Infrared spectral changes with crystallization in poly(vinylchloride): Correlations with X-ray and density data

The influence of crystallinity and stereoregularity on the infrared (IR) spectrum of atactic PVC in the solid state has been studied by many researchers [1-12]. Although the molecules in commercial PVC consist of both syndiotactic and isotactic sequences, the bulk polymer is not highly stereoregular, having approximately 50% syndiotacticity. Its infrared spectrum is different from that of highly syndiotactic PVC [3,5,7,9,10-12], particularly in the carbon-to-chlorine stretching region where there are three bands located at 610(615), 635, and 690 cm^?1. These three bands are known to be of complex origin, since each band consists of more than one absorption frequency and its relative intensity depends on the physical state or history of the specimen [3,5,7,9,10-12]. The spectrum in this region is most rigorously interpreted in terms of chain conformational structure, the spatial arrangement of the atoms around the C-C1 bond. Thus, while changes in absorbance intensities for the bands with history do not necessarily reflect changes in crystallinity, their history dependence renders these bands potentially useful as crystallinity indicators.     

Raman Scattering Tensors in Biological Molecules and Their Assemblies

INTRODUCTION

The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration.     

Investigating the mechanisms of diamond polishing using Raman spectroscopy

Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe₃O₄) and haematite (α-Fe₂O₃), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides.     

Benchmark calculations with correlated molecular wavefunctions. XIII. Potential energy curves for He2, Ne2 and Ar2 using correlation consistent basis sets through augmented sextuple zeta

The potential energy curves of the rare gas dimers He2, Ne2, and Ar2 have been computed using correlation consistent basis sets ranging from singly augmented aug-cc-pVDZ sets through triply augmented t-aug-cc-pV6Z sets, with the augmented sextuple basis sets being reported herein. Several methods for including electron correlation were investigated, namely Møller—Plesset perturbation theory (MP2, MP3 and MP4) and coupled cluster theory [CCSD and CCSD(T)]. For He2 CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 7.35 cm-1 (10.58 K), with an estimated complete basis set (CBS) limit of 7.40 cm-1 (10.65 K). The latter is smaller than the 'exact' well depth (Aziz, R. A., Janzen, A. R., and Moldover, M. R., 1995, Phys. Rev. Lett., 74, 1586) by about 0.2 cm-1 (0.35 K). The Ne2 well depth, computed with the CCSD(T)/d-aug-cc-pV6Z method, is 28.31 cm-1 and the estimated CBS limit is 28.4 cm-1, approximately 1 cm-1 smaller than the empirical potential of Aziz, R. A., and Slaman, M., J., 1989, Chem. Phys., 130, 187. Inclusion of core and core—valence correlation effects has a negligible effect on the Ne2 well depth, decreasing it by only 0.04 cm-1. For Ar2, CCSD(T)/d-aug-cc-pV6Z calculations yield a well depth of 96.2 cm-1. The corresponding HFDID potential of Aziz, R. A., 1993, J. chem. Phys., 99, 4518 predicts of De of 99.7 cm-1. Inclusion of core and core-valence effects in Ar2 increases the well depth and decreases the discrepancy by approximately 1 cm-1.     

Polymerizable derivatives of long-chain fatty acids. IV. Vinyl esters

Contrary to some published reports, the vinyl esters of saturated fatty acids polymerize readily and rapidly. Vinyl oleate, when present in excess of 5%, and oxygen exert marked retarding effects. Techniques are described for the free-radical-initiated polymerization of the vinyl esters of caprylic, capric, lauric, myristic, palmitic, and stearic acids in bulk, dispersion, solution, and emulsion. Some data are given for polymerization in the presence of chain-transfer agents, such as carbon tetrachloride, dodecylmercaptan, and ethylbenzene. Conditions are reported for obtaining degrees of polymerization from about 2 (when chain-transfer agents are employed) to 10,000 (weight average). The weight average degree of polymerization increases markedly as the conversion increases, particularly above 80%. Even up to extremely high conversions, soluble polymers are obtained in most cases. Solubility characteristics, transition point data, molecular weights (osmometric and light-scattering), and isolation and purification techniques are also reported.     

OPTIMAL FISH HARVESTING FOR A POPULATION MODELED BY A NONLINEAR PARABOLIC PARTIAL DIFFERENTIAL EQUATION

As the human population continues to grow, there is a need for better management of our natural resources in order for our planet to be able to produce enough to sustain us. One important resource we must consider is marine fish populations. We use the tool of optimal control to investigate harvesting strategies for maximizing yield of a fish population in a heterogeneous, finite domain. We determine whether these solutions include no‐take marine reserves as part of the optimal solution. The fishery stock is modeled using a nonlinear, parabolic partial differential equation with logistic growth, movement by diffusion and advection, and with Robin boundary conditions. The objective for the problem is to find the harvest rate that maximizes the discounted yield. Optimal harvesting strategies are found numerically.     

Understanding the inelastic electron-tunneling spectra of alkanedithiols on gold

We present results for a simulated inelastic electron-tunneling spectra (IETS) from calculations using the "gDFTB" code. The geometric and electronic structure is obtained from calculations using a local-basis density-functional scheme, and a nonequilibrium Green's function formalism is employed to deal with the transport aspects of the problem. The calculated spectrum of octanedithiol on gold(111) shows good agreement with experimental results and suggests further details in the assignment of such spectra. We show that some low-energy peaks, unassigned in the experimental spectrum, occur in a region where a number of molecular modes are predicted to be active, suggesting that these modes are the cause of the peaks rather than a matrix signal, as previously postulated. The simulations also reveal the qualitative nature of the processes dominating IETS. It is highly sensitive only to the vibrational motions that occur in the regions of the molecule where there is electron density in the low-voltage conduction channel. This result is illustrated with an examination of the predicted variation of IETS with binding site and alkane chain length.     

Hydrogen bonding and reactivity of water to azines in their S1 (n,π*) electronic excited states in the gas phase and in solution

A unified picture is presented of water interacting with pyridine, pyridazine, pyrimidine, and pyrazine on the S(1) manifold in both gas-phase dimers and in aqueous solution. As (n,π*) excitation to the S(1) state removes electrons from the ground-state hydrogen bond, this analysis provides fundamental understanding of excited-state hydrogen bonding. Traditional interpretations view the excitation as simply breaking hydrogen bonds to form dissociated molecular products, but reactive processes such as photohydrolysis and excited-state proton coupled electron transfer (PCET) are also possible. Here we review studies performed using equations-of-motion coupled-cluster theory (EOM-CCSD), multireference perturbation theory (CASPT2), time-dependent density-functional theory (TD-DFT), and excited-state Monte Carlo liquid simulations, adding new results from symmetry-adapted-cluster configuration interaction (SAC-CI) and TD-DFT calculations. Invariably, gas-phase molecular dimers are identified as stable local minima on the S(1) surface with energies less than those for dissociated molecular products. Lower-energy biradical PCET minima are also identified that could lead to ground-state recombination and hence molecular dissociation, dissociation into radicals or ions, or hydration reactions leading to ring cleavage. For pyridine.water, the calculated barriers to PCET are low, suggesting that this mechanism is responsible for fluorescence quenching of pyridine.water at low energies rather than accepted higher-energy Dewar-benzene based "channel three" process. Owing to (n,π*) excitation localization, much higher reaction barriers are predicted for the diazines, facilitating fluorescence in aqueous solution and predicting that the as yet unobserved fluorescence from pyridazine.water and pyrimidine.water should be observable. Liquid simulations based on the assumption that the solvent equilibrates on the fluorescence timescale quantitatively reproduce the observed spectral properties, with the degree of (n,π*) delocalization providing a critical controlling factor.     

The structure,thermodynamic properties and infrared spectra of liquid water and ice

Monte Carlo simulations are used, together with models of the intramolecular and intermolecular potential surfaces, to model liquid water and several phases of ice. Intramolecular relaxation makes important contributions to both thermodynamic and structural properties. A quantum local mode analysis of the Monte Carlo configurations is used to predict the density of states and infrared absorption intensities for the intramolecular bending and stretching vibrations. The large shifts from the gas phase OH stretch frequencies observed experimentally in the liquid and solid phases are due to anharmonic terms in the intramolecular surface rather than to harmonic intermolecular coupling. A significant contribution to observed changes in IR intensity on condensation arises from the large molecular polarisability.     

连续波锁模Pr3+:YLF激光器

本文报导了采用氩离子激光器来泵浦Pr³⁺:YLF晶体,应用声光调制器实现了主动锁模;同时应用振动─高反射平面镜也实现了被动锁模,两种锁模均得到了ps光脉冲.据作者了解这是这种晶体材料的第一次锁模运转.