The ν2, 2ν2, 3ν2, ν4 and ν2+ν4 bands of 15NH3

The ir absorption of gaseous 15NH3 between 510 and 3040 cm−1 was recorded with a resolution of 0.06 cm−1. The ν2, 2ν2, 3ν2, ν4, and ν2 + ν4 bands were measured and analyzed on the basis of the vibration-rotation Hamiltonian developed by V. Špirko, J. M. R. Stone, and D. Papoušek (J. Mol. Spectrosc. 60, 159–178 (1976)). A set of effective molecular parameters for the ν2 = 1, 2, 3 states was derived, which reproduced the transition frequencies within the accuracy of the experimental measurements. For ν4 and ν2 + ν4 bands the standard deviation of the calculated spectrum is about four times larger than the measurements accuracy: a similar result was found for ν4 in 14NH3 by Š. Urban et al. (J. Mol. Spectrosc. 79, 455–495 (1980)). This result suggests that the present treatment takes into account only the most significant part of the rovibration interaction in the doubly degenerate vibrational states of ammonia.

Vibration-rotation bands of diazomethane

Some absorption bands of diazomethane vapour between 1950-3500 cm-1 have been measured with very high resolving power. The rotational structure of two parallel bands and of one perpendicular band has been resolved, and approximate values have been determined for the rotational constants. The results are consistent with the geometrical structure usually accepted for this molecule. A peculiarity in the results for the band near 2100 cm-1, together with other facts, leads to the suggestion that a tautomeric form of this molecule exists, HCN=NH, being an isoelectronic analogue of hydrazoic acid.

Second order Coriolis resonance in the v2, v5 Raman bands of CH3F

The vibration-rotation Raman spectrum of the ν2 and ν5 fundamentals of CH3F is reported, from 1320 to 1640 cm−1, with a resolution of about 0.3 cm−1. The Coriolis resonance between the two bands leads to many perturbation-allowed transitions. Where the resonance is still sufficiently weak that the quantum number K′ retains its meaning, perturbation-allowed transitions are observed for all values of ΔK from +4 to −4; in regions of strong resonance, however, we can only say that the observed transitions obey the selection rule Δ(k−l) = 0 or ±3. The spectrum has been analyzed by band contour simulation using a computer program based on exact diagonalization of the Hamiltonian within the ν2, ν5 vibrational levels, and improved vibration-rotation constants for these bands are reported. The relative magnitudes and relative sings of polarizability derivatives involved in these vibrations are also reported.

Intensities in infrared bands V: Bond polar properties in dimethylacetylene

The absolute intensities of all except one of the infra-red fundamental vibration bands of dimethyl acetylene have been determined, and the results have been used to compute polar properties of the C—H and C—C bonds. It has been found that if the very probable assumption is made that the acetylenic carbon atoms carry a residual negative charge, the hydrogen atoms in the C—H bonds must carry a residual positive charge. The probable value of the C—H dipole is about 04 Debye, and that of the C—C bond about 1 Debye. Comparisons have been made with the results of similar work with related molecules.

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.

l-resonance perturbations in infrared perpendicular bands

The effects of ℓ-type resonance on rovibrational bands in infrared spectra are reviewed. Observed spectra are compared with computer-simulated spectra obtained by solving the Hamiltonian matrix numerically and calculating the true (perturbed) wavenumber and intensity of each line in the band. The most obvious effects in the spectra are shown to result from intensity perturbations rather than line-shifts; in oblate symmetric tops the Q branch structure near the band center may show anomalies due to ℓ-resonance even at quite low resolution and even when the accidental resonance is not very exact. Numerical values of ℓ-doubling constants are obtained for several cyclopropane bands by comparing observed band contours at about 0.2-cm−1 resolution with computed contours. Although the constants are not determined with great precision, the sign of the ℓ-doubling constants is determined unambiguously.

Simultaneous analysis of v1, v4, 2v2, v2+v5, and 2v5 bands of 12CH3F

The Fourier-transform spectrum of CH3F from 2800 to 3100 cm−1, obtained by Guelachvili in Orsay at a resolution of about 0.003 cm−1, was analyzed. The effective Hamiltonian used contained all symmetry allowed interactions up to second order in the Amat-Nielsen classification, together with selected third-order terms, amongst the set of nine vibrational basis functions represented by the states ν1(A1), ν4(E), 2ν2(A1), ν2 + ν5(E), 2ν50(A1), and 2ν5±2(E). A number of strong Fermi and Coriolis resonances are involved. The vibrational Hamiltonian matrix was not factorized beyond the requirements of symmetry. A total of 59 molecular parameters were refined in a simultaneous least-squares analysis to over 1500 upper-state energy levels for J ≤ 20 with a standard deviation of 0.013 cm−1. Although the standard deviation remains an order of magnitude greater than the precision of the measurements, this work breaks new ground in the simultaneous analysis of interacting symmetric top vibrational levels, in terms of the number of interacting vibrational states and the number of parameters in the Hamiltonian.

The fundamental vibration-rotation bands of 13C16O and 12C18O

Rotation lines in the fundamental vibration bands of 13C16O and 12C180 have been measured, using very high resolving power and more accurate wavelength calibrations than previously. The molecular rotational and vibrational constants have been deduced and compared in relation to the mass differences between these molecules and the main species 12C160.

The infrared spectrum of the ν2 and ν3 bands of H16OF, H18OF, and D16OF

Fourier transform IR spectra in the ν2 and ν3 regions between 800 and 1500 cm−1 have been measured of H16OF with a resolution of 0.007 cm−1 and of H18OF and DOF with a resolution of 0.040 cm−1. Ground state constants have been improved for H16OF and have been obtained for the first time for H18OF. Parameters of the v2 = 1 and v3 = 1 excited states have been determined from rovibrational analyses of ca. 1000 ν2/ν3 lines which were fitted with σ 0.36, 4.5, and 7.6 × 10−3 cm−1 for H16OF, H18OF, and D16OF, respectively. Band centers of ν2/ν3 are 1353.40466(5)/889.07974(6), 1350.3976(5)/862.2967(7), and 1002.0083(9)/891.0014(15) cm−1, respectively, for the three isotopic species. While ν2 and ν3 are sufficiently separated in HOF to be treated independently, a Coriolis resonance is evident in DOF, the interaction constant ξ23c = 0.19073(16) cm−1 being in agreement with the prediction from the harmonic force field.

Small towns as 'sub-poles' in English rural development: Investigating rural-urban linkages using sub-regional social accounting matrices

This paper uses spatial economic data from four small English towns to measure the strength of economic integration between town and hinterland and to estimate the magnitude of town-hinterland spill-over effects. Following estimation of local integration indicators and inter-locale flows, sub-regional social accounting matrices (SAMs) are developed to estimate the strength of local employment and output multipliers for various economic sectors. The potential value of a town as a 'sub-pole' in local economic development is shown to be dependent on structural differences in the local economy, such as the particular mix of firms within towns. Although the multipliers are generally small, indicating a low level of local linkages, some sectors, particularly financial services and banking, show consistently higher multipliers for both output and employment. (c) 2007 Elsevier Ltd. All rights reserved.

Small-scale mining, poverty and economic development in sub-Saharan Africa: An overview

Artisanal and small-scale mining (ASM)-low tech, labour intensive mineral processing and excavation activity-is an economic mainstay in rural sub-Saharan Africa, providing direct employment to over two million people. This paper introduces a special issue on 'Small-scale mining, poverty and development in sub-Saharan Africa'. It focuses on the core conceptual issues covered in the literature, and the policy implications of the findings reported in the papers in this special issue. (C) 2009 Elsevier Ltd. All rights reserved.

Good governance and the extractive industries in sub-saharan Africa

This article critically examines the challenges that come with implementing the Extractive Industries Transparency Initiative (EITI)a policy mechanism marketed by donors and Western governments as a key to facilitating economic improvement in resource-rich developing countriesin sub-Saharan Africa. The forces behind the EITI contest that impoverished institutions, the embezzlement of petroleum and/or mineral revenues, and a lack of transparency are the chief reasons why resource-rich sub-Saharan Africa is underperforming economically, and that implementation of the EITI, with its foundation of good governance, will help address these problems. The position here, however, is that the task is by no means straightforward: that the EITI is not necessarily a blueprint for facilitating good governance in the region's resource-rich countries. It is concluded that the EITI is a policy mechanism that could prove to be effective with significant institutional change in host African countries but, on its own, it is incapable of reducing corruption and mobilizing citizens to hold government officials accountable for hoarding profits from extractive industry operations.

A framework for revitalisation of rural education and training systems in sub-Saharan Africa: Strengthening the human resource base for food security and sustainable livelihoods

Recent studies of the current state of rural education and training (RET) systems in sub-Saharan Africa have assessed their ability to provide for the learning needs essential for more knowledgeable and productive small-scale rural households. These are most necessary if the endemic causes of rural poverty (poor nutrition, lack of sustainable livelihoods, etc.) are to be overcome. A brief historical background and analysis of the major current constraints to improvement in the sector are discussed. Paramount among those factors leading to its present 'malaise' is the lack of a whole-systems perspective and the absence of any coherent policy framework in most countries. There is evidence of some recent innovations, both in the public sector and through the work of non-governmental organisations (NGOs), civil society organisations (CSOs) and other private bodies. These provide hope of a new sense of direction that could lead towards meaningful 'revitalisation' of the sector. A suggested framework offers 10 key steps which, it is argued, could largely be achieved with modest internal resources and very little external support, provided that the necessary leadership and managerial capacities are in place. (C) 2006 Elsevier Ltd. All rights reserved.