Calculated rotational and rovibrational spectra of D2S and HDS

Rovibrational energy levels, transition frequencies, and linestrengths are computed variationally for the sulfur hydrides D2S and HDS, using ab initio potential energy and dipole surfaces. Wave-numbers for the pure rotational transitions agree to within 0.2 cm−1 of the experimental lines. For the fundamental vibrational transitions, the band origins for D2S are 860.4, 1900.6, and 1912.0 cm−1 for ν2, ν1, and ν3, respectively, compared with the corresponding experimental values of 855.4, 1896.4, and 1910.2 cm−1. For HDS, we compute ν2 to be 1039.4 cm−1, compared with the experimental value of 1032.7 cm−1. The relative merits of local and normal mode descriptions for the overtone stretching band origins are discussed. Our results confirm the local mode nature of the H2S, D2S, and HDS system.

Understanding spectra of highly excited vibrational states

Some of the characteristics of high overtone spectra observed in the near infrared are discussed, particularly in relation to local mode effects, the increasing density of states, and the effect of inter-state resonances and intramolecular vibrational redistribution.

Vibration-rotation spectra of deuterated nitrous acid, DONO

High-resolution Fourier transform infrared spectra have been recorded and analyzed for the ν3, ν4, ν5, and ν6 fundamental bands of trans-DONO, and for the ν4 fundamental of cis-DONO. The spectral resolution was better than 0.01 cm−1, and the bands have been fitted using an asymmetric top Hamiltonian with a standard deviation of around 0.0006 cm−1.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Time-varying coefficients in the almost ideal demand system: An empirical appraisal

This paper provides a generalisation of the structural time series version of the Almost Ideal Demand System (AIDS) that allows for time-varying coefficients (TVC/AIDS) in the presence of cross-equation constraints. An empirical appraisal of the TVC/AIDS is made using a dynamic AIDS with trending intercept as the baseline model with a data set from the Italian Household Budget Survey (1986-2001). The assessment is based on four criteria: adherence to theoretical constraints, statistical diagnostics on residuals, forecasting performance and economic meaningfulness. No clear evidence is found for superior performance of the TVC/AIDS, apart from improved short-term forecasts.

Predictive empirical modelling of Orobanche life cycle and seed ecology

Abstract 1.7.4

Plant variety protection, innovation, and transferability: Some empirical evidence

Under the Agreement on Trade-Related Aspects of Intellectual Property Rights, all member-countries of the World Trade Organization are required to provide an "effective" system of plant variety protection within a specific time frame. In many developing countries, this has led to a divisive debate about the fundamental desirability of extending intellectual property rights to agriculture. Empirical studies on the economic impacts of plant variety protection, especially its ability to generate large private sector investments in plant breeding and to facilitate the transfer of technology, have been very limited. This paper examines two aspects of the international experience of plant variety protection: (a) the relationship between legislation, research, and development expenditures and plant variety protection grants, i.e., the innovation effect and (b) the role of plant variety protection in facilitating the flow of varieties across countries, i.e., the transferability effect.

A GIS-based empirical model for vegetation prediction in Lefka Ori, Crete

The aim of the study was to establish and verify a predictive vegetation model for plant community distribution in the alti-Mediterranean zone of the Lefka Ori massif, western Crete. Based on previous work three variables were identified as significant determinants of plant community distribution, namely altitude, slope angle and geomorphic landform. The response of four community types against these variables was tested using classification trees analysis in order to model community type occurrence. V-fold cross-validation plots were used to determine the length of the best fitting tree. The final 9node tree selected, classified correctly 92.5% of the samples. The results were used to provide decision rules for the construction of a spatial model for each community type. The model was implemented within a Geographical Information System (GIS) to predict the distribution of each community type in the study site. The evaluation of the model in the field using an error matrix gave an overall accuracy of 71%. The user's accuracy was higher for the Crepis-Cirsium (100%) and Telephium-Herniaria community type (66.7%) and relatively lower for the Peucedanum-Alyssum and Dianthus-Lomelosia community types (63.2% and 62.5%, respectively). Misclassification and field validation points to the need for improved geomorphological mapping and suggests the presence of transitional communities between existing community types.

UV absorption spectra of methyl-substituted hydroxy-cyclohexadienyl radicals in the gas phase

UV absorption spectra of five methyl-substituted hydroxy-cyclohexadienyl radicals, formed by the addition of the hydroxyl radical (OH) to toluene (methyl benzene), o-, m- and p-xylene (1,2-, 1,3- and 1,4-dimethyl benzene, respectively) and mesitylene (1,3,5-trimethylbenzene), have been determined at 298 K, 1 atm pressure (N-2 + O-2), and the corresponding absolute absorption cross-sections measured, using laser flash photolysis and time-resolved UV absorption detection. As observed for other cyclohexadienyl-type radicals, a strong absorption band is present in the 260-340 nm spectral region, with maximum cross-sections in the range (0.9-2.2) x 10(-17) cm(2) molecule(-1). The shape of the band varies significantly from one radical to the next for the series of aromatic precursors investigated. The nature and yields of hydroxylated ring-retaining oxidation products, identified in previous studies of the OH-initiated oxidation of aromatic hydrocarbons, and the results of theoretical density functional theory (DFT) calculations indicate that one or more possible isomers of the various OH-adducts may contribute to the observed spectra. Isomers where the OH-group is ortho- (or both ortho- and ipso-) to a substituent methyl-group are likely to be the most abundant but other isomers may also be formed to a significant extent. Nonetheless, the present study provides absorption spectra of the adduct radicals formed from the gas phase addition of OH to the aromatic hydrocarbons considered, near room temperature and I atm pressure. (c) 2005 Elsevier B.V. All rights reserved.

Inelastic neutron scattering in spectroscopic studies of hydrogen on carbon-supported catalysts-experimental spectra and computed spectra of model systems

Inelastic neutron scattering spectroscopy has been used to observe and characterise hydrogen on the carbon component of a Pt/C catalyst. INS provides the complete vibration spectrum of coronene, regarded as a molecular model of a graphite layer. The vibrational modes are assigned with the aid of ab initio density functional theory calculations and the INS spectra by the a-CLIMAX program. A spectrum for which the H modes of coronene have been computationally suppressed, a carbon-only coronene spectrum, is a better representation of the spectrum of a graphite layer than is coronene itself. Dihydrogen dosing of a Pt/C catalyst caused amplification of the surface modes of carbon, an effect described as H riding on carbon. From the enhancement of the low energy carbon modes (100-600 cm(-1)) it is concluded that spillover hydrogen becomes attached to dangling bonds at the edges of graphitic regions of the carbon support. (C) 2003 Elsevier Science B.V. All rights reserved.