The calculation of force constants and normal coordinates IV: XH4 and XH3 molecules

Normal coordinate calculations of XH4 and XH3 molecules are reviewed and discussed. It is shown that for most of these molecules the true values of the force constants in the most General Harmonic Force Field can be uniquely determined only by making use of vibration-rotation interaction constants. It is emphasized that without these extra data the GFF is not determined. The results are compared with various model force fields for these molecules.

Microwave spectrum of CHD2CN and CHD2NC, and the harmonic force field and rz structure of methyl cyanide and isocyanide

The microwave spectra of CHD2CN and CHD2NC have been measured from 18 to 40 GHz; about 20 type A and 30 type C transitions have been observed for each molecule. These have been fitted to a Hamiltonian using 3 rotational constants, and 5 quartic and 4 sextic distortion constants, in the IrS reduction of Watson [in “Vibrational spectra and structure” Vol. 6 (1977)]; the standard error of the fit is 26 kHz. For methyl cyanide the 5 quartic distortion constants have been used to further refine the recent harmonic force field of Duncan et al. [J. Mol. Spectrosc. 69, 123 (1978)], but the changes are small. Finally, for both molecules, the harmonic force field has been used to determine zero point average moments of inertia Iz from the ground state rotational constants for many isotopic species, and these have been used to determine an rz structure. The results are compared with rs structure calculations.

Coriolis perturbations in the infrared spectrum of allene

High resolution infrared spectra of the ν9 and ν10 perpendicular fundamentals of the allene molecule are reported, in which the J structure in the sub-bands has been partially resolved. Analysis of the latter shows that the vibrational origin ν9 = 999 cm−1, some 35 cm−1 below previous assignments. The pronounced asymmetry in the intensity distribution of the rotational structure which this assignment implies is shown to be expected theoretically, due to the Coriolis perturbations involved, and it is interpreted in terms of the sign and magnitude of the ratio of the dipole moment derivatives in the two fundamentals. The results of this analysis are shown to be in good agreement with observations on allene-1.1-d2, where similar intensity perturbations are observed, and with an independent analysis of the ν8 band of allene-h4. The A rotational constant of allene-h4 is found to have the value 4.82 ± 0.01 cm−1, and for the molecular geometry we obtain r(CH) = 1.084 A, r(CC) = 1.308 A, and HCH = 118.4°. A partial analysis of the rotational structure of the hot bands (ν9 + ν11 − ν11) and (ν10 + ν11 − ν11) is presented; these provide an example of a strong Coriolis interaction between nearly degenerate A1A2 and B1B2 pairs of vibrational levels. Some localized rotational perturbations in the ν9 and ν10 fundamentals are also noted, and their possible interpretations are discussed.

Goal sketching from a concise business case

This paper describes how the business case can be characterized and used to quickly make an initial and structurally complete goal-responsibility model. This eases the task of bringing disciplined support to key decision makers in a development project in such a way that it can be instantiated quickly and thereafter support all key decisions. This process also greatly improves the understanding shared by the key decision makers and helps to identify and manage loadbearing assumptions. Recent research has revealed two interesting issues, which are highlighted in this paper.

Determination of the vibrational transition moment ratio for the Coriolis interacting v9 and v10 fundamentals of allene

Comparison between observed and calculated infrared band contours has been made to determine the vibrational transition moment ratio |M10/M9| for the Coriolis interacting ν9 and ν10 perpendicular fundamentals of allene-h4. The ratio obtained is appreciably lower than that of a previous estimate and the result obtained by integrated band intensity measurements of Overend and Crawford. From the best estimate of the ratio, the dipole moment derivatives of the two bands are determined; the value for the weaker band ν9 is subject to a large uncertainty.

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.

The general harmonic force field of methyl fluoride

The complete general harmonic force field of methyl flouride was recalculated using the most recent literature frequency, Coriolis ζ, and centrifugal distortion data for 12CH3F, 13CH3F, 12CD3F, 12CHD2F and 12CH2DF. The anharmonic corrections applied to the observed frequency data and the adopted molecular geometry are considered to be more realistic than those used hitherto. There is excellent overall agreement between the fitted force constants and the highest quality ab initio force field currently available.

Local mode and normal mode interpretations of the CH and CD stretching vibrational manifolds of 1,1-dideuteroethene

The =CH2 AND =CD2 stretching vibrational overtones of H2C=CD2 have been studied up to V= 6 and V= 3, respectively. We report their interpretation in terms of a transition from normal to local modes, involving Fermi resonance with the C=C stretching and CH2 scissoring vibrations. We discuss the alternative representation of the vibrational Hamiltonian matrix in local mode and normal mode basis functions, and conclude that the normal mode basis offers greater flexibility in representing small anharmonic couplings with other modes.

Hay strewing, brush harvesting of seed and soil disturbance as tools for the enhancement of botanical diversity in grasslands

Since the middle of the last century agricultural intensification within Europe has led to a drastic decline in the extent of botanically diverse grasslands. Whilst measures to enhance the diversity of agriculturally-improved grasslands are in place, success has often been limited. One of the primary factors limiting success is the paucity of sources of propagules of desirable species in the surrounding landscape. The restoration of two contrasting grassland types lowland hay meadow and chalk grassland) was examined using a replicated block experiment to assess the effectiveness of two methods of seed application (hay strewing and brush harvesting) and two methods of pre-treatment disturbance (power harrowing and turf stripping). The resulting changes in botanical composition were monitored for 4 years. Seed addition by both methods resulted in significant temporal trends in plant species composition and increases in plant species richness, which were further enhanced by disturbance. Power harrowing increased the effectiveness of the seed addition treatments at the lowland hay meadow site. At the chalk grassland site a more severe disturbance created by turf stripping was used and shown to be preferable. Whilst both hay strewing and brush harvesting increased plant species richness, hay strewing was more effective at creating a sward similar to that of the donor site. Soil disturbance and seed application rate at the recipient site and timing of the hay cut at the donor site are all factors to be considered prior to the commencement of restoration management. (c) 2006 Elsevier Ltd. All rights reserved.