Force constants and dipole‐moment derivatives of molecules from perturbed Hartree–Fock calculations

General expressions for the force constants and dipole‐moment derivatives of molecules are derived, and the problems arising in their practical application are reviewed. Great emphasis is placed on the use of the Hartree–Fock function as an approximate wavefunction, and a number of its properties are discussed and re‐emphasised. The main content of this paper is the development of a perturbed Hartree–Fock theory that makes possible the direct calculation of force constants and dipole‐moment derivatives from SCF–MO wavefunctions. Essentially the theory yields ∂ϕi / ∂RJα, the derivative of an MO with respect to a nuclear coordinate.

Force constants and dipole moment derivatives of molecules from perturbed Hartree-Fock calculations II. Applications to limited basis set SCF-MO wavefunctions

The perturbed Hartree–Fock theory developed in the preceding paper is applied to LiH, BH, and HF, using limited basis‐set SCF–MO wavefunctions derived by previous workers. The calculated values for the force constant ke and the dipole‐moment derivative μ(1) are (experimental values in parentheses): LiH, ke  =  1.618(1.026)mdyn/Å,μ(1)  =  −18.77(−2.0±0.3)D/ÅBH,ke  =  5.199(3.032)mdyn/Å,μ(1)  =  −1.03(−)D/Å;HF,ke  =  12.90(9.651)mdyn/Å,μ(1)  =  −2.15(+1.50)D/Å. The values of the force on the proton were calculated exactly and according to the Hellmann–Feynman theorem in each case, and the discrepancies show that none of the wavefunctions used are close to the Hartree–Fock limit, so that the large errors in ke and μ(1) are not surprising. However no difficulties arose in the perturbed Hartree–Fock calculation, so that the application of the theory to more accurate wavefunctions appears quite feasible.

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.

Inequality and GM crops: a case study of Bt cotton in India

Critics of genetically modified (GM) crops often contend that their introduction enhances the gap between rich and poor farmers, as the former group are in the best position to afford the expensive seed as well as provide other inputs such as fertilizer and irrigation. The research reported in this paper explores this issue with regard to Bt cotton (cotton with the endotoxtin gene from Bacillus thuringiensis conferring resistance to some insect pests) in Jalgaon, Maharashtra State, India, spanning the 2002 and 2003 seasons. Questionnaire–based survey results from 63 non–adopting and 94 adopting households of Bt cotton were analyzed, spanning 137 Bt cotton plots and 95 non–Bt cotton plots of both Bt adopters and non–adopters. For these households, cotton income accounted for 85 to 88% of total household income, and is thus of vital importance. Results suggest that in 2003 Bt adopting households have significantly more income from cotton than do non–adopting households (Rp 66,872 versus Rp 46,351) but inequality in cotton income, measured with the Gini coefficient (G), was greater amongst non–adopters than adopters. While Bt adopters had greater acreage of cotton in 2003 (9.92 acres versus 7.42 for non–adopters), the respective values of G were comparable. The main reason for the lessening of inequality amongst adopters would appear to be the consistency in the performance of Bt cotton along with the preferred non–Bt cultivar of Bt adopters—Bunny. Taking gross margin as the basis for comparison, Bt plots had 2.5 times the gross margin of non–Bt plots of non–adopters, while the advantage of Bt plots over non–Bt plots of adopters was 1.6 times. Measured in terms of the Gini coefficient of gross margin/acre it was apparent that inequality was lessened with the adoption of Bunny (G = 0.47) and Bt (G = 0.3) relative to all other non–Bt plots (G = 0.63). Hence the issue of equality needs to be seen both in terms of differences between adopters and non–adopters as well as within each of the groups.

Force distribution in manipulation by a robot hand with equality and inequality constraints

The problem of the appropriate distribution of forces among the fingers of a four-fingered robot hand is addressed. The finger-object interactions are modelled as point frictional contacts, hence the system is indeterminate and an optimal solution is required for controlling forces acting on an object. A fast and efficient method for computing the grasping and manipulation forces is presented, where computation has been based on using the true model of the nonlinear frictional cone of contact. Results are compared with previously employed methods of linearizing the cone constraints and minimizing the internal forces.

Characterising the variability and extremes of the stratospheric polar vortices using 2D moment analysis

The mean state, variability and extreme variability of the stratospheric polar vortices, with an emphasis on the Northern Hemisphere vortex, are examined using 2-dimensional moment analysis and Extreme Value Theory (EVT). The use of moments as an analysis to ol gives rise to information about the vortex area, centroid latitude, aspect ratio and kurtosis. The application of EVT to these moment derived quantaties allows the extreme variability of the vortex to be assessed. The data used for this study is ECMWF ERA-40 potential vorticity fields on interpolated isentropic surfaces that range from 450K-1450K. Analyses show that the most extreme vortex variability occurs most commonly in late January and early February, consistent with when most planetary wave driving from the troposphere is observed. Composites around sudden stratospheric warming (SSW) events reveal that the moment diagnostics evolve in statistically different ways between vortex splitting events and vortex displacement events, in contrast to the traditional diagnostics. Histograms of the vortex diagnostics on the 850K (∼10hPa) surface over the 1958-2001 period are fitted with parametric distributions, and show that SSW events comprise the majority of data in the tails of the distributions. The distribution of each diagnostic is computed on various surfaces throughout the depth of the stratosphere, and shows that in general the vortex becomes more circular with higher filamentation at the upper levels. The Northern Hemisphere (NH) and Southern Hemisphere (SH) vortices are also compared through the analysis of their respective vortex diagnostics, and confirm that the SH vortex is less variable and lacks extreme events compared to the NH vortex. Finally extreme value theory is used to statistically mo del the vortex diagnostics and make inferences about the underlying dynamics of the polar vortices.

Inequality, intergenerational mobility and redistributive policies under endogenous information

This paper presents a dynamic model to study how different levels of information about the root determinants of wealth (luck versus effort) can impact inequality and intergenerational mobility through societal beliefs, individual choices and redistributive policies. To my knowledge, the model presented is the first dynamicmodel in which skills are stochastic and both beliefs and voted redistribution are determined endogenously. The model is able to explain a number of empirical facts. Large empirical evidence shows that the difference in the political support for redistribution appears to reflect differences in the social perceptions regarding the determinants of individual wealth and the underlying sources of income inequality. Moreover the beliefs about the determinants of wealth impact individual choices of effort and therefore the beliefs about the determinants of wealth impact inequality and mobility both through choices of effort and redistributive policies. The model generates multiple equilibria (US versus Europe-type) which may account for the observed features not only in terms of societal beliefs and redistribution but also in terms of perceived versus real mobility and inequality.

Intergenerational persistence in health in developing countries : the penalty of gender inequality?

This paper is motivated to investigate the often neglected payoff to investments in the health of girls and women in terms of next generation outcomes. This paper investigates the intergenerational persistence of health across time and region as well as across the distribution of maternal health. It uses comparable microdata on as many as 2.24 million children born of about 0.6 million mothers in 38 developing countries in the 31 year period, 1970–2000. Mother's health is indicated by her height, BMI and anemia status. Child health is indicated by mortality risk and anthropometric failure. We find a positive relationship between maternal and child health across indicators and highlight non-linearities in these relationships. The results suggest that both contemporary and childhood health of the mother matter and that the benefits to the next generation are likely to be persistent. Averaging across the sample, persistence shows a considerable decline over time. Disaggregation shows that the decline is only significant in Latin America. Persistence has remained largely constant in Asia and has risen in Africa. The paper provides the first cross-country estimates of the intergenerational persistence in health and the first estimates of trends.

Inequality of educational opportunity in India: changes over time and across states

This paper documents the extent of inequality of educational opportunity in India spanning the period 1983–2004 using National Sample Surveys. We build on recent developments in the literature that have operationalized concepts of inequality of opportunity theory and construct several indices of inequality of educational opportunity for an adult sample. Kerala stands out as the least opportunity-unequal state. Rajasthan, Gujarat, and Uttar Pradesh experienced large-scale falls in the ranking of inequality of opportunities. By contrast, West Bengal and Orissa made significant progress in reducing inequality of opportunity. We also examine the links between progress toward equality of opportunity and a selection of pro-poor policies.