Soviet-American Cooperative Research on Marine Mammals. Volume 1- Pinnipeds: Under Project V.6. Marine Mammals, of the US-USSR Agreement on Cooperation in the Field of Environmental Protection

Some 25 to 30 yr ago, when we as students were beginning our respective careers and were developing for the first time our awareness of marine mammals in the waters separating western North America from eastern Asia, we had visions of eventually bridging the communication gap which existed between our two countries at that time. Each of us was anxious to obtain information on the distribution, biology, and ecological relations of "our" seals and walruses on "the other side," beyond our respective political boundari~s where we were not permitted to go to study them. We were concerned that the resource management practices on the other side of the Bering and Chukchi Seas, implemented in isolation, on a purely unilateral basis, might endanger the species which we had come to know and were striving to conserve. At once apparent to both of us was the need for free exchange of biological information between our two countries and, ultimately, joint management of our shared resources. In a small way, we and others made some initial efforts to generate that exchange by personal correspondence and through vocal interchange at the annual meetings of the North Pacific Fur Seal Commission. By the enabling Agreement on Cooperation in the Field of Environmental Protection, reached between our two countries in 1972, our earlier visions at last came true. Since that time, within the framework of the Marine Mammal Project under Area V of that Agreement, we and our colleagues have forged a strong bond of professional accord and respect, in an atmosphere of free intercommunication and mutual understanding. The strength and utility of this arrangement from the beginning of our joint research are reflected in the reports contained in this, the first compendium of our work. The need for a series of such a compendia became apparent to us in 1976, and its implementation was agreed on by the regular meeting of the Project in La Jolla, Calif., in January 1977. Obviously, the preparation and publication of this first volume has been excessively delayed, in part by continuing political distrust between our governments but mainly by increasing demands placed on the time of the contributors. In this period of growing environmental concern in both countries, we and our colleagues have been totally immersed in other tasks and have experienced great difficulty in drawing together the works presented here. Much of the support for doing so was provided by the State of Alaska, through funding for Organized Research at the University of Alaska-Fairbanks. For its ultimate completion in publishable form we wish to thank Helen Stockholm, Director of Publications, Institute of Marine Science, University of Alaska, and her staff, especially Ruth Hand, and the numerous referees narned herein who gave willingly oftheir time to review each ofthe manuscripts critically and to provide a high measure of professionalism to the final product. (PDF file contains 110 pages.)

Proceedings of the International Workshop on age determination of oceanic pelagic fishes: Tunas, billfishes, and sharks, Miami, Florida, February 15-18,1982

Accurate and precise estimates of age and growth rates are essential parameters in understanding the population dynamics of fishes. Some of the more sophisticated stock assessment models, such as virtual population analysis, require age and growth information to partition catch data by age. Stock assessment efforts by regulatory agencies are usually directed at specific fisheries which are being heavily exploited and are suspected of being overfished. Interest in stock assessment of some of the oceanic pelagic fishes (tunas, billfishes, and sharks) has developed only over the last decade, during which exploitation has increased steadily in response to increases in worldwide demand for these resources. Traditionally, estimating the age of fishes has been done by enumerating growth bands on skeletal hardparts, through length frequency analysis, tag and recapture studies, and raising fish in enclosures. However, problems related to determining the age of some of the oceanic pelagic fishes are unique compared with other species. For example, sampling is difficult for these large, highly mobile fishes because of their size, extensive distributions throughout the world's oceans, and for some, such as the marlins, infrequent catches. In addition, movements of oceanic pelagic fishes often transect temperate as well as tropical oceans, making interpretation of growth bands on skeletal hardparts more difficult than with more sedentary temperate species. Many oceanic pelagics are also long-lived, attaining ages in excess of 30 yr, and more often than not, their life cycles do not lend themselves easily to artificial propagation and culture. These factors contribute to the difficulty of determining ages and are generally characteristic of this group-the tunas, billfishes, and sharks. Accordingly, the rapidly growing international concern in managing oceanic pelagic fishes, as well as unique difficulties in ageing these species, prompted us to hold this workshop. Our two major objectives for this workshop are to: I) Encourage the interchange of ideas on this subject, and 2) establish the "state of the art." A total of 65 scientists from 10 states in the continental United States and Hawaii, three provinces in Canada, France, Republic of Senegal, Spain, Mexico, Ivory Coast, and New South Wales (Australia) attended the workshop held at the Southeast Fisheries Center, Miami, Fla., 15-18 February 1982. Our first objective, encouraging the interchange of ideas, is well illustrated in the summaries of the Round Table Discussions and in the Glossary, which defines terms used in this volume. The majority of the workshop participants agreed that the lack of validation of age estimates and the means to accomplish the same are serious problems preventing advancements in assessing the age and growth of fishes, particularly oceanic pelagics. The alternatives relating to the validation problem were exhaustively reviewed during the Round Table Discussions and are a major highlight of this workshop. How well we accomplished our second objective, to establish the "state of the art" on age determination of oceanic pelagic fishes, will probably best be judged on the basis of these proceedings and whether future research efforts are directed at the problem areas we have identified. In order to produce high-quality papers, workshop participants served as referees for the manuscripts published in this volume. Several papers given orally at the workshop, and included in these proceedings, were summarized from full-length manuscripts, which have been submitted to or published in other scientific outlets-these papers are designated as SUMMARY PAPERS. In addition, the SUMMARY PAPER designation was also assigned to workshop papers that represented very preliminary or initial stages of research, cursory progress reports, papers that were data shy, or provide only brief reviews on general topics. Bilingual abstracts were included for all papers that required translation. We gratefully acknowledge the support of everyone involved in this workshop. Funding was provided by the Southeast Fisheries Center, and Jack C. Javech did the scientific illustrations appearing on the cover, between major sections, and in the Glossary. (PDF file contains 228 pages.)

Testing the performance and feasibility of Bluetooth communications in pervasive systems

Smart and mobile environments require seamless connections. However, due to the frequent process of ''discovery'' and disconnection of mobile devices while data interchange is happening, wireless connections are often interrupted. To minimize this drawback, a protocol that enables an easy and fast synchronization is crucial. Bearing this in mind, Bluetooth technology appears to be a suitable solution to carry on such connections due to the discovery and pairing capabilities it provides. Nonetheless, the time and energy spent when several devices are being discovered and used at the same time still needs to be managed properly. It is essential that this process of discovery takes as little time and energy as possible. In addition to this, it is believed that the performance of the communications is not constant when the transmission speeds and throughput increase, but this has not been proved formally. Therefore, the purpose of this project is twofold: Firstly, to design and build a framework-system capable of performing controlled Bluetooth device discovery, pairing and communications. Secondly, to analyze and test the scalability and performance of the \emph{classic} Bluetooth standard under different scenarios and with various sensors and devices using the framework developed. To achieve the first goal, a generic Bluetooth platform will be used to control the test conditions and to form a ubiquitous wireless system connected to an Android Smartphone. For the latter goal, various stress-tests will be carried on to measure the consumption rate of battery life as well as the quality of the communications between the devices involved.

Reactions of platinum(II) complexes with dioxygen: progress toward alkane functionalization

Whereas stoichiometric activation of C-H bonds by complexes of transition metals is becoming increasingly common, selective functionalization of alkanes remains a formidable challenge in organometallic chemistry. The recent advances in catalytic alkane functionalization by transition-metal complexes are summarized in Chapter I.

The studies of the displacement of pentafluoropyridine in [(tmeda)Pt(CH_3)(NC_5F_5)][BAr^f_4] (1) with γ- tetrafluoropicoline, a very poor nucleophile, are reported in Chapter II. The ligand substitution occurs by a dissociative interchange mechanism. This result implies that dissociative loss of pentafluoropyridine is the rate-limiting step in the C-H activation reactions of 1.

Oxidation of dimethylplatinum(II) complexes (N-N)Pt(CH_3)_2 (N-N = tmeda(1), α-diimines) by dioxygen is described in Chapter III. Mechanistic studies suggest a two-step mechanism. First, a hydroperoxoplatinum(IV) complex is formed in a reaction between (N-N)Pt(CH_3)_2 and dioxygen. Next, the hydroperoxy complex reacts with a second equivalent of (N-N)Pt(CH_3)_2 to afford the final product, (N-N)Pt(OH)(OCH_3)(CH_3)_2. The hydroperoxy intermediate, (tmeda)Pt(OOH)(OCH_3)(CH_3)_2 (2), was isolated and characterized. The reactivity of 2 with several dime thylplatinum(II) complexes is reported.

The studies described in Chapter IV are directed toward the development of a platinum(II)-catalyzed oxidative alkane dehydrogenation. Stoichiometric conversion of alkanes (cyclohexane, ethane) to olefins (cyclohexene, ethylene) is achieved by C-H activation with [(N-N)Pt(CH_3)(CF_3CH_2OH)]BF_4 (1, N-N is N,N'-bis(3,5-di-t- butylphenyl)-1,4-diazabutadiene) which results in the formation of olefin hydride complexes. The first step in the C-H activation reaction is formation of a platinum(II) alkyl which undergoes β-hydrogen elimination to afford the olefin hydride complex. The cationic ethylplatinum(II) intermediate can be generated in situ by treating diethylplatinum(II) compounds with acids. Treatment of (phen)PtEt_2 with [H(OEt_2)_2]Bar^f_4 at low temperatures resulted in the formation of a mixture of [(phen)PtEt(OEt_2)]Bar^f_4 (8) and [(phen)Pt(C_2H_4)H] Bar^f_4 (7). The cationic olefin complexes are unreactive toward dioxygen or hydrogen peroxide. Since the success of the overall catalytic cycle depends on our ability to oxidize the olefin hydride complexes, a series of neutral olefin complexes of platinum(II) with monoanionic ligands (derivatives of pyrrole-2-carboxyaldehyde N-aryl imines) was prepared. Unfortunately, these are also stable to oxidation.

Model studies of Ziegler-Natta olefin polymerization using group 3 and group 4 metallocenes

Evidence for the stereochemical isomerization of a variety of ansa metallocene compounds is presented. For the scandocene allyl derivatives described here, we have established that the process is promoted by a variety of salts in both ether and hydrocarbon solvents and is not accelerated by light. A plausible mechanism based on an earlier proposal by Marks, et al., is offered as an explanation of this process. It involves coordination of anions and/or donor solvents to the metal center with cation assistance to encourage metalcyclopentadienyl bond heterolysis, rotation about the Si-Cp bond of the detached cyclopentadienide and recoordination of the opposite face. Our observations in some cases of thermodynamic racemic:meso ratios under the reaction conditions commonly used for the synthesis of the metallocene chlorides suggests that the interchange is faster than metallation, such that the composition of the reaction mixture is determined by thermodynamic, not kinetic, control in these cases.

Two new ansa-scandocene alkenyl compounds react with olefins resulting in the formation of η³-allyl complexes. Kinetics and labeling experiments indicate a tuck-in intermediate on the reaction pathway; in this intermediate the metal is bound to the carbon adjacent to the silyllinker in the rear of the metallocene wedge. In contrast, reaction of permethylscandocene alkenyl compounds with olefins results, almost exclusively, in vinylic C-H bond activation. It is proposed that relieving transition state steric interactions between the cyclopentadienyl rings and the olefin by either linking the rings together or using a larger lanthanide metal may allow for olefin coordination, stabilizing the transition state for allylic σ-bond metathesis.

A selectively isotopically labeled propylene, CH₂CD(¹³CH₃), was synthesized and its polymerization was carried out at low concentration in toluene solution using isospecific metallocene catalysts. Analysis of the NMR spectra (¹³C, ¹H, and ²H) of the resultant polymers revealed that the production of stereoerrors through chain epimerization proceeds exclusively by the tertiaryalkyl mechanism. Additionally, enantiofacial inversion of the terminally unsaturated polymer chain occurs by a non-dissociative process. The implications of these results on the mechanism of olefin polymerization with these catalysts is discussed.

I. The attenuation and dispersion of sound in a condensing medium. II. The flow of a gas-particle mixture downstream of a normal shock in a nozzle

I. The attenuation of sound due to particles suspended in a gas was first calculated by Sewell and later by Epstein in their classical works on the propagation of sound in a two-phase medium. In their work, and in more recent works which include calculations of sound dispersion, the calculations were made for systems in which there was no mass transfer between the two phases. In the present work, mass transfer between phases is included in the calculations.

The attenuation and dispersion of sound in a two-phase condensing medium are calculated as functions of frequency. The medium in which the sound propagates consists of a gaseous phase, a mixture of inert gas and condensable vapor, which contains condensable liquid droplets. The droplets, which interact with the gaseous phase through the interchange of momentum, energy, and mass (through evaporation and condensation), are treated from the continuum viewpoint. Limiting cases, for flow either frozen or in equilibrium with respect to the various exchange processes, help demonstrate the effects of mass transfer between phases. Included in the calculation is the effect of thermal relaxation within droplets. Pressure relaxation between the two phases is examined, but is not included as a contributing factor because it is of interest only at much higher frequencies than the other relaxation processes. The results for a system typical of sodium droplets in sodium vapor are compared to calculations in which there is no mass exchange between phases. It is found that the maximum attenuation is about 25 per cent greater and occurs at about one-half the frequency for the case which includes mass transfer, and that the dispersion at low frequencies is about 35 per cent greater. Results for different values of latent heat are compared.

II. In the flow of a gas-particle mixture through a nozzle, a normal shock may exist in the diverging section of the nozzle. In Marble’s calculation for a shock in a constant area duct, the shock was described as a usual gas-dynamic shock followed by a relaxation zone in which the gas and particles return to equilibrium. The thickness of this zone, which is the total shock thickness in the gas-particle mixture, is of the order of the relaxation distance for a particle in the gas. In a nozzle, the area may change significantly over this relaxation zone so that the solution for a constant area duct is no longer adequate to describe the flow. In the present work, an asymptotic solution, which accounts for the area change, is obtained for the flow of a gas-particle mixture downstream of the shock in a nozzle, under the assumption of small slip between the particles and gas. This amounts to the assumption that the shock thickness is small compared with the length of the nozzle. The shock solution, valid in the region near the shock, is matched to the well known small-slip solution, which is valid in the flow downstream of the shock, to obtain a composite solution valid for the entire flow region. The solution is applied to a conical nozzle. A discussion of methods of finding the location of a shock in a nozzle is included.

I. Site effects and exciton structure in molecular crystals - Benzene. II. The first and second triplet states of solid benzene

The effect of intermolecular coupling in molecular energy levels (electronic and vibrational) has been investigated in neat and isotopic mixed crystals of benzene. In the isotopic mixed crystals of C₆H₆, C₆H₅D, m-C₆H₄D₂, p-C₆H₄D₂, sym-C₆H₃D₃, C₆D₅H, and C₆D₆ in either a C₆H₆ or C₆D₆ host, the following phenomena have been observed and interpreted in terms of a refined Frenkel exciton theory: a) Site shifts; b) site group splittings of the degenerate ground state vibrations of C₆H₆, C₆D₆, and sym-C₆H₃D₃; c) the orientational effect for the isotopes without a trigonal axis in both the ¹B_2u electronic state and the ground state vibrations; d) intrasite Fermi resonance between molecular fundamentals due to the reduced symmetry of the crystal site; and e) intermolecular or intersite Fermi resonance between nearly degenerate states of the host and guest molecules. In the neat crystal experiments on the ground state vibrations it was possible to observe many of these phenomena in conjunction with and in addition to the exciton structure.

To theoretically interpret these diverse experimental data, the concepts of interchange symmetry, the ideal mixed crystal, and site wave functions have been developed and are presented in detail. In the interpretation of the exciton data the relative signs of the intermolecular coupling constants have been emphasized, and in the limit of the ideal mixed crystal a technique is discussed for locating the exciton band center or unobserved exciton components. A differentiation between static and dynamic interactions is made in the Frenkel limit which enables the concepts of site effects and exciton coupling to be sharpened. It is thus possible to treat the crystal induced effects in such a fashion as to make their similarities and differences quite apparent.

A calculation of the ground state vibrational phenomena (site shifts and splittings, orientational effects, and exciton structure) and of the crystal lattice modes has been carried out for these systems. This calculation serves as a test of the approximations of first order Frenkel theory and the atom-atom, pair wise interaction model for the intermolecular potentials. The general form of the potential employed was V(r) = Be^-Cr - A/r⁶ ; the force constants were obtained from the potential by assuming the atoms were undergoing simple harmonic motion.

In part II the location and identification of the benzene first and second triplet states (³B_1u and ³E_1u) is given.

Corpos distópicos: o dualismo grotesco na cinematografia cyberpunk

O presente trabalho pretende realizar o estudo sobre o modelo de corporalidade que foi difundido pela cinematografia recente inspirada pelo movimento cyberpunk. Marcados pela expressão de uma nova forma de dualismo que se funde com os pressupostos antes associados à chamada estética grotesca de um corpo pouco individualizado e aberto ao intercâmbio com o mundo externo e ao mesmo tempo bastante marcado por um novo tipo de conflito agora entre memória e organicidade. O texto discutirá também a contextualização social do movimento cyberpunk que pretendeu unificar a contracultura dos anos 60 com as discussões derivadas das novas tecnologias contemporâneas e seus efeitos nas novas concepções sobre corporeidade e conflito mente/corpo.

Teatro sombrio: o demônio em cena nos trópicos: o papel do teatro Anchietano no processo de colonização da América portuguesa no século XVI

O teatro anchietano, que articula a educação, a arte e a religião por meio de um interessante intercâmbio de signos, configurou-se como um dos mais relevantes instrumentos pedagógicos utilizados pela Companhia de Jesus na América Portuguesa durante o século XVI. Suas práticas discursivas acerca do Diabo e de seu séquito infernal tinham por objetivos, a partir da construção de uma pedagogia do medo, a promoção do catolicismo entre os indígenas e a adaptação desses povos à cultura euro-cristã, garantindo, desta forma, a viabilidade da colonização desses domínios ultramarinos pertencentes à coroa portuguesa. O processo de elaboração das representações culturais, característico dos encontros e confrontos entre os mundos europeu e indígena, a gestação de novos modelos de organização social e de valores, por meio do crivo da mestiçagem cultural, serão levados em conta para a análise da ação missionária jesuítica. Na presente dissertação analisaremos esses aspectos tendo por base o Auto de São Lourenço escrito pelo padre José de Anchieta.

Modelagem do padrão TISS por meio do enfoque dual da Fundação openEHR

Em 2005, a Agência Nacional de Saúde Suplementar (ANS) estabelece o padrão TISS (Troca de Informação na Saúde Suplementar), intercâmbio eletrônico obrigatório entre as operadoras de planos de saúde (cerca de 1500 registradas na ANS) e prestadores de serviços (cerca de 200 mil) sobre os eventos de assistência prestados aos beneficiários. O padrão TISS foi desenvolvido seguindo a estrutura do Comitê ISO/TC215 de padrões para informática em saúde e se divide em quatro partes: conteúdo e estrutura, que compreende a estrutura das guias em papel; representação de conceitos em saúde, que se refere às tabelas de domínio e vocabulários em saúde; comunicação, que contempla as mensagens eletrônicas; e segurança e privacidade, seguindo recomendação do Conselho Federal de Medicina (CFM). Para aprimorar sua metodologia de evolução, essa presente tese analisou o grau de interoperabilidade do padrão TISS segundo a norma ISO 20514 (ISO 20514, 2005) e a luz do modelo dual da Fundação openEHR, que propõe padrões abertos para arquitetura e estrutura do Registro Eletrônico de Saúde (RES). O modelo dual da Fundação openEHR é composto, no primeiro nível, por um modelo de referência genérico e, no segundo, por um modelo de arquétipos, onde se detalham os conceitos e atributos. Dois estudos foram realizados: o primeiro se refere a um conjunto de arquétipos demográficos elaborados como proposta de representação da informação demográfica em saúde, baseado no modelo de referência da Fundação openEHR. O segundo estudo propõe um modelo de referência genérico, como aprimoramento das especificações da Fundação openEHR, para representar o conceito de submissão de autorização e contas na saúde, assim como um conjunto de arquétipos. Por fim, uma nova arquitetura para construção do padrão TISS é proposta, tendo como base o modelo dual da Fundação openEHR e como horizonte a evolução para o RES centrado no paciente

Agrupamento espacial em robótica de enxame.

Os Sistemas Multi-Robôs proporcionam vantagens sobre um robô individual, quando da realização de uma tarefa com maiores velocidade, precisão e tolerância a falhas. Os estudos dos comportamentos sociais na natureza têm permitido desenvolver algoritmos bio-inspirados úteis na área da robótica de enxame. Seguindo instruções simples e repetitivas, grupos de robôs, fisicamente limitados, conseguem solucionar problemas complexos. Quando existem duas ou mais tarefas a serem realizadas e o conjunto de robôs é heterogêneo, é possível agrupá-los de acordo com as funcionalidades neles disponíveis. No caso em que o conjunto de robôs é homogêneo, o agrupamento pode ser realizado considerando a posição relativa do robô em relação a uma tarefa ou acrescentando alguma característica distintiva. Nesta dissertação, é proposta uma técnica de clusterização espacial baseada simplesmente na comunicação local de robôs. Por meio de troca de mensagens entre os robôs vizinhos, esta técnica permite formar grupos de robôs espacialmente próximos sem precisar movimentar os robôs. Baseando-se nos métodos de clusterização de fichas, a técnica proposta emprega a noção de fichas virtuais, que são chamadas de cargas, sendo que uma carga pode ser estática ou dinâmica. Se uma carga é estática permite determinar a classe à qual um robô pertence. Dependendo da quantidade e do peso das cargas disponíveis no sistema, os robôs intercambiam informações até alcançar uma disposição homogênea de cargas. Quando as cargas se tornam estacionárias, é calculada uma densidade que permite guiar aquelas que estão ainda em movimento. Durante as experiências, foi observado visualmente que as cargas com maior peso acabam se agrupando primeiro enquanto aquelas com menor peso continuam se deslocando no enxame, até que estas cargas formem faixas de densidades diferenciadas para cada classe, alcançando assim o objetivo final que é a clusterização dos robôs.

Folhas e curas em imagens: a circulação do conhecimento no Rio de Janeiro e na Paraíba

No estado do Rio de Janeiro e no agreste da Paraíba, há centenas de grupos de mulheres voluntárias comprometidas com o resgate de saberes tradicionais sobre cuidados com a saúde por meio de plantas medicinais. Esses grupos produzem preparações medicamentosas, suplementos alimentares, sabonetes e pomadas, vendidos a preço de custo ou doados. No Rio de Janeiro, a Rede Fitovida conta com mais de cem grupos espalhados por diversas regiões, promove eventos culturais e reivindica o reconhecimento de seus saberes como patrimônio imaterial. Já no agreste da Paraíba, as mulheres se organizam em comissões nos sindicatos de trabalhadores rurais do Polo Sindical da Borborema, a fim de promover a melhoria da qualidade de vida dos agricultores familiares locais. Elas promovem oficinas, encontros e visitas mútuas para difundir o uso de plantas medicinais, motivadas não só pela solidariedade, mas pela bandeira de não deixar esse conhecimento ser vencido pelo tempo. A proposta desta pesquisa é comparar as formas de transmissão de conhecimento de tais grupos, evidenciando, por consequência, os resultados decorrentes dessa ação. Para efeito de uma análise aprofundada.

Distribution and abundance of humpback whales (Megaptera novaeangliae) and other marine mammals off the northern Washington coast

We examined the summer distribution of marine mammals off the northern Washington coast based on six ship transect surveys conducted between 1995 and 2002, primarily from the NOAA ship McArthur. Additionally, small boat surveys were conducted in the same region between 1989 and 2002 to gather photographic identification data on humpback whales (Megaptera novaeangliae) and killer whales (Orcinus orca) to examine movements and population structure. In the six years of ship survey effort, 706 sightings of 15 marine mammal species were made. Humpback whales were the most common large cetacean species and were seen every year and a total of 232 sightings of 402 animals were recorded during ship surveys. Highest numbers were observed in 2002, when there were 79 sightings of 139 whales. Line-transect estimates for humpback whales indicated that about 100 humpback whales inhabited these waters each year between 1995 and 2000; in 2002, however, the estimate was 562 (CV= 0.21) whales. A total of 191 unique individuals were identified photographically and mark recapture estimates also indicated that the number of animals increased from under 100 to over 200 from 1995 to 2002. There was only limited interchange of humpback whales between this area and feeding areas off Oregon and California. Killer whales were also seen on every ship survey and represented all known ecotypes of the Pacific Northwest, including southern and northern residents, transients, and offshore-type killer whales. Dall’s porpoise (Phocoenoides dalli) were the most frequently sighted small cetacean; abundance was estimated at 181−291 individuals, except for 2002 when we observed dramatically higher numbers (876, CV= 0.30). Northern fur seals (Callorhinus ursinus) and elephant seals (Mirounga angustirostris) were the most common pinnipeds observed. There were clear habitat differences related to distance offshore and water depth for different species.

Growth of straight InAs-on-GaAs nanowire heterostructures.

One of the main motivations for the great interest in semiconductor nanowires is the possibility of easily growing advanced heterostructures that might be difficult or even impossible to achieve in thin films. For III-V semiconductor nanowires, axial heterostructures with an interchange of the group III element typically grow straight in only one interface direction. In the case of InAs-GaAs heterostructures, straight nanowire growth has been demonstrated for growth of GaAs on top of InAs, but so far never in the other direction. In this article, we demonstrate the growth of straight axial heterostructures of InAs on top of GaAs. The heterostructure interface is sharp and we observe a dependence on growth parameters closely related to crystal structure as well as a diameter dependence on straight nanowire growth. The results are discussed by means of accurate first principles calculations of the interfacial energies. In addition, the role of the gold seed particle, the effect of its composition at different stages during growth, and its size are discussed in relation to the results observed.

Bonding and correlation analysis of various SiCO isomers

The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.