排序方式: 共有33条查询结果,搜索用时 0 毫秒
1.
The Monte Carlo computer simulation technique of classical statistical mechanics is employed to determine the structure and thermodynamics of binary microclusters of Lennard-Jones atoms as a function of cluster size, composition and temperature. Further, amorphous microclusters are prepared by a Monte Carlo quench, and their structural properties are examined. The properties of interest include the internal energy, instantaneous “snapshot” pictures of the microcluster's atomic configuration, and the single-particle and pair distribution functions. The Lennard-Jones potential parameters are chosen to model Ar13, Ar7Kr6, Ar36Kr19 and Ar19Kr36, as well as to crudely model the bimetallic clusters of Cu19Ni36, Cu19Ru36 and Cu19Os36. A large variety of interesting features associated with these systems are described. 相似文献
2.
Gwenaelle Pound Zaskia Eksteen Rueben Pfukwa Jean M. McKenzie Ronald F. M. Lange Bert Klumperman 《Journal of polymer science. Part A, Polymer chemistry》2008,46(19):6575-6593
The monomer N‐vinylpyrrolidone (NVP) undergoes side reactions in the presence of R group functional xanthates and impurities. The fate of the monomer NVP and a selection of six O‐ethyl xanthates during xanthate‐mediated polymerization were studied via NMR spectroscopy. A high number of by‐products were identified. Significant side reactions affecting NVP include the formation of an unsaturated dimer and hydration products in bulk or in solution in C6D6. In addition, the xanthate adjacent to a NVP unit was found to undergo elimination at moderate temperature (60–70 °C), resulting in unsaturated species and the formation of new xanthate species. The presence of the chlorinated compound α‐chlorophenyl acetic acid, ethyl ester, a precursor in the synthesis of the xanthate S‐(2‐ethyl phenylacetate) O‐ethyl xanthate, resulted in a dramatic increase in the rate of side reactions such as unsaturated dimer formation and a high ratio of unsaturated chain ends. The conditions for the occurrence of such side reactions are discussed in this article, with relevance to increasing the control over the polymerization kinetics, endgroup functionality, and control over the molar mass distribution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6575–6593, 2008 相似文献
3.
4.
Pound GJ Pletnev AA Fang X Pletneva EV 《Chemical communications (Cambridge, England)》2011,47(20):5714-5716
A new thiol-specific reagent introduces a small bis(methylamino)terephthalic acid fluorophore into proteins. The noninvasive probe with distinct spectroscopic properties offers many advantages for protein labeling, purification, and mechanistic work promising to serve as a powerful tool in studies of protein folding and heme redox reactions. 相似文献
5.
6.
An Einstein model is used to calculate the internal vibrational free energy of approximately spherical fcc crystallites as a function of crystallite size at T/θ = 1. It is found that the free energy per surface atom does not become convergent until a size of about 3 × 107 atoms is reached. The excess free energy at convergence is used to define the macroscopic surface tension for use in the capillarity approximation. The internal free energy of microcrystallites containing of the order of 100 atoms is fortuitously well described by the capillarity approximation. A good estimate of the total free energy of the microcrystallite (nucleus) is obtained from the capillarity approximation only by adding the contributions from free translation and rotation and the replacement partition function. 相似文献
7.
We employ the Monte Carlo simulation method of classical statistical mechanics to study the structure and energetics of the crystal/amorphous interface. The interface is found to be approximately four atomic layers thick and provides good bonding between the amorphous and crystalline phases. 相似文献
8.
The theory of homogeneous nucleation of liquid drops in supersaturated vapours is reviewed. A new kinetic treatment which accounts for the heating of the growing clusters due to the latent heat of condensation is presented, and the irreversible thermodynamics of non-isothermal nucleation discussed. It is found that growing clusters are generally colder than the surrounding vapour during their sub-critical growth period. Time dependent nucleation is discussed and a simple estimate for the time-lag in establishing the steady state is given. The nucleation in cloud chambers expanding with constant speed is discussed in detail, and the number of droplets formed and their final mean size is calculated as a function of the terminal expansion ratio. Re-evaporation of nucleated clusters is discussed. Numerical results are given for a number of typical situations in experiments on water-vapour. These results for the nucleation rate as corrected by Lothe and Pound predict much lower ‘critical’ expansion ratios than indicated by the limited experimental data available, even when the non-isothermal theory is used. To restore agreement between theory and experiments the surface tension for small droplets (?100 molecules) could be increased some 15% above that of the bulk liquid, or the pre-exponential in the nucleation rate could be decreased by some 10?15. This latter expedient roughly corresponds to use of the ‘classical’ instead of the Lothe-Pound nucleation rate. These two alterations would, however, affect the theoretical curves in different manners and careful experiments could possibly distinguish between them. 相似文献
9.
Pound G McKenzie JM Lange RF Klumperman B 《Chemical communications (Cambridge, England)》2008,(27):3193-3195
Aldehyde omega-endfunctional poly(N-vinylpyrrolidone) was synthesised via quantitative conversion of a xanthate endfunctional precursor obtained via RAFT-mediated polymerisation. 相似文献
10.
Lavison G Bertoncini F Thiébaut D Beziau JF Carrazé B Valette P Duteurtre X 《Journal of chromatography. A》2007,1161(1-2):300-307
Car lubricant additives are added to mineral or synthetic base stocks to improve viscosity and resistance to oxidation of the lubricant and to limit wear of engines. Their total amount in the commercial lubricant varies from a few percents to 20-25%. As they belong to various chemical classes and are added to a very complex medium, the base stock, their detailed chromatographic analysis is very difficult and time consuming as it should involve sample treatment and preparative scale separations in order to simplify the sample. The aim of this work is to determine the feasibility of the separation of low molecular weight lubricant additives using various packed columns with pure CO(2) as a mobile phase to enable implementation of flame ionisation detection as universal detector. This is part of a hypernated system including more sophisticated specific detectors, such as AED, FTIR or MS to obtain detailed structural information of compounds. This paper is devoted to the comparison of some stationary phases supposed to provide hydrocarbon group type separation (silica and normal phase) or separations on alkyl-bonded silica in non-aqueous mode of some selected classes of additives in test mixtures or in base stocks. Adsorption chromatography allows partial separation of additives from the base stocks while the direct elution of test additives can only be obtained on reversed phase supports having a very efficient silanol group protection so the interaction of the more polar compounds is much reduced. A two-dimensional scheme of analysis is also described. It combines adsorption chromatography to separate most of the polar additives from the base stock and alkyl-bonded silica for more detailed separation of the additives. However, overlapping between groups of compounds and the lack of resolution between some additives and the base stock should be addressed by the implementing of selective detectors. 相似文献