Variations in the copper(I)-copper(I) distances in multinuclear clusters with identical coordination geometries. Short metal-metal contacts induced by oligomerization

Factors contributing to the variations in the Cu(I)-Cu(I) distances in two clusters with identical ligand and coordination geometries have been analyzed. While the hexamer, 4, exhibits metal-metal distances in the range 2.81-3.25 Angstrom, shorter contacts are found in the corresponding tetramer, 3 (2.60-2.77 Angstrom). EHT calculations reveal relatively little attractive interactions in the corresponding Cu-4(4+) and Cu-6(6+) cores. Introduction of the ligands lowers the reduced overlap populations between the metals further. MNDO calculations with model electrophiles have been carried out to determine the bite angle requirements of the ligands. These are satisfactorily met in the structures of both 3 and 4. The key geometric feature distinguishing 3 and 4 is the Cu-S-Cu angle involving the bridging S- unit. In 4, the corresponding angles are about 90 degrees, while the values in 3 are smaller (70-73 degrees). Wider angles are computed to be energetically favored and are characterized by an open three-center bond and a long Cu-Cu distance. The bridging angles are suggested to be primarily constrained by the mode of oligomerization. Implications of these results for the stability and reactivity of these clusters and for short metal-metal distances in d(10) systems in general are discussed.

Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?

Recently, it was found that a reduction in atmospheric CO2 concentration leads to a temporary increase in global precipitation. We use the Hadley Center coupled atmosphere-ocean model, HadCM3L, to demonstrate that this precipitation increase is a consequence of precipitation sensitivity to changes in atmospheric CO2 concentrations through fast tropospheric adjustment processes. Slow ocean cooling explains the longer-term decrease in precipitation. Increased CO2 tends to suppress evaporation/precipitation whereas increased temperatures tend to increase evaporation/precipitation. When the enhanced CO2 forcing is removed, global precipitation increases temporarily, but this increase is not observed when a similar negative radiative forcing is applied as a reduction of solar intensity. Therefore, transient precipitation increase following a reduction in CO2-radiative forcing is a consequence of the specific character of CO2 forcing and is not a general feature associated with decreases in radiative forcing. Citation: Cao, L., G. Bala, and K. Caldeira (2011), Why is there a short-term increase in global precipitation in response to diminished CO2 forcing?, Geophys. Res. Lett., 38, L06703, doi:10.1029/2011GL046713.

Effect of Short Duration of Load increment on the Compressibility of Soils

This study concerns the effect of duration of load increment (up to 24 h) on the consolidation properties of expansive black cotton soil (liquid limit = 81%) and nonexpansive kaolinite (liquid limit = 49%). It indicates that the amount and rate of compression are not noticeably affected by the duration of loading for a standard sample of 25 mm in height and 76.2 mm in diameter with double drainage. Hence, the compression index and coefficient of consolidation can be obtained with reasonable accuracy even if the duration of each load increment is as short as 4 h. The secondary compression coefficient (C-alpha epsilon) for kaolinite can be obtained for any pressure range with 1/2 h of loading, which, however, requires 4 h for black cotton soil. This is because primary consolidation is completed early in the case of kaolinite. The paper proves that the conventional consolidation test can be carried out with much shorter duration of loading (less than 4 h) than the standard specification of 24 h or more even for remolded fine-grained soils.

Short-bite chiral diphosphazanes derived from (S)-?-methyl benzyl amine and their Pd, Pt and Rh metal complexes

New chiral diphosphazane ligands of the type Ph(2)PN(S-*CHMePh)PYY' {YY'= Ph(2) (2), O2C6H4 (3); Y= Ph, Y'= Cl {4a (SS), 4b (SR)}, N(2)C(3)HMe(2)-3,5 {5a (SR), 5b (SS)} are synthesised starting from a chiral aminophosphine, Ph(2)PNH(S-*CHMePh) (1). The structure of one of the diastereomer 5a has been confirmed by single crystal X-ray diffraction {Orthorhombic system, P2(1)2(1)2(1); a=10.456 (4), b=15.362 (7), c=17.379 (6) Angstrom, Z=4}. Transition metal mononuclear complexes [Rh{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}(2)](+)(BF4)(-) (6), [PdCl2{eta(2)-(Ph(2)P)(2)N(S-*CHMePh)}] (7) and [PtCl2{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}] (8) have also been synthesised. The structure of the palladium complex 7 is solved by X-ray crystallography {Orthorhombic system, P2(1)2(1)2(1); a=8.746 (2), b=18.086 (2), c=20.811 (3) Angstrom, Z=4}. All these compounds are characterised by micro analyses, IR and NMR spectroscopic data.

A short, formal synthesis of (+/-)-2-pupukeanone

A short approach to (+/-)-2-pupukeanone, starting from 2,6-dimethylcyclohexenone employing a combination of Michael-Michael reaction and an intramolecular rhodium carbenoid C-H insertion as key reactions, is described.

Investigation of short-time isomerization dynamics in p-nitroazobenzene from resonance Raman intensity analysis

Resonance Raman (RR) spectra are presented for p-nitroazobenzene dissolved in chloroform using 18 excitation Wavelengths, covering the region of (1)(n --> pi*) electronic transition. Raman intensities are observed for various totally symmetric fundamentals, namely, C-C, C-N, N=N, and N-O stretching vibrations, indicating that upon photoexcitation the excited-state evolution occurs along all of these vibrational coordinates. For a few fundamentals, interestingly, in p-nitroazobenzene, it is observed that the RR intensities decrease near the maxima of the resonant electronic (1)(n --> pi*) transition. This is attributed to the interference from preresonant scattering due to the strongly allowed (1)(pi --> pi*) electronic transition. The electronic absorption spectrum and the absolute Raman cross section for the nine Franck-Condon active fundamentals of p-nitroazobenzene have been successfully modeled using Heller's time-dependent formalism for Raman scattering. This employs harmonic description of the lowest energy (1)(n --> pi*) potential energy surface. The short-time isomerization dynamics is then examined from a priori knowledge of the ground-state normal mode descriptions of p-nitroazobenzene to convert the wave packet motion in dimensionless normal coordinates to internal coordinates. It is observed that within 20 fs after photoexcitation in p-nitroazobenzene, the N=N and C-N stretching vibrations undergo significant changes and the unsubstituted phenyl ring and the nitro stretching vibrations are also distorted considerably.

An appraisal of electric automobile power sources

Road transportation, as an important requirement of modern society, is presently hindered by restrictions in emission legislations as well as the availability of petroleum fuels, and as a consequence, the fuel cost. For nearly 270 years, we burned our fossil cache and have come to within a generation of exhausting the liquid part of it. Besides, to reduce the greenhouse gases, and to obey the environmental laws of most countries, it would be necessary to replace a significant number of the petroleum-fueled internal-combustion-engine vehicles (ICEVs) with electric cars in the near future. In this article, we briefly describe the merits and demerits of various proposed electrochemical systems for electric cars, namely the storage batteries, fuel cells and electrochemical supercapacitors, and determine the power and energy requirements of a modern car. We conclude that a viable electric car could be operated with a 50 kW polymer-electrolyte fuel cell stack to provide power for cruising and climbing, coupled in parallel with a 30 kW supercapacitor and/or battery bank to deliver additional short-term burst-power during acceleration.

A Note On The Effect Of Short And Long Laminar Separation-Bubbles On Desinent Cavitation

Earlier desinent cavitation studies on a 1/8 caliber ogive by one of the authors (J. W. H.) showed a sudden change in the magnitude of the desinent cavitation number at a critical velocity. In the present work it is shown by means of oil-film flow visualization that below the critical velocity a long laminar separation bubble exists whereas above the critical velocity the laminar separation bubble is short. Thus the desinent cavitation characteristics of a 1/8 caliber ogive are governed by the nature of the viscous flow around the body.

An Investigation into the Dependence of the Arc Voltage on the Parameters of the Short-Circuit Current and the Design of the Vacuum Interrupter

The vacuum interrupter is extensively employed in the medium voltage switchgear for the interruption of the short-circuit current. The voltage across the arc during current interruption is termed as the arc voltage. The nature and magnitude of this arc voltage is indicative of the performance of the contacts and the vacuum interrupter as a whole. Also, the arc voltage depends on the parameters like the magnitude of short-circuit current, the arcing time, the point of opening of the contacts, the geometry and area of the contacts and the type of magnetic field. This paper investigates the dependency of the arc voltage on some of these parameters. The paper also discusses the usefulness of the arc voltage in diagnosing the performance of the contacts.

Community-based Natural Resource Management: Issues and Cases from South Asia

Community-based natural resource management (CBNRM) is the joint management of natural resources by a community based on a community strategy, through a participatory mechanism involving all legitimate stakeholders. The approach is community-based in that the communities managing the resources have the legal rights, the local institutions and the economic incentives to take substantial responsibility for sustained use of these resources. This implies that the community plays an active role in the management of natural resources, not because it asserts sole ownership over them, but because it can claim participation in their management and benefits for practical and technical reasons1–4. This approach emerged as the dominant conservation concept in the late 1970s and early 1980s, of the disillusionment with the developmental state. Governments across South and South East Asia, Africa and Latin America have adopted and implemented CBNRM in various ways, viz. through sectoral programmes such as forestry, irrigation or wildlife management, multisectoral programmes such as watershed development and efforts towards political devolution. In India, the principle of decentralization through ‘gram swaraj’ was introduced by Mahatma Gandhi. The 73rd and 74th constitution amendments in 1992 gave impetus to the decentralized planning at panchayat levels through the creation of a statutory three-level local self-government structure5,6. The strength of this book is that it includes chapters by CBNRM advocates based on six seemingly innovative initiatives being implemented by nongovernmental organizations (NGOs) in ecologically vulnerable regions of South Asia: two in the Himalayas (watershed development programme in Lingmutechhu, Bhuthan and Thalisain tehsil, Paudi Grahwal District, Uttarakhand), three in semi-arid parts of western India (watershed development in Hivre Bazar, Maharashtra and Nathugadh village, Gujarat and water-harvesting structures in Gopalapura, Rajasthan) and one in the flood-plains of the Brahmaputra–Jamuna (Char land, Galibanda and Jamalpur districts, Bangladesh). Watersheds in semi-arid regions fall in the low-rainfall region (500–700 mm) and suffer the vagaries of drought 2–3 years in every five-year cycle. In all these locations, the major occupation is agriculture, most of which is rainfed or dry. The other two cases (in Uttarakhand) fall in the Himalayan region (temperate/sub-temperate climate), which has witnessed extensive deforestation in the last century and is now considered as one of the most vulnerable locations in South Asia. Terraced agriculture is being practised in these locations for a long time. The last case (Gono Chetona) falls in the Brahmaputra–Jamuna charlands which are the most ecologically vulnerable regions in the sub-continent with constantly changing landscape. Agriculture and livestock rearing are the main occupations, and there is substantial seasonal emigration for wage labour by the adult males. River erosion and floods force the people to adopt a semi-migratory lifestyle. The book attempts to analyse the potential as well as limitations of NGOdriven CBNRM endeavours across agroclimatic regions of South Asia with emphasis on four intrinsically linked normative concerns, namely sustainability, livelihood enhancement, equity and demographic decentralization in chapters 2–7. Comparative analysis of these case studies done in chapter 8, highlights the issues that require further research while portraying the strengths and limits of NGO-driven CBNRM. In Hivre Bazar, the post-watershed intervention scenario is such that farmers often grow three crops in a year – kharif bajra, rabi jowar and summer vegetable crops. Productivity has increased in the dry lands due to improvement in soil moisture levels. The revival of johads in Gopalpura has led to the proliferation of wheat and increased productivity. In Lingmuteychhu, productivity gains have also arisen, but more due to the introduction of both local and high-yielding, new varieties as opposed to increased water availability. In the case of Gono Chetona, improvements have come due to diversification of agriculture; for example, the promotion of vegetable gardens. CBNRM interventions in most cases have also led to new avenues of employment and income generation. The synthesis shows that CBNRM efforts have made significant contributions to livelihood enhancement and only limited gains in terms of collective action for sustainable and equitable access to benefits and continuing resource use, and in terms of democratic decentralization, contrary to the objectives of the programme. Livelihood benefits include improvements in availability of livelihood support resources (fuelwood, fodder, drinking water), increased productivity (including diversification of cropping pattern) in agriculture and allied activities, and new sources of livelihood. However, NGO-driven CBNRM has not met its goal of providing ‘alternative’ forms of ‘development’ due to impediments of state policy, short-sighted vision of implementers and confrontation with the socio-ecological reality of the region, which almost always are that of fragmented communities (or communities in flux) with unequal dependence and access to land and other natural resources along with great gender imbalances. Appalling, however, is the general absence of recognition of the importance of and the will to explore practical ways to bring about equitable resource transfer or benefit-sharing and the consequent innovations in this respect that are evident in the pioneering community initiatives such as pani panchayat, etc. Pertaining to the gains on the ecological sustainability front, Hivre Bazar and Thalisain initiatives through active participation of villagers have made significant regeneration of the water table within the village, and mechanisms such as ban on number of bore wells, the regulation of cropping pattern, restrictions on felling of trees and free grazing to ensure that in the future, the groundwater is neither over-exploited nor its recharge capability impaired. Nevertheless, the longterm sustainability of the interventions in the case of Ghoga and Gopalpura initiatives as the focus has been mostly on regeneration of resources, and less on regulating the use of regenerated resources. Further, in Lingmuteychhu and Gono Chetona, the interventions are mainly household-based and the focus has been less explicit on ecological components. The studies demonstrate the livelihood benefits to all of the interventions and significant variation in achievements with reference to sustainability, equity and democratic decentralization depending on the level and extent of community participation apart from the vision of implementers, strategy (or nature of intervention shaped by the question of community formation), the centrality of community formation and also the State policy. Case studies show that the influence of State policy is multi-faceted and often contradictory in nature. This necessitates NGOs to engage with the State in a much more purposeful way than in an ‘autonomous space’. Thus the role of NGOs in CBNRM is complementary, wherein they provide innovative experiments that the State can learn. This helps in achieving the goals of CBNRM through democratic decentralization. The book addresses the vital issues related to natural resource management and interests of the community. Key topics discussed throughout the book are still at the centre of the current debate. This compilation consists of well-written chapters based on rigorous synthesis of CBNRM case studies, which will serve as good references for students, researchers and practitioners in the years to come.

A new 6-component accelerometer force balance for short duration ground testing facilities

A new six-component accelerometer force balance is developed and used in the HST2 shock tunnel of Indian Institute of Science. Aerodynamic forces and moments for a hypersonic slender body measured using this balance system at a free stream Mach number of 5.75 and Reynolds number of 1.5 million and stagnation enthalpy of 1.5 and 2 MJ/kg are presented. These measured values compare well with the theoretical values estimated using modified Newtonian theory.

Creep behaviour of short fibre reinforced QE22 magnesium alloy using impression creep test

Creep properties of QE22 magnesium based alloy and composites reinforced with 20 volume percent of short-fibers - Maftech (R), Saffil (R) or Supertech (R), were evaluated using the impression creep test. In the impression creep test, a load is applied with the help of a cylindrical tungsten carbide indenter of 1 mm diameter. This has advantages over conventional creep testing in terms of small specimen size requirement and simple machining. Depth of impression is recorded with time and steady state strain rate is obtained from the slope of the secondary strain (depth of impression divided by indenter diameter) vs. time plot. The results are compared with the creep obtained from conventional creep performed in tension on the same materials earlier. Microstructural examination of the plastically deformed regions is carried out to explain creep behaviour of these composites.

Decentralized peak power control based on short-term forecast using modified Kalman filter

This paper proposes a method of short term load forecasting with limited data, applicable even at 11 kV substation levels where total power demand is relatively low and somewhat random and weather data are usually not available as in most developing countries. Kalman filtering technique has been modified and used to forecast daily and hourly load. Planning generation and interstate energy exchange schedule at load dispatch centre and decentralized Demand Side Management at substation level are intended to be carried out with the help of this short term load forecasting technique especially to achieve peak power control without enforcing load-shedding.