1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

Four decades of research in solid state chemistry

Solid state chemistry was in its infancy when the author got interested in the subject. In this article, the author outlines the manner in which the subject has grown over the last four decades, citing representative examples from his own contributions to the different facets of the subject. The various aspects covered include synthesis, structure, defects, phase transitions, transition metal oxides, catalysts, superconductors, metal clusters and fullerenes. In an effort to demonstrate the breadth and vitality of the subject, the author shares his own experiences and aspirations and gives expression to the agony and ecstacy in carrying out experimental research in such a frontier area in India.

Denumerable state stochastic games with limiting average payoff

We study stochastic games with countable state space, compact action spaces, and limiting average payoff. ForN-person games, the existence of an equilibrium in stationary strategies is established under a certain Liapunov stability condition. For two-person zero-sum games, the existence of a value and optimal strategies for both players are established under the same stability condition.

Influence of state of stress on the processing map for hot working of stainless steel type AISI 304L: compression vs. torsion

Processing maps for hot working of stainless steel of type AISI 304L have been developed on the basis of the flow stress data generated by compression and torsion in the temperature range 600–1200 °C and strain rate range 0.1–100 s−1. The efficiency of power dissipation given by 2m/(m+1) where m is the strain rate sensitivity is plotted as a function of temperature and strain rate to obtain a processing map, which is interpreted on the basis of the Dynamic Materials Model. The maps obtained by compression as well as torsion exhibited a domain of dynamic recrystallization with its peak efficiency occurring at 1200 °C and 0.1 s−1. These are the optimum hot-working parameters which may be obtained by either of the test techniques. The peak efficiency for the dynamic recrystallization is apparently higher (64%) than that obtained in constant-true-strain-rate compression (41%) and the difference in explained on the basis of strain rate variations occurring across the section of solid torsion bar. A region of flow instability has occurred at lower temperatures (below 1000 °C) and higher strain rates (above 1 s−1) and is wider in torsion than in compression. To achieve complete microstructure control in a component, the state of stress will have to be considered.

Interaction of C60 and C70 with aromatic amines in the ground and excited states. Evindence for fullerene—benzene interaction in the ground state

While C60 interacts with aromatic amines such as dimethylaniline in the ground state, C70 does not. Fluorescence spectroscopic studies, including lifetime measurements, show the formation of exciplexes of both C60 and C70 with aromatic amines in nonaromatic solvents such as methylcyclohexane. Exciplexes are however not formed in benzene solvent, due to π—π interaction between benzene and the fullerene. Based on spectroscopic absorption measurements, it is shown that both C60 and C70 do indeed interact with benzene in the ground state.

Is tetramethyleneethane a ground state triplet?

We have examined a number of possible ways by which tetramethyleneethane (TME) can be a ground state triplet, as claimed by experimental studies, in violation of Ovchinnikov’s theorem for alternant hydrocarbons of equal bond lengths. Model exact π calculations of the low-lying states of TME, 3,4-dimethylenefuran and 3,4-dimethylenepyrrole were carried out using a diagrammatic valence bond approach. The calculations failed to yield a triplet ground state even after (a) tuning of electron correlation, (b) breaking alternancy symmetry, and (c) allowing for geometric distortions. In contrast to earlier studies of fine structure constants in other conjugated systems, the computedD andE values of all the low-lying triplet states of TME for various geometries are at least an order of magnitude different from the experimentally reported values. Incorporation of σ-π mixing by means of UHF MNDO calculations is found to favour a singlet ground state even further. A reinterpretation of the experimental results of TME is therefore suggested to resolve the conflict.

Current State of Domestic Concealed Wiring Practices in Bangalore, India

In a modernising world, building and construction trends in recent urban centres such as Bangalore, set precedence for developments in other urban centres of the country. Under such conditions, evaluating the current state of building practices could prove useful for identifying the likely nature of nationwide building trends. This paper comprises a study to evaluate the current state of domestic concealed wiring practices in the context of a modern urban centre area in India. Presently, concealed wiring is the predominant wiring method adopted for residences, both bungalows and apartments. A modern residential block in the city of Bangalore (India) was chosen as the study area. The study included extensive interaction and surveys amongst residents, professionals (architects and engineers) and site personnel (contractors and electricians). In addition, the study also included site verification on the state of wiring practices in the residential block. The study indicates that while aesthetics was the prime reason that dictated the choice of concealed wiring, its effectiveness as an appropriate and safe wiring method is severely compromised. Details of the study, results and recommendations are presented in this paper.

Part-of-Speech Tagging using Parallel Weighted Finite-State Transducers

We use parallel weighted finite-state transducers to implement a part-of-speech tagger, which obtains state-of-the-art accuracy when used to tag the Europarl corpora for Finnish, Swedish and English. Our system consists of a weighted lexicon and a guesser combined with a bigram model factored into two weighted transducers. We use both lemmas and tag sequences in the bigram model, which guarantees reliable bigram estimates.

Finite-State Spell-Checking with Weighted Language and Error Models

In this paper we present simple methods for construction and evaluation of finite-state spell-checking tools using an existing finite-state lexical automaton, freely available finite-state tools and Internet corpora acquired from projects such as Wikipedia. As an example, we use a freely available open-source implementation of Finnish morphology, made with traditional finite-state morphology tools, and demonstrate rapid building of Northern Sámi and English spell checkers from tools and resources available from the Internet.

Building and Using Existing Hunspell Dictionaries and TEX Hyphenators as Finite-State Automata

There are numerous formats for writing spellcheckers for open-source systems and there are many descriptions for languages written in these formats. Similarly, for word hyphenation by computer there are TEX rules for many languages. In this paper we demonstrate a method for converting these spell-checking lexicons and hyphenation rule sets into finite-state automata, and present a new finite-state based system for writer’s tools used in current open-source software such as Firefox, OpenOffice.org and enchant via the spell-checking library voikko.

Guessers for Finite-State Transducer Lexicons

Language software applications encounter new words, e.g., acronyms, technical terminology, names or compounds of such words. In order to add new words to a lexicon, we need to indicate their inflectional paradigm. We present a new generally applicable method for creating an entry generator, i.e. a paradigm guesser, for finite-state transducer lexicons. As a guesser tends to produce numerous suggestions, it is important that the correct suggestions be among the first few candidates. We prove some formal properties of the method and evaluate it on Finnish, English and Swedish full-scale transducer lexicons. We use the open-source Helsinki Finite-State Technology to create finitestate transducer lexicons from existing lexical resources and automatically derive guessers for unknown words. The method has a recall of 82-87 % and a precision of 71-76 % for the three test languages. The model needs no external corpus and can therefore serve as a baseline.