Simple finite field method for calculation of static and dynamic vibrational hyperpolarizabilities: curvature contributions

In the static field limit, the vibrational hyperpolarizability consists of two contributions due to: (1) the shift in the equilibrium geometry (known as nuclear relaxation), and (2) the change in the shape of the potential energy surface (known as curvature). Simple finite field methods have previously been developed for evaluating these static field contributions and also for determining the effect of nuclear relaxation on dynamic vibrational hyperpolarizabilities in the infinite frequency approximation. In this paper the finite field approach is extended to include, within the infinite frequency approximation, the effect of curvature on the major dynamic nonlinear optical processes

Variational calculation of static and dynamic vibrational nonlinear optical properties

The vibrational configuration interaction method used to obtain static vibrational (hyper)polarizabilities is extended to dynamic nonlinear optical properties in the infinite optical frequency approximation. Illustrative calculations are carried out on H2 O and N H3. The former molecule is weakly anharmonic while the latter contains a strongly anharmonic umbrella mode. The effect on vibrational (hyper)polarizabilities due to various truncations of the potential energy and property surfaces involved in the calculation are examined

Calculation of Franck-Condon factors including anharmonicity: simulation of the C2 H4+ X̃2B 3u←C2 H4X̃1 Ag band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B 3u←C2H4X̃1 Ag band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2 D4 results to be not as good as those for C2 H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested

A comparative analysis of two methods for the calculation of electric-field-induced perturbations to molecular vibration

Two common methods of accounting for electric-field-induced perturbations to molecular vibration are analyzed and compared. The first method is based on a perturbation-theoretic treatment and the second on a finite-field treatment. The relationship between the two, which is not immediately apparent, is made by developing an algebraic formalism for the latter. Some of the higher-order terms in this development are documented here for the first time. As well as considering vibrational dipole polarizabilities and hyperpolarizabilities, we also make mention of the vibrational Stark effec

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Reductions in insecticide use from adoption of Bt cotton in South Africa: impacts on economic performance and toxic load to the environment

The study reported presents the findings relating to commercial growing of genetically-modified Bt cotton in South Africa by a large sample of smallholder farmers over three seasons (1998/99, 1999/2000, 2000/01) following adoption. The analysis presents constructs and compares groupwise differences for key variables in Bt v. non-Bt technology and uses regressions to further analyse the production and profit impacts of Bt adoption. Analysis of the distribution of benefits between farmers due to the technology is also presented. In parallel with these socio-economic measures, the toxic loads being presented to the environment following the introduction of Bt cotton are monitored in terms of insecticide active ingredient (ai) and the Biocide Index. The latter adjusts ai to allow for differing persistence and toxicity of insecticides. Results show substantial and significant financial benefits to smallholder cotton growers of adopting Bt cotton over three seasons in terms of increased yields, lower insecticide spray costs and higher gross margins. This includes one particularly wet, poor growing season. In addition, those with the smaller holdings appeared to benefit proportionately more from the technology (in terms of higher gross margins) than those with larger holdings. Analysis using the Gini-coefficient suggests that the Bt technology has helped to reduce inequality amongst smallholder cotton growers in Makhathini compared to what may have been the position if they had grown conventional cotton. However, while Bt growers applied lower amounts of insecticide and had lower Biocide Indices (per ha) than growers of non-Bt cotton, some of this advantage was due to a reduction in non-bollworm insecticide. Indeed, the Biocide Index for all farmers in the population actually increased with the introduction of Bt cotton. The results indicate the complexity of such studies on the socio-economic and environmental impacts of GM varieties in the developing world.

Hydrochemical variations and contaminant load in the Rio Tinto (Spain) during flood events

The aim of this work is to study the hydrochemical variations during flood events in the Rio Tinto, SW Spain. Three separate rainfall/flood events were monitored in October 2004 following the dry season. In general, concentrations markedly increased following the first event (Fe from 99 to 1130 mg/L; Q(max) = 0.78 m(3)/s) while dissolved loads peaked in the second event (Fe = 7.5 kg/s, Cu = 0.83 kg/s, Zn = 0.82 kg/s; Q(max) = 77 m(3)/s) and discharge in the third event (Q(max) = 127 m(3)/s). This pattern reflects a progressive depletion of metals and sulphate stored in the dry summer as soluble evaporitic salt minerals and concentrated pore fluids, with dilution by freshwater becoming increasingly dominant as the month progressed. Variations in relative concentrations were attributed to oxyhydroxysulphate Fe precipitation, to relative changes in the sources of acid mine drainage (e.g. salt minerals, mine tunnels, spoil heaps etc.) and to differences in the rainfall distributions along the catchment. The contaminant load carried by the river during October 2004 was enormous, totalling some 770 t of Fe, 420 t of Al, 100 t of Cu, 100 t of Zn and 71 t of Mn. This represents the largest recorded example of this flush-out process in an acid mine drainage setting. Approximately 1000 times more water and 1408 200 times more dissolved elements were carried by the river during October 2004 than during the dry, low-flow conditions of September 2004, highlighting the key role of flood Events in the annual pollutant transport budget of semi-arid and and systems and the need to monitor these events in detail in order to accurately quantify pollutant transport. (c) 2007 Elsevier B.V. All rights reserved.