I. Electronic states of heavily-doped molecular crystals--naphthalene. I. Theoretical. II. Experimental. II. Lowest singlet and triplet excited states of pyrazine

PART I

The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.

PART II

The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h₈ and d₈, (2) naphthalene--h₈ and αd₄, and (3) naphthalene--h₈ and βd₁, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.

PART III

The phosphorescence, fluorescence and absorption spectra of pyrazine-h₄ and d₄ have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h₄ in d₄ were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.

The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as ¹B_3u ← ¹A_1g. The forbidden component ¹B_2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.

The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as ³B_3u.

The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v_6a exists. Under the high resolution attainable in our work, the supposed v_6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v_9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d₄ spectrum, but a band of 1207 cm^-1 in the pyrazine in benzene system and 1231 cm^-1 in the mixed crystal system is also observed. This band is assigned as 2v_6b and of a_1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v_6a and v_9a band.

To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.

一种新型光纤光栅无啁啾调谐方法

分析了基于弹性梁的光纤光栅调谐原理，引入了轴向直变传递系数的概念，提出利用部分纯弯曲调谐方法，可实现光纤光栅宽带无啁嗽调谐。在实验中，利用部分纯弯曲调谐法，获得了20．1nm的光纤光栅无啁嗽调谐范围，调谐线性拟合度为0．9996，调谐过程中光栅反射谱的3dB带宽变化小于0．07nm，峰值反射率变化小于0．2dB，基本无啁嗽现象产生，实验结果和理论分析一致。

平面弯曲波导耦合器的特性分析

根据耦合模理论和弯曲波导耦合器的结构特点,对平面弯曲波导耦合器的特性进行了分析,结果表明弯曲波导耦合器的弯曲半径和最小间距两个可调变量,增加了波导器件设计的灵活性;同时由于等效耦合长度的调制作用使得弯曲波导耦合器在波分复用/解复用中比平行直波导耦合器具有更大的复用带宽;分析了弯曲半径和最小间距对弯曲波导耦合器复用带宽的影响,为实际波导器件的设计制作提供了一定的理论依据.

Strength of thin-walled elliptical cylinders supported at the minor axis

In this investigation it was found that the instability failure of curved sheet is nearly independent of the type of loading and is primarily a function of the maximum stress, radius-thickness ration and modulus of elasticity. A method of correlating the critical stress of thin sheet under several different types of loading is given. An explanation for the experimental critical stress of thin walled cylinders under bending being greater than that for pure compression is given. The strength of unstiffened thin walled circular nose sections under pure bending was found to be controlled by local instability of the section, rather than a large scale instability. The equation of local instability of curved sheet gives values which are in fair agreement with those found experimentally.

The strength of elliptical cylinders supported at the minor axis under bending plus shear loads is governed primarily by the bending strength, and is little effected by the sheer force unless the amount of shear is quite large with respect to the moment. The effect of increasing the amount of elliptically greatly reduces the bending and shear strength of nose sections. Under torsional loads the stress at buckling falls off as the ration of the major to minor axis increases but the failure stress decreases at a slower rate than the buckling stress. The length effect of semi-circular sections under torsion is similar to that of a circular tube, and can be obtained by Donnell's theoretical equation.

Transmission matrices and lumped parameter models for continuous systems

The use of transmission matrices and lumped parameter models for describing continuous systems is the subject of this study. Non-uniform continuous systems which play important roles in practical vibration problems, e.g., torsional oscillations in bars, transverse bending vibrations of beams, etc., are of primary importance.

A new approach for deriving closed form transmission matrices is applied to several classes of non-uniform continuous segments of one dimensional and beam systems. A power series expansion method is presented for determining approximate transmission matrices of any order for segments of non-uniform systems whose solutions cannot be found in closed form. This direct series method is shown to give results comparable to those of the improved lumped parameter models for one dimensional systems.

Four types of lumped parameter models are evaluated on the basis of the uniform continuous one dimensional system by comparing the behavior of the frequency root errors. The lumped parameter models which are based upon a close fit to the low frequency approximation of the exact transmission matrix, at the segment level, are shown to be superior. On this basis an improved lumped parameter model is recommended for approximating non-uniform segments. This new model is compared to a uniform segment approximation and error curves are presented for systems whose areas very quadratically and linearly. The effect of varying segment lengths is investigated for one dimensional systems and results indicate very little improvement in comparison to the use of equal length segments. For purposes of completeness, a brief summary of various lumped parameter models and other techniques which have previously been used to approximate the uniform Bernoulli-Euler beam is a given.

I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

Characteristics of 980/1550 nm WDM coupler based on planar curved waveguides

A wavelength division multiplexer (WDM) for 980/1550 nm based on planar curved waveguide coupler (CWC) is proposed. Compared with conventional parallel straight waveguide coupler (SWC), this structure has more flexibility with two variable parameters of bending radius R and minimum edge-to-edge spacing do, which are the two main parameters for the splitting ratio of coupler and decrease the complexity of device design and fabrication. Based on coupled mode theory (CMT) and waveguide theory, R and do of the WDM CWC are designed to be R = 13.28 m and d(0) = 4.39 mu m. The contrast ratio (CR) and insertion loss (IL) for 980 and 1550 nm are CR1 = 24.62 dB, CR2 = 24.56 dB and IL1 = 0.014 dB, IL2 = 0.015 dB, respectively. The 3D beam propagation method (BPM) is used to verify the validity of the design result. The influence of R and d(0) variations on the device performance is analyzed. For CR > 20 dB, the variation ranges of R and d(0) should be within -0.10 to +0.44 m and -0.05 to + 0.02 mu m, respectively. (c) 2006 Elsevier GmbH. All rights reserved.

Influence of the second cladding on the properties of four-layer large flattened mode fibers

A theoretical method to analyze four-layer large flattened mode (LFM) fibers is presented. The influence of the second cladding on the properties of four-layer LFM fiber, including the fundamental and higher-order modal fields, effective area, bending loss, and dispersion, are studied by comparison. At the same time, the reasons for the different characteristics are considered. The obtained results indicate that the effective area of the four-layer LFM fiber is about 1.6 times larger than that of the conventional standard step-index fiber and the fibers have better bend-induced filtering ability than three-layer LFM fibers. (C) 2007 Society of Photo-Optical Instrumentation Engineers.

Design and analysis of a kind of large flattened mode optical fibre

In this paper, a refractive index pro. le design enabling us to obtain a. at modal field around the fibre centre is investigated. The theoretical approach for designing such multilayer large flattened mode (LFM) optical fibres is presented. A comparison is made between the properties of a three-layer LFM structure and a standard step-index pro. le with the same core size. The obtained results indicate that the effective area of the LFM fibre is about twice as large as that of the standard step-index fibre, but the LFM fibre has less effective ability to filter out the higher order modes than the standard step-index fibre with the same bending radius.

Influence of the second cladding on the properties of four-layer large flattened mode fibers

A theoretical method to analyze four-layer large flattened mode (LFM) fibers is presented. The influence of the second cladding on the properties of four-layer LFM fiber, including the fundamental and higher-order modal fields, effective area, bending loss, and dispersion, are studied by comparison. At the same time, the reasons for the different characteristics are considered. The obtained results indicate that the effective area of the four-layer LFM fiber is about 1.6 times larger than that of the conventional standard step-index fiber and the fibers have better bend-induced filtering ability than three-layer LFM fibers. (C) 2007 Society of Photo-Optical Instrumentation Engineers.

Design guidelines and characteristics for a kind of four-layer large flattened mode fibers

A theoretical method to analyze a kind of four-layer large flattened mode (LFM) fibers is presented. The properties of the fiber, including the fundamental and higher-order modal fields, effective area and bending loss are discussed by comparison. At the same time, the reasons for the different characteristics are considered. The obtained results indicate that the effective area of the four-layer LFM fiber is about 1.3 times larger than that of the conventional standard step-index fiber and the fiber can suppress the higher-order modes via bending effectively. The four-layer LFM fiber has less efficient bend-induced filtering ability than the conventional step-index fiber; however, it has more efficient filtering ability than the three-layer LFM fiber. (C) 2007 Elsevier GmbH. All rights reserved.

弯曲直径对多模光纤激光器输出性能的影响

大模场面积(LMA)多模光纤激光器的输出性能与光纤的弯曲程度有关。为研究两者之间的关系，在光纤不同弯曲直径下，对多模光纤激光器的输出性能进行了实验测量和理论计算。采用刀口法测量了不同弯曲直径下的激光光束质量因子M2，并对每种情况下光纤激光器的斜率效率进行了测量。光纤弯曲直径分别为285 mm,195 mm和130 mm时，多模光纤激光器光束质量因子M2为2.88,1.82和1.67，斜率效率为39%,35%和34%。另外，对于实验所采用的大模场面积多模光纤，理论计算了各模式损耗与光纤弯曲直径的关系。

Influência da variação da intensidade de luz, para uma mesma exposição radiante, no comportamento mecânico de uma resina convencional e de uma resina de baixa contração

O presente estudo teve como objetivo avaliar a influência da variação da intensidade de luz, para uma mesma exposição radiante, na resistência à flexão, na microdureza e na resistência à tração diametral de uma resina convencional e de uma resina de baixa contração. Para a confecção dos corpos de prova foram utilizadas as resinas Filtek Z250 (3M ESPE) e Filtek P90 LS (3M ESPE) fotoativadas por meio dos seguintes protocolos: Convencional (400mW/cm por 60 s), Média intensidade (700mW/cm por 34 s) e Alta intensidade (950mW/cm por 26 s). Todos os corpos de prova receberam a mesma exposição radiante de 24J/cm. A resistência à flexão foi avaliada por meio do ensaio de flexão três pontos. Para este ensaio foram confeccionados trinta corpos de prova de cada material (n=10) com dimensões de 10mm x 2mm x 1mm. A avaliação da microdureza Knoop foi obtida a partir de seis discos de cada resina com 5mm de diâmetro por 2mm de espessura (n=2), sendo realizadas cinco indentações em cada espécime. Trinta corpos de prova cílindricos de cada compósito (n=10) com 3mm de diâmetro por 6mm de altura foram confeccionados para a realização do teste de tração diametral. A análise estatística dos resultados obtidos foi realizada por meio do teste de análise de variância (ANOVA) e do teste de múltiplas comparações de Tukey (p < 0.05). A resistência à flexão da resina P90 não foi influenciada de forma significativa pelas diferentes formas de ativação, enquanto a Z250 obteve resultados significantemente maiores para o protocolo de alta intensidade em relação ao convencional. Em todas as intensidades de luz, os resultados da Z250 foram significativamente maiores que os da P90. A microdureza da resina P90 foi estatisticamente maior para o grupo de média intensidade em relação aos outros, já a Z250 não obteve resultados com diferença estatística em relação às formas de ativação. Para a mesma irradiância, a Z250 obteve maiores valores de microdureza do que a P90, com exceção para o protocolo de média intensidade em que não houve diferença estatística entre os materiais. Os valores de resistência à tração não foram influenciados de forma significativa nem pelas diferentes intensidades de luz, nem pelos materiais utilizados. A influência da variação da intensidade de luz depende do tipo de compósito utilizado e da propriedade mecânica avaliada.

Avaliação in vitro do efeito da incorporação de clorexidina nas propriedades físicas e na atividade antibacteriana de resinas acrílicas autopolimerizáveis

Objetivo. O objetivo do presente estudo foi avaliar o efeito da incorporação de diacetato de clorexidina (CDA), em diferentes concentrações e tempos de armazenamento, nas propriedades físicas e na atividade antibacteriana de resinas acrílicas, utilizadas na confecção de coroas e pontes provisórias. Métodos. Fase I: Foram confeccionados 150 corpos de prova retangulares (3,0 mm X 10 mm X 64 mm), de acordo com a norma ISO 1567 e 150 corpos de prova quadrados (10 mm X 10 mm X 2,0 mm), utilizando-se duas resinas acrílicas autopolimerizáveis, Duralay (Reliance Dental Mfg. Co.) e Dencor (Clássico). Os corpos de prova foram distribuídos em 30 grupos (n=10/grupo) de acordo com a concentração de CDA incorporada às resinas (p/p) (A) 0%, (B) 1%, (C) 2%, (D) 4%, (E) 5%, em função do tempo de armazenamento em água destilada, a 37C (T0 2h, T1 7 dias, T2 30 dias). Foram realizados os ensaios de microdureza Knoop, em microdurômetro Micromet 5104, Buehler (N), rugosidade superficial (Ra), em rugosímetro digital Mitutoyo Surftest SJ-201 (n=5) e resistência à flexão em três pontos (MPa), em uma máquina de ensaio universal EMIC MF 200 DL (n=5). Fase II: Adicionalmente, a atividade antibacteriana dos materiais sobre Streptococcus mutans foi determinada através da realização de testes de difusão em meio BHI, sendo para isso confeccionados 30 corpos de prova em forma de disco (12 mm X 3,0 mm) com as mesmas 5 concentrações (n=3/grupo). Os resultados foram tabulados e submetidos à análise estatística three-way ANOVA (Fase I) e two-way ANOVA (Fase II). Resultados. ANOVA mostrou que a adição de CDA não provocou alteração significativa na resistência à flexão dos materiais testados. A resistência à flexão é inversamente proporcional ao tempo para a resina Dencor e diretamente proporcional ao tempo para a resina Duralay. Houve aumento da microdureza com o acréscimo de CDA ao material Dencor com relação ao grupo controle, enquanto que no material Duralay a CDA não interferiu significativamente nesta propriedade. A rugosidade superficial aumentou significativamente (p<0,001) com o tempo e com o aumento da concentração de clorexidina na resina Dencor e não provocou alteração significativa em Duralay. Os testes de difusão em ágar demonstraram atividade antimicrobiana significativa (p<0,05) em todos os grupos, quando comparados ao grupo-controle. A inibição ao crescimento de Streptococcus mutans foi maior com o aumento da concentração desta substância. A resina Dencor apresentou maior halo de inibição do que a resina Duralay. Conclusões. Os resultados deste estudo sugerem que a incorporação de clorexidina aos materiais testados exibiu efeito antibacteriano contra S. mutans, sem contudo afetar de maneira crítica as propriedades físicas avaliadas.

Modelagem numérica de elementos tracionados em aço inoxidável com parafusos defasados

Atualmente, a utilização do aço inoxidável em elementos estruturais é considerada uma solução cara para os problemas da engenharia estrutural. Todavia, mudanças de atitudes dentro da construção civil, uma transição global para um desenvolvimento sustentável e redução em impactos ambientais têm seguramente provocado um aumento na utilização do aço inoxidável. As normas de projeto de aço inoxidável atuais são, em grande parte, baseadas em analogias assumidas com o comportamento de estruturas desenvolvidas com aço carbono. Todavia, o aço inoxidável apresenta quatro curvas não-lineares tensão versus deformação (tensão e compressão, paralela e perpendicular a laminação do material), sem patamar de escoamento e região de encruamento claramente definidos, modificando assim, o comportamento global das estruturas que o utilizam. Em elementos estruturais submetidos a forças axiais de tração, a ruptura da seção líquida representa um dos estados limites últimos a serem verificados. Com o objetivo de se avaliar a resistência a tração de elementos estruturais aparafusados em aço inoxidável S304, este trabalho apresenta um modelo numérico baseado no método dos elementos finitos através do programa Ansys (versão 11). A não-linearidade do material foi considerada através do critério de plastificação de Von Mises e curvas tensão versus deformação verdadeira. A não-linearidade geométrica foi introduzida no modelo através da Formulação de Lagrange atualizado. O modelo numérico foi calibrado com resultados experimentais obtidos em ensaios de laboratório, a partir de ligações aparafusadas alternadas rígidas, onde não se ocorre nenhuma rotação entre os membros, transferindo nenhum momento fletor, apenas esforço normal e cisalhante.