Analytical potentials for triatomic molecules IX. The prediction of anharmonic force constants from potential energy surfaces based on harmonic force fields and dissociation energies for SO2 and O3

Analytical potential energy functions which are valid at all dissociation limits have been derived for the ground states of SO2 and O3. The procedure involves minimizing the errors between the observed vibrational spectra and spectra calculated by a variational procedure. Good agreement is obtained between the observed and calculated spectra for both molecules. Comparisons are made between anharmonic force fields, previously determined from the spectral data, and the force fields obtained by differentiating the derived analytical functions at the equilibrium configurations.

A model for stretch-bend interactions in molecular force fields

Interaction force constants between bond-stretching and angle-bending co-ordinates in polyatomic molecules have been attributed, by some authors, to changes of hybridization due to orbital-following of the bending co-ordinate, and consequent changes of bond length due to the change of hybridization. A method is described for using this model quantitatively to reduce the number of independent force constants in the potential function of a polyatomic molecule, by relating stretch-bend interaction constants to the corresponding diagonal stretching constants. It is proposed to call this model the Hybrid Orbital Force Field. The model is applied to the tetrahedral four co-ordinated carbon atom (as in methane) and to the trigonal planar three coordinated carbon atom (as in formaldehyde).

General derivative relations for anharmonic force fields

The brace notation, introduced by Allen and Csaszar (1993, J. chem. Phys., 98, 2983), provides a simple and compact way to deal with derivatives of arbitrary non-tensorial quantities. One of its main advantages is that it builds the permutational symmetry of the derivatives directly into the formalism. The brace notation is applied to formulate the general nth-order Cartesian derivatives of internal coordinates, and to provide closed forms for general, nth-order transformation equations of anharmonic force fields, expressed as Taylor series, from internal to Cartesian or normal coordinate spaces.

The calculation of force constants and normal coordinates III: constrained force fields for the methyl halides

A method is discussed for imposing any desired constraint on the force field obtained in a force constant refinement calculation. The application of this method to force constant refinement calculations for the methyl halide molecules is reported. All available data on the vibration frequencies, Coriolis interaction constants and centrifugal stretching constants of CH3X and CD3X molecules were used in the refinements, but despite this apparent abundance of data it was found that constraints were necessary in order to obtain a unique solution to the force field. The results of unconstrained calculations, and of three different constrained calculations, are reported in this paper. The constrained models reported are a Urey—Bradley force field, a modified valence force field, and a constraint based on orbital-following bond-hybridization arguments developed in the following paper. The results are discussed, and compared with previous results for these molecules. The third of the above models is found to reproduce the observed data better than either of the first two, and additional reasons are given for preferring this solution to the force field for the methyl halide molecules.

Quantifying mesoscale variability in ocean transient tracer fields

A powerful way to test the realism of ocean general circulation models is to systematically compare observations of passive tracer concentration with model predictions. The general circulation models used in this way cannot resolve a full range of vigorous mesoscale activity (on length scales between 10–100 km). In the real ocean, however, this activity causes important variability in tracer fields. Thus, in order to rationally compare tracer observations with model predictions these unresolved fluctuations (the model variability error) must be estimated. We have analyzed this variability using an eddy‐resolving reduced‐gravity model in a simple midlatitude double‐gyre configuration. We find that the wave number spectrum of tracer variance is only weakly sensitive to the distribution of (large scale slowly varying) tracer sources and sinks. This suggests that a universal passive tracer spectrum may exist in the ocean. We estimate the spectral shape using high‐resolution measurements of potential temperature on an isopycnal in the upper northeast Atlantic Ocean, finding a slope near k −1.7 between 10 and 500 km. The typical magnitude of the variance is estimated by comparing tracer simulations using different resolutions. For CFC‐ and tritium‐type transient tracers the peak magnitude of the model variability saturation error may reach 0.20 for scales shorter than 100 km. This is of the same order as the time mean saturation itself and well over an order of magnitude greater than the instrumental uncertainty.

Carbon addition alters vegetation composition on ex-arable fields

1. Recent changes in European agricultural policy have led to measures to reverse the loss of species-rich grasslands through the creation of new areas on ex-arable land. Ex-arable soils are often characterized by high inorganic nitrogen (N) levels, which lead to the rapid establishment of annual and fast-growing perennial species during the initial phase of habitat creation. The addition of carbon (C) to the soil has been suggested as a countermeasure to reduce plant-available N and alter competitive interactions among plant species. 2. To test the effect of C addition on habitat creation on ex-arable land, an experiment was set up on two recently abandoned fields in Switzerland and on two 6-year-old restoration sites in the UK. Carbon was added as a mixture of either sugar and sawdust or wood chips and sawdust during a period of 2 years. The effects of C addition on soil parameters and vegetation composition were assessed during the period of C additions and 1 year thereafter. 3. Soil nitrate concentrations were reduced at all sites within weeks of the first C addition, and remained low until cessation of the C additions. The overall effect of C addition on vegetation was a reduction in above-ground biomass and cover. At the Swiss sites, the addition of sugar and sawdust led to a relative increase in legume and forb cover and to a decrease in grass cover. The soil N availability, composition of soil micro-organisms and vegetation characteristics continued to be affected after cessation of C additions. 4. Synthesis and applications. The results suggest that C addition in grassland restoration is a useful management method to reduce N availability on ex-arable land. Carbon addition alters the vegetation composition by creating gaps in the vegetation that facilitates the establishment of late-seral plant species, and is most effective when started immediately after the abandonment of arable fields and applied over several years.

Long-term effectiveness of sowing high and low diversity seed mixtures to enhance plant community development on ex-arable fields

Questions: How is succession on ex-arable land affected by sowing high and low diversity mixtures of grassland species as compared to natural succession? How long do effects persist? Location: Experimental plots installed in the Czech Republic, The Netherlands, Spain, Sweden and the United Kingdom. Methods: The experiment was established on ex-arable land, with five blocks, each containing three 10 m x 10 m experiment tal plots: natural colonization, a low- (four species) and high-diversity (15 species) seed mixture. Species composition and biomass was followed for eight years. Results: The sown plants considerably affected the whole successional pathway and the effects persisted during the whole eight year period. Whilst the proportion of sown species (characterized by their cover) increased during the study period, the number of sown species started to decrease from the third season onwards. Sowing caused suppression of natural colonizing species, and the sown plots had more biomass. These effects were on average larger in the high diversity mixtures. However, the low diversity replicate sown with the mixture that produced the largest biomass or largest suppression of natural colonizers fell within the range recorded at the five replicates of the high diversity plots. The natural colonization plots usually had the highest total species richness and lowest productivity at the end of the observation period. Conclusions: The effect of sowing demonstrated dispersal limitation as a factor controlling the rate of early secondary succession. Diversity was important primarily for its 'insurance effect': the high diversity mixtures were always able to compensate for the failure of some species.

The role of weeds in supporting biological diversity within crop fields

Weeds are major constraints on crop production, yet as part of the primary producers within farming systems, they may be important components of the agroecosystem. Using published literature, the role of weeds in arable systems for other above-ground trophic levels are examined. In the UK, there is evidence that weed flora have changed over the past century, with some species declining in abundance, whereas others have increased. There is also some evidence for a decline in the size of arable weed seedbanks. Some of these changes reflect improved agricultural efficiency, changes to more winter-sown crops in arable rotations and the use of more broad-spectrum herbicide combinations. Interrogation of a database of records of phytophagous insects associated with plant species in the UK reveals that many arable weed species support a high diversity of insect species. Reductions in abundances of host plants may affect associated insects and other taxa. A number of insect groups and farmland birds have shown marked population declines over the past 30 years. Correlational studies indicate that many of these declines are associated with changes in agricultural practices. Certainly reductions in food availability in winter and for nestling birds in spring are implicated in the declines of several bird species, notably the grey partridge, Perdix perdix . Thus weeds have a role within agroecosystems in supporting biodiversity more generally. An understanding of weed competitivity and the importance of weeds for insects and birds may allow the identification of the most important weed species. This may form the first step in balancing the needs for weed control with the requirements for biodiversity and more sustainable production methods.

Vegetation dynamics in abandoned crop fields on a Mediterranean island: Development of succession model and estimation of disturbance thresholds

This case study on the Sifnos island, Greece, assesses the main factors controlling vegetation succession following crop abandonment and describes the vegetation dynamics of maquis and phrygana formations in relation to alternative theories of secondary succession. Field survey data were collected and analysed at community as well as species level. The results show that vegetation succession on abandoned crop fields is determined by the combined effects of grazing intensity, soil and geological characteristics and time. The analysis determines the quantitative grazing thresholds that modify the successional pathway. Light grazing leads to dominance by maquis vegetation while overgrazing leads to phryganic vegetation. The proposed model shows that vegetation succession following crop abandonment is a complex multi-factor process where the final or the stable stage of the process is not predefined but depends on the factors affecting succession. An example of the use of succession models and disturbance thresholds as a policy assessment tool is presented by evaluating the likely vegetation impacts of the recent reform of the Common Agricultural Policy on Sifnos island over a 20-30-year time horizon. (c) 2006 Elsevier B.V. All rights reserved.

Chalcogenide-halides of niobium (V). 1. Gas-phase structures of NbOBr3, NbSBr3, and NbSCl3. 2. Matrix infrared spectra and vibrational force fields of NbOBr3, NbSBr3, NbSCl3, and NbOCl3

The molecular structures of NbOBr3, NbSCl3, and NbSBr3 have been determined by gas-phase electron diffraction (GED) at nozzle-tip temperatures of 250 degreesC, taking into account the possible presence of NbOCl3 as a contaminant in the NbSCl3 sample and NbOBr3 in the NbSBr3 sample. The experimental data are consistent with trigonal-pyramidal molecules having C-3v symmetry. Infrared spectra of molecules trapped in argon or nitrogen matrices were recorded and exhibit the characteristic fundamental stretching modes for C-3v species. Well resolved isotopic fine structure (Cl-35 and Cl-37) was observed for NbSCl3, and for NbOCl3 which occurred as an impurity in the NbSCl3 spectra. Quantum mechanical calculations of the structures and vibrational frequencies of the four YNbX3 molecules (Y = O, S; X = Cl, Br) were carried out at several levels of theory, most importantly B3LYP DFT with either the Stuttgart RSC ECP or Hay-Wadt (n + 1) ECP VDZ basis set for Nb and the 6-311 G* basis set for the nonmetal atoms. Theoretical values for the bond lengths are 0.01-0.04 Angstrom longer than the experimental ones of type r(a), in accord with general experience, but the bond angles with theoretical minus experimental differences of only 1.0-1.5degrees are notably accurate. Symmetrized force fields were also calculated. The experimental bond lengths (r(g)/Angstrom) and angles (angle(alpha)/deg) with estimated 2sigma uncertainties from GED are as follows. NbOBr3: r(Nb=O) = 1.694(7), r(Nb-Br) = 2.429(2), angle(O=Nb-Br) = 107.3(5), angle(Br-Nb-Br) = 111.5(5). NbSBr3: r(Nb=S) = 2.134(10), r(Nb-Br) = 2.408(4), angle(S=Nb-Br) = 106.6(7), angle(Br-Nb-Br) = 112.2(6). NbSCl3: Nb=S) = 2.120(10), r(Nb-Cl) = 2.271(6), angle(S=Nb-Cl) = 107.8(12), angle(Cl-Nb-Cl) = 111.1(11).