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11.
We present a numerically exact calculation of rovibrational levels of a five-atom molecule. Two contracted basis Lanczos strategies are proposed. The first and preferred strategy is a two-stage contraction. Products of eigenfunctions of a four-dimensional (4D) stretch problem and eigenfunctions of 5D bend-rotation problems, one for each K, are used as basis functions for computing eigenfunctions and eigenvalues (for each K) of the Hamiltonian without the Coriolis coupling term, denoted H0. Finally, energy levels of the full Hamiltonian are calculated in a basis of the eigenfunctions of H0. The second strategy is a one-stage contraction in which energy levels of the full Hamiltonian are computed in the product contracted basis (without first computing eigenfunctions of H0). The two-stage contraction strategy, albeit more complicated, has the crucial advantage that it is trivial to parallelize the calculation so that the CPU and memory costs are independent of J. For the one-stage contraction strategy the CPU and memory costs of the difficult part of the calculation scale linearly with J. We use the polar coordinates associated with orthogonal Radau vectors and spherical harmonic type rovibrational basis functions. A parity-adapted rovibrational basis suitable for a five-atom molecule is proposed and employed to obtain bend-rotation eigenfunctions in the first step of both contraction methods. The effectiveness of the two methods is demonstrated by calculating a large number of converged J = 1 rovibrational levels of methane using a global potential energy surface. 相似文献
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Small organic molecules can be entrapped within inorganic crystalline materials during precipitation. The material has no apparent influence on solid-solid transition temperatures, but some of it is released during the transition.Detection of the escape is reproducible within 1°C and may be used for temperature calibration. More generally, the escape of the organic during chemical reactions could be used for many of the applications of emanation thermal analysis.In coupled systems such as DTA or TG with mass spectrometry, or other systems involving gas transport, the time delay of the system can be measured accurately.
The authors are grateful to the National Science Foundation for support of parts of this work through institutional and research grants and to the Goodyear Tire and Rubber Company for use of the Chromatograph and other facilities. 相似文献
Zusammenfassung Kleine organische Moleküle können während der Fällung in anorganische kristalline Substanzen eingeschlossen werden. Die Substanz hat keine scheinbare Wirkung auf Fest-Fest-Übergangstemperaturen, doch wird ein Teil derselben während des Überganges freigesetzt. Der Nachweis der freigesetzten Substanz ist innerhalb von 1°C reproduzierbar und kann zur Temperatureichung eingesetzt werden. Verallgemeinert könnte das Entfliehen organischer Substanzen im Laufe chemischer Reaktionen bei vielen Anwendungen der Emanations-Thermalanalyse eingesetzt werden. In gekoppelten Systemen, wie z.B. DTA oder TG mit Massenspektrometrie, oder andere Systeme mit Gastransport, kann die Verzögerung des Systems genau gemessen werden.
Résumé De petites molécules organiques peuvent se trouver incluses dans des substances inorganiques cristallines, au moment de la précipitation. Les températures de transition solidesolide ne s'en trouvent apparemment pas affectées mais une partie de ces molécules incluses peut être éliminée pendant la transition. La détection du matériau qui s'échappe est reproductible à 1°C près et se prête à l'étalonnage de la température. En termes plus généraux, le départ de la substance organique au cours des réactions chimiques peut être utilisé pour de nombreuses applications de l'analyse thermique d'émanation. Dans le cas de techniques associées, comme l'ATD ou la TG avec la spectrométrie de masse, ou encore d'autres techniques avec transport de gaz, on peut mesurer exactement le temps de réponse du système.
. —, . 1°, . . , , - , , , .
The authors are grateful to the National Science Foundation for support of parts of this work through institutional and research grants and to the Goodyear Tire and Rubber Company for use of the Chromatograph and other facilities. 相似文献
15.
Marshall Ledbetter John Cuculo Paul Tucker 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1435-1459
The structure and properties of a poly(ethylene terephthalate) extrudate, prepared by converging flow and high pressure, were examined. Relatively high levels of crystallinity and orientation were produced by the combination of an orienting flow and high-pressure quench. The fine structure was examined in detail by x-ray diffraction, negative staining–transmission electron microscopy, and amine etching–gel permeation chromatography. The morphology was directly relatable to this unique preparative technique. Modulus was determined by a compressive Rheovibron technique. Low shrinkage and the compressive modulus were related to the structure in the development of a structural model. 相似文献
16.
Penfold J Tucker I Thomas RK 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11757-11764
This paper describes how the cationic polyelectrolyte, polyDMDAAC (poly(dimethyl diallylammonium chloride)), is used to manipulate the adsorption of the anionic surfactant SDS and the mixed ionic/nonionic surfactant mixture of SDS (sodium dodecyl sulfate)/C(12)E(6) (monododecyl hexaethylene glycol) onto the surface of hydrophilic silica. The deposition of a thin robust polymer layer from a dilute polymer/surfactant solution promotes SDS adsorption and substantially modifies the adsorption of SDS/C(12)E(6) mixtures in favor of a surface relatively rich in SDS compared to the solution composition. Different deposition conditions for the polyDMDAAC layer are discussed. In particular, at higher solution polymer concentrations and in the presence of 1 M NaCl, a thicker polymer layer is deposited and the reversibility of the surfactant adsorption is significantly altered. 相似文献
17.
Penfold J Tucker I Thomas RK Zhang J 《Langmuir : the ACS journal of surfaces and colloids》2005,21(22):10061-10073
Neutron reflectivity and surface tension have been used to characterize the adsorption of the polyelectrolyte/ionic surfactant mixture of poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) at the air-water interface. The surface tension behavior and adsorption patterns show a strong dependence upon the solution pH. However, the SDS adsorption at the interface is unexpectedly most pronounced when the pH is high (when the polymer is essentially a neutral polymer) and when the polymer architecture is branched rather than linear. For both the branched and the linear PEI polymer/surfactant complex formation results in a significant enhancement of the amount of SDS at the interface, down to surfactant concentrations approximately 10(-6) M. For the branched PEI a transition from a monolayer to a multilayer adsorption is observed, which depends on surfactant concentration and pH. In contrast, for the linear polymer, only monolayer adsorption is observed. This substantial increase in the surface activity of SDS by complexation with PEI results in spontaneous emulsification of hexadecane in water and the efficient wetting of hydrophobic substrates such as Teflon. In regions close to charge neutralization the multilayer adsorption is accentuated, and more extensively ordered structures, giving rise to Bragg peaks in the reflectivity data, are evident. 相似文献
18.
Bruce S. Dien Nick Nagle Kevin B. Hicks Vijay Singh Robert A. Moreau Melvin P. Tucker Nancy N. Nichols David B. Johnston Michael A. Cotta Quang Nguyen Rodney J. Bothast 《Applied biochemistry and biotechnology》2004,115(1-3):937-949
Approximately 9% of the 9.7 billion bushels of corn harvested in the United States was used for fuel ethanol production in 2002, half of which was prepared for fermentation by dry grinding. The University of Illinois has developed a modified dry grind process that allows recovery of the fiber fractions prior to fermentation. We report here on conversion of this fiber (Quick Fiber [QF]) to ethanol. QF was analyzed and found to contain 32%wt glucans and 65%wt total carbohydrates. QF was pretreated with dilute acid and converted into ethanol using either ethanologenic Escherichia coli strain FBR5 or Saccharomyces cerevisiae. For the bacterial fermentation the liquid fraction was fermented, and for the yeast fermentation both liquid and solids were fermented. For the bacterial fermentation, the final ethanol concentration was 30 g/L, a yield of 0.44 g ethanol/g of sugar(s) initially present in the hydrolysate, which is 85% of the theoretical yield. The ethanol yield with yeast was 0.096 gal/bu of processed corn assuming a QF yield of 3.04 lb/bu. The residuals from the fermentations were also evaluated as a source of corn fiber oil, which has value as a nutraceutical. Corn fiber oil yields were 8.28%wt for solids recovered following prtetreatment. 相似文献
19.
S. D. Christian E. E. Tucker J. F. Scamehorn H. Uchiyama 《Colloid and polymer science》1994,272(6):745-754
The interpretation of intramicellar solubilization data obtained from semi-equilibrium dialysis (SED) experiments is described, and methods are presented for determining equilibrium constants for the solubilization of organic species by aqueous surfactant solutions as well as activity coefficients of both the organic solute and the surfactant within the micelle. The solubilization equilibrium constant of an organic solute in an aqueous micellar solution (K) is defined as the ratio of the mole fraction of organic solute in the micellar pseudophase (X) to the concentration of the unsolubilized monomeric organic solute in the aqueous phase (c
0). Expressions compatible with the Gibbs-Duhem equation are used to represent the concentration dependence of activity coefficients of both the solubilizate and surfactant in the micellar pseudophase; the analysis leads to calculated values of the concentrations of free and intramicellar surfactant and organic solute in both compartments of the equilibrium dialysis cell. Solubilization equilibrium constants for many amphiphiles are well correlated by the simple expressionK=K
0(1-BX)2, whereB is an empirical constant andK
0 is the limiting value ofK asX approaches 0. 相似文献
20.