Vibrational energy levels for the electronic ground state of the diazocarbene (CNN) molecule

The vibrational energy levels of diazocarbene (diazomethylene) in its electronic ground state, (X) over tilde (3) Sigma(-) CNN, have been predicted using the variational method. The potential energy surfaces of (X) over tilde (3) A" CNN were determined by employing ab initio single reference coupled cluster with single and double excitations (CCSD), CCSD with perturbative triple excitations [CCSD(T)], multi-reference complete active space self-consistent-field (CASSCF), and internally contracted multi-reference configuration interaction (ICMRCI) methods. The correlation-consistent polarised valence quadruple zeta (cc-pVQZ) basis set was used. Four sets of vibrational energy levels determined from the four distinct analytical potential functions have been compared with the experimental values from the laser-induced fluorescence measurements of Wurfel et al. obtained in 1992. The CCSD, CCSD(T), and CASSCF potentials have not provided satisfactory agreement with the experimental observations. In this light, the importance of both non-dynamic (static) and dynamic correlation effects in describing the ground state of CNN is emphasised. Our best theoretical fundamental frequencies at the cc-pVQZ ICMRCI level of theory, v(1) = 1230, v(2) = 394, and v(3) = 1420 cm(-1) are in excellent agreement with the experimental values of v(1) = 1235, v(2) = 396, and v(3) = 1419cm(-1) and the mean absolute deviation between the 23 calculated and experimental vibrational energy levels is only 7.4 cm(-1). It is shown that the previously suggested observation of the v(3) frequency at about 2847cm(-1) was in fact the first overtone 2v(3).

Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

Miscibility studies of the blends of chitosan with some cellulose ethers

The polymeric films have been prepared based on blends of chitosan with two cellulose ethers-hydroxypropylmethylcellulose and methylcellulose by casting from acetic acid solutions. The films were transparent and brittle in a dry state but an immersion of the samples in deionized water for over 24 h leads to their disintegration or partial dissolution. The miscibility of the polymers in the blends has been assessed by infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis. It was shown that although weak hydrogen bonding exists between the polymer functional groups the blends are not fully miscible in a dry state. (c) 2005 Elsevier Ltd. All rights reserved.

Experimental structure determination of the chemisorbed overlayers of chlorine and iodine on Au{111}

We have performed an experimental structure determination of the ordered p(sqrt[3] x sqrt[3])R30 degrees structures of chlorine and iodine on Au{111} using low-energy electron diffraction (LEED). Despite great similarities in the structure of the underlying substrate, which shows only minor deviations from the bulk positions in both cases, chlorine and iodine are found to adsorb in different adsorption sites, fcc and hcp hollow sites, respectively. The experimental Au-Cl and Au-I bond lengths of 2.56 and 2.84 A are close to the sums of the covalent radii, supporting the view that the bond is essentially covalent in nature; however, they are significantly shorter than predicted theoretically.

Small business legislation in Australia: does it provide a solution to part of the UK lease reform debate?

This paper addresses the commercial leases policy issue of how to deal with small business tenants. The UK has adopted a voluntary solution to commercial lease reform by using Codes of Practice which is in contrast to the legislative approach adopted by Australia to attempt to solve its perceived problems with small business retail tenancies. The major aim of the research was to examine the perceptions of the effectiveness of the legislation in Australia and discuss any implications for the UK policy debate but the results of the research also raise questions for the Australian regime. The research used a combination of literature and legislation review and a semi structured interview survey to investigate the policy aims and objectives of Australian Federal and State Governments, identify the nature and scope of the Australian legislation and examine perceptions of effectiveness of the legislation in informing small business tenants. The situation is complicated in Australia due to leases being a State rather than Federal responsibility therefore the main fieldwork was carried out in one case study State, Victoria. The paper concludes that some aspects of the Australian system can inform the UK policy debate including mandatory information provision at the commencement of negotiations and the use of lease registrars/commissioners. However, there are a number of issues that the Australian legislation does not appear to have successfully addressed including the difficulties of legislating across partial segments of the commercial property market and the collection of data for enforcement purposes.

A study of the ethene-ozone reaction with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications

The ozone-ethene reaction has been investigated at low pressure in a flow-tube interfaced to a u.v. photoelectron spectrometer. Photoelectron spectra recorded as a function of reaction time have been used to estimate partial pressures of the reagents and products, using photoionization cross-sections for selected photoelectron bands of the reagents and products, which have been measured separately. Product yields compare favourably with results of other studies, and the production of oxygen and acetaldehyde have been measured as a function of time for the first time. A reaction scheme developed for the ozone-ethene reaction has been used to simulate the reagents and products as a function of time. The results obtained are in good agreement with the experimental measurements. For each of the observed products, the simulations allow the main reaction (or reactions) for production of that product to be established. The product yields have been used in a global model to estimate their global annual emissions in the atmosphere. Of particular interest are the calculated global annual emissions of formaldehyde (0.96 ± 0.10 Tg) and formic acid, (0.05 ± 0.01 Tg) which are estimated as 0.04% and 0.7% of the total annual emission respectively.

The distribution of the ring current: Cluster observations

Extending previous studies, a full-circle investigation of the ring current has been made using Cluster 4-spacecraft observations near perigee, at times when the Cluster array had relatively small separations and nearly regular tetrahedral configurations, and when the Dst index was greater than −30 nT (non-storm conditions). These observations result in direct estimations of the near equatorial current density at all magnetic local times (MLT) for the first time and with sufficient accuracy, for the following observations. The results confirm that the ring current flows westward and show that the in situ average measured current density (sampled in the radial range accessed by Cluster 4–4.5RE) is asymmetric in MLT, ranging from 9 to 27 nAm−2. The direction of current is shown to be very well ordered for the whole range of MLT. Both of these results are in line with previous studies on partial ring extent. The magnitude of the current density, however, reveals a distinct asymmetry: growing from 10 to 27 nAm−2 as azimuth reduces from about 12:00MLT to 03:00 and falling from 20 to 10 nAm−2 less steadily as azimuth reduces from 24:00 to 12:00MLT. This result has not been reported before and we suggest it could reflect a number of effects. Firstly, we argue it is consistent with the operation of region-2 field aligned-currents (FACs), which are expected to flow upward into the ring current around 09:00MLT and downward out of the ring current around 14:00MLT. Secondly, we note that it is also consistent with a possible asymmetry in the radial distribution profile of current density (resulting in higher peak at 4– 4.5RE). We note that part of the enhanced current could reflect an increase in the mean AE activity (during the periods in which Cluster samples those MLT).

The implications of the 2003 Common Agricultural Policy reforms for land use and landscape quality in England

The assessment of the potential landscape impacts of the latest Common Agricultural Policy reforms constitutes a challenge for policy makers and it requires the development of models that can reliably project the likely spatial distribution of land uses. The aim of this study is to investigate the impact of 2003 CAP reforms to land uses and rural landscapes across England. For this purpose we modified an existing economic model of agriculture, the Land-Use Allocation Model (LUAM) to provide outputs at a scale appropriate for informing a semi-quantitative landscape assessment at the level of ‘Joint Character Areas’ (JCAs). Overall a decline in the cereal and oilseed production area is projected but intensive arable production will persist in specific locations (East of England, East Midlands and South East), having ongoing negative effects on the character of many JCAs. The impacts of de-coupling will be far more profound on the livestock sector; extensification of production will occur in traditional mixed farming regions (e.g. the South West), a partial displacement of cattle by sheep in the upland regions and an increase in the sheep numbers is expected in the lowlands (South East, Eastern and East Midlands). This extensification process will affect positively those JCAs of mixed farming conditions, but it will have negative impacts on the JCAs of historically low intensity farming (e.g. the uplands of north-west) because they will suffer from under-management and land idling. Our analysis shows that the territorialisation between intensively and extensively agricultural landscapes will continue.

Inner plasma structure of the low-latitude reconnection layer

We report a clear transition through a reconnection layer at the low-latitude magnetopause which shows a complete traversal across all reconnected field lines during northwestward interplanetary magnetic field (IMF) conditions. The associated plasma populations confirm details of the electron and ion mixing and the time history and acceleration through the current layer. This case has low magnetic shear with a strong guide field and the reconnection layer contains a single density depletion layer on the magnetosheath side which we suggest results from nearly field-aligned magnetosheath flows. Within the reconnection boundary layer, there are two plasma boundaries, close to the inferred separatrices on the magnetosphere and magnetosheath sides (Ssp and Ssh) and two boundaries associated with the Alfvén waves (or Rotational Discontinuities, RDsp and RDsh). The data are consistent with these being launched from the reconnection site and the plasma distributions are well ordered and suggestive of the time elapsed since reconnection of the field lines observed. In each sub-layer between the boundaries the plasma distribution is different and is centered around the current sheet, responsible for magnetosheath acceleration. We show evidence for a velocity dispersion effect in the electron anisotropy that is consistent with the time elapsed since reconnection. In addition, new evidence is presented for the occurrence of partial reflection of magnetosheath electrons at the magnetopause current layer.

The expression of the end-Cenomanian oceanic anoxic event (OAE 2) in the Helvetic Alps

Upper Cenomanian pelagic sediments from the northern Alpine Helvetic fold-and-thrust belt (northern Tethyan margin) coeval with Oceanic Anoxic Event (OAE) 2 are characterized by the temporal persistence of micrite sedimentation and lack of organic carbon-rich layers. We studied an expanded section in the Chrummflueschlucht (east of Euthal, Switzerland), which encompasses the OAE 2 time interval. In order to identify the paleoceanographic and paleoenvironmental conditions during OAE 2 in this part of the northern Tethyan margin, and more specifically to trace eventual changes in nutrient levels and oxic conditions, we investigated the biostratigraphy (planktonic foraminifera), the bulk-rock mineralogy, and measured stable carbon- and oxygen-isotopes, total phosphorus (P) and redox-sensitive trace-element (RSTE) contents. We were able to determine – with some remaining uncertainties – the different planktonic foraminiferal biozones characteristic of the Cenomanian–Turonian boundary interval (Rotalipora cushmani, Whiteinella archaeocretacea and Helvetoglobotruncana helvetica zones). In the lower part of the section (R. cushmani total range zone), the bulk-rock δ13C record shows a long-term increase. Within sediments attributed to the W. archaeocretacea partial range zone, δ13C values reach a maximum of 3.3‰ (peak “a”). In the following the values decrease and increase again to arrive at a plateau with high δ13C values of around 3.1‰, which ends with a peak of 3.3‰ (peak “c”). At the top of the section, in sediments belonging to the H. helvetica total range zone, δ13C values decrease to post-OAE values of around 2.2‰. The last occurrence of R. cushmani is observed just above the positive δ13C shift characterizing OAE 2. P contents display small variations along the section with a long-term decreasing trend towards the top. Before the OAE 2 interval, P values show higher values and relatively good covariation with detrital input, indicating higher nutrient input before OAE 2. In sediments corresponding to the onset of the δ13C positive excursion, P content is marked by a sharp peak probably linked to a slowdown in sedimentation rates and/or the presence of a small hiatus, as is shown by the presence of glauconite and phosphatic grains. In the interval corresponding to OAE 2, P values remain low and increase slightly at the end of the positive shift in the δ13C record (in the H. helvetica total range zone). The average contents of RSTE (U, V, As, Co, Mo and Mn) remain low throughout the section and appreciable RSTE enrichments have not been observed for the sedimentary interval corresponding to OAE 2. No correlation is observed with stratigraphic trends in RSTE contents in organic-rich deeper-water sections. The presence of double-keeled planktonic foraminifera species during most of the Cenomanian/Turonian boundary event is another evidence of relatively well-oxygenated conditions in this part of the northern Tethyan outer shelf. Our results show that the Chrummflueschlucht section corresponds to one of the most complete section for the Cenomanian–Turonian boundary interval known from the Helvetic realm even if a small hiatus may be present at the onset of the δ13C record (peak “a”). The evolution of P contents suggests an increase in input of this nutritive element at the onset of OAE2. However, the trends in RSTE contents and the planktonic foraminifera assemblages show that the Helvetic realm has not been affected by strongly depleted oxygen conditions during OAE 2.

Influence of the quasi-biennial oscillation on the extratropical winter stratosphere in an atmospheric general circulation model and in reanalysis data

The interannual variability of the stratospheric polar vortex during winter in both hemispheres is observed to correlate strongly with the phase of the quasi-biennial oscillation (QBO) in tropical stratospheric winds. It follows that the lack of a spontaneously generated QBO in most atmospheric general circulation models (AGCMs) adversely affects the nature of polar variability in such models. This study examines QBO–vortex coupling in an AGCM in which a QBO is spontaneously induced by resolved and parameterized waves. The QBO–vortex coupling in the AGCM compares favorably to that seen in reanalysis data [from the 40-yr ECMWF Re-Analysis (ERA-40)], provided that careful attention is given to the definition of QBO phase. A phase angle representation of the QBO is employed that is based on the two leading empirical orthogonal functions of equatorial zonal wind vertical profiles. This yields a QBO phase that serves as a proxy for the vertical structure of equatorial winds over the whole depth of the stratosphere and thus provides a means of subsampling the data to select QBO phases with similar vertical profiles of equatorial zonal wind. Using this subsampling, it is found that the QBO phase that induces the strongest polar vortex response in early winter differs from that which induces the strongest late-winter vortex response. This is true in both hemispheres and for both the AGCM and ERA-40. It follows that the strength and timing of QBO influence on the vortex may be affected by the partial seasonal synchronization of QBO phase transitions that occurs both in observations and in the model. This provides a mechanism by which changes in the strength of QBO–vortex correlations may exhibit variability on decadal time scales. In the model, such behavior occurs in the absence of external forcings or interannual variations in sea surface temperatures.

Multimodel assessment of the factors driving stratospheric ozone evolution over the 21st century

The evolution of stratospheric ozone from 1960 to 2100 is examined in simulations from 14 chemistry‐climate models, driven by prescribed levels of halogens and greenhouse gases. There is general agreement among the models that total column ozone reached a minimum around year 2000 at all latitudes, projected to be followed by an increase over the first half of the 21st century. In the second half of the 21st century, ozone is projected to continue increasing, level off, or even decrease depending on the latitude. Separation into partial columns above and below 20 hPa reveals that these latitudinal differences are almost completely caused by differences in the model projections of ozone in the lower stratosphere. At all latitudes, upper stratospheric ozone increases throughout the 21st century and is projected to return to 1960 levels well before the end of the century, although there is a spread among models in the dates that ozone returns to specific historical values. We find decreasing halogens and declining upper atmospheric temperatures, driven by increasing greenhouse gases, contribute almost equally to increases in upper stratospheric ozone. In the tropical lower stratosphere, an increase in upwelling causes a steady decrease in ozone through the 21st century, and total column ozone does not return to 1960 levels in most of the models. In contrast, lower stratospheric and total column ozone in middle and high latitudes increases during the 21st century, returning to 1960 levels well before the end of the century in most models.

Characterization of the complex locus of bean encoding polygalacturonase-inhibiting proteins reveals subfunctionalization for defense against fungi and insects.

Polygalacturonase-inhibiting proteins (PGIPs) are extracellular plant inhibitors of fungal endopolygalacturonases (PGs) that belong to the superfamily of Leu-rich repeat proteins. We have characterized the full complement of pgip genes in the bean (Phaseolus vulgaris) genotype BAT93. This comprises four clustered members that span a 50-kb region and, based on their similarity, form two pairs (Pvpgip1/Pvpgip2 and Pvpgip3/Pvpgip4). Characterization of the encoded products revealed both partial redundancy and subfunctionalization against fungal-derived PGs. Notably, the pair PvPGIP3/PvPGIP4 also inhibited PGs of two mirid bugs (Lygus rugulipennis and Adelphocoris lineolatus). Characterization of Pvpgip genes of Pinto bean showed variations limited to single synonymous substitutions or small deletions. A three-amino acid deletion encompassing a residue previously identified as crucial for recognition of PG of Fusarium moniliforme was responsible for the inability of BAT93 PvPGIP2 to inhibit this enzyme. Consistent with the large variations observed in the promoter sequences, reverse transcription-PCR expression analysis revealed that the different family members differentially respond to elicitors, wounding, and salicylic acid. We conclude that both biochemical and regulatory redundancy and subfunctionalization of pgip genes are important for the adaptation of plants to pathogenic fungi and phytophagous insects.

Efficient calculation of the green function for acoustic propagation above a homogeneous impedance plane

This paper is concerned with the problem of propagation from a monofrequency coherent line source above a plane of homogeneous surface impedance. The solution of this problem occurs in the kernel of certain boundary integral equation formulations of acoustic propagation above an impedance boundary, and the discussion of the paper is motivated by this application. The paper starts by deriving representations, as Laplace-type integrals, of the solution and its first partial derivatives. The evaluation of these integral representations by Gauss-Laguerre quadrature is discussed, and theoretical bounds on the truncation error are obtained. Specific approximations are proposed which are shown to be accurate except in the very near field, for all angles of incidence and a wide range of values of surface impedance. The paper finishes with derivations of partial results and analogous Laplace-type integral representations for the case of a point source.

Exploring the climatic impact of the continental vegetation on the Mezosoic atmospheric CO2 and climate history

In this contribution, we continue our exploration of the factors defining the Mesozoic climatic history. We improve the Earth system model GEOCLIM designed for long term climate and geochemical reconstructions by adding the explicit calculation of the biome dynamics using the LPJ model. The coupled GEOCLIM-LPJ model thus allows the simultaneous calculation of the climate with a 2-D spatial resolution, the coeval atmospheric CO2, and the continental biome distribution. We found that accounting for the climatic role of the continental vegetation dynamics (albedo change, water cycle and surface roughness modulations) strongly affects the reconstructed geological climate. Indeed the calculated partial pressure of atmospheric CO2 over the Mesozoic is twice the value calculated when assuming a uniform constant vegetation. This increase in CO2 is triggered by a global cooling of the continents, itself triggered by a general increase in continental albedo owing to the development of desertic surfaces. This cooling reduces the CO2 consumption through silicate weathering, and hence results in a compensating increase in the atmospheric CO2 pressure. This study demonstrates that the impact of land plants on climate and hence on atmospheric CO2 is as important as their geochemical effect through the enhancement of chemical weathering of the continental surface. Our GEOCLIM-LPJ simulations also define a climatic baseline for the Mesozoic, around which exceptionally cool and warm events can be identified.