due to the imperfect rank correlation of absorption spectra at different pressures in the profile. The spectral overlap of m different gases is treated by considering an m-dimensional hypercube where each axis corresponds to the reordered spectrum of one of the gases. This hypercube is then divided up into a number of volumes, each approximated by a single quadrature point, such that the total number of quadrature points is slightly fewer than the sum of the number that would be required to treat each of the gases separately. The gaseous absorptions for each quadrature point are optimized such that they minimize a cost function expressing the deviation of the heating rates and fluxes calculated by the FSCK method from line-by-line calculations for a number of training profiles. This approach is validated for atmospheres containing water vapor, carbon dioxide, and ozone, in which it is found that in the troposphere and most of the stratosphere, heating-rate errors of less than 0.2 K/day can be achieved using a total of 23 quadrature points, decreasing to less than 0.1 K/day for 32 quadrature points. It would be relatively straightforward to extend the method to include other gases.

The full-spectrum correlated k method for longwave atmospheric radiative transfer: treatment of gaseous overlap

The correlated k-distribution (CKD) method is widely used in the radiative transfer schemes of atmospheric models, and involves dividing the spectrum into a number of bands and then reordering the gaseous absorption coefficients within each one. The fluxes and heating rates for each band may then be computed by discretizing the reordered spectrum into of order 10 quadrature points per major gas, and performing a pseudo-monochromatic radiation calculation for each point. In this paper it is first argued that for clear-sky longwave calculations, sufficient accuracy for most applications can be achieved without the need for bands: reordering may be performed on the entire longwave spectrum. The resulting full-spectrum correlated k (FSCK) method requires significantly fewer pseudo-monochromatic calculations than standard CKD to achieve a given accuracy. The concept is first demonstrated by comparing with line-by-line calculations for an atmosphere containing only water vapor, in which it is shown that the accuracy of heating-rate calculations improves approximately in proportion to the square of the number of quadrature points. For more than around 20 points, the root-mean-squared error flattens out at around 0.015 K d−1 due to the imperfect rank correlation of absorption spectra at different pressures in the profile. The spectral overlap of m different gases is treated by considering an m-dimensional hypercube where each axis corresponds to the reordered spectrum of one of the gases. This hypercube is then divided up into a number of volumes, each approximated by a single quadrature point, such that the total number of quadrature points is slightly fewer than the sum of the number that would be required to treat each of the gases separately. The gaseous absorptions for each quadrature point are optimized such they minimize a cost function expressing the deviation of the heating rates and fluxes calculated by the FSCK method from line-by-line calculations for a number of training profiles. This approach is validated for atmospheres containing water vapor, carbon dioxide and ozone, in which it is found that in the troposphere and most of the stratosphere, heating-rate errors of less than 0.2 K d−1 can be achieved using a total of 23 quadrature points, decreasing to less than 0.1 K d−1 for 32 quadrature points. It would be relatively straightforward to extend the method to include other gases.

The potential of 1 h refractivity changes from an operational C-band magnetron-based radar for numerical weather prediction validation and data assimilation

Refractivity changes (ΔN) derived from radar ground clutter returns serve as a proxy for near-surface humidity changes (1 N unit ≡ 1% relative humidity at 20 °C). Previous studies have indicated that better humidity observations should improve forecasts of convection initiation. A preliminary assessment of the potential of refractivity retrievals from an operational magnetron-based C-band radar is presented. The increased phase noise at shorter wavelengths, exacerbated by the unknown position of the target within the 300 m gate, make it difficult to obtain absolute refractivity values, so we consider the information in 1 h changes. These have been derived to a range of 30 km with a spatial resolution of ∼4 km; the consistency of the individual estimates (within each 4 km × 4 km area) indicates that ΔN errors are about 1 N unit, in agreement with in situ observations. Measurements from an instrumented tower on summer days show that the 1 h refractivity changes up to a height of 100 m remain well correlated with near-surface values. The analysis of refractivity as represented in the operational Met Office Unified Model at 1.5, 4 and 12 km grid lengths demonstrates that, as model resolution increases, the spatial scales of the refractivity structures improve. It is shown that the magnitude of refractivity changes is progressively underestimated at larger grid lengths during summer. However, the daily time series of 1 h refractivity changes reveal that, whereas the radar-derived values are very well correlated with the in situ observations, the high-resolution model runs have little skill in getting the right values of ΔN in the right place at the right time. This suggests that the assimilation of these radar refractivity observations could benefit forecasts of the initiation of convection.