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151.
Jean -Paul Malrieu 《Theoretical chemistry accounts》1982,62(2):163-174
Using the canonical problem of N separate electron pairs, theN dependence of approximate multireference CI schemes is analyzed. When the DCI is taken as multireference space, the second order Quasi Degenerate Many Body Perturbation Theory (QD(MB)PT) gives twice the expected correction, while the CIPSI algorithm gives 66% of it, and the MRDCI a vanishing part of it. A modified QDPT effective hamiltonian, and a combination of CIPSI and QDPT algorithms seem to give better trends. 相似文献
152.
InteractionbetweenMetalinMetalloEnzymeandSmallBiologicalMolecules¥HuJie-Han;ShuZan-Yong;TaoLi-Mei;ChengGuo-Bao(DalianInstitut... 相似文献
153.
The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied
by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using
isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant
was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO
chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was
found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular
surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions
stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions
were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and
Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing
a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both
surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function
of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius
produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation.
Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed
concerned the extent of the linear viscoelasticity region.
Received: 22 November 1996 Accepted: 24 March 1997 相似文献
154.
155.
The excess Gibb's free energy of mixing, GE, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The HE and GE values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and GE>HE. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A2B molecular species describes well (within±10 J-mol–1 in the worst case) the general dependence of HE on XA (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA2B reactions along with the enthalpies of formation of AB and A2B molecular species have been calculated. 相似文献
156.
Methane reforming by carbon dioxide has been studied over ultra-stable Ni catalysts. The catalyst was characterized by XRD, IR and TEM and temperature programmed hydrogenation. The nickel–magnesia solid solution catalyst containing low nickel has shown excellent stability (>3000 h) and no carbon deposition in the methane reforming by carbon dioxide. It was also found that the small nickel metal particle interaction with support surface is effective for the inhibition of carbon formation. 相似文献
157.
Tse-Chiang Chang 《中国化学会会志》1996,43(4):371-374
The homonuclear diatomic molecules are the simplest systems having both the σ framework and the lone pair orbitals na and b for investigating their through space and through bond interaction. The striking orbital energy order ng~ na+ nb > nn ~ na - nb has been accounted for by the through bond interaction. However, when the p-content in the lone pair orbitals na and nb decreases, one may have the reverse orbital energy order: ng < ng. A reverse orbital energy order has been found in F2 and Cl2, whose na and nb are almost pure s-type atomic orbitals. The reverse order also occurs in molecule N2 when the internuclear distance is larger man 1.5 Å. It is also found that the detail through space and through bond interaction and the eventual orbital energy order for ng and nu can be accounted for by the Fock operator within the localized molecular orbital space. 相似文献
158.
159.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
160.
Grell E. Lewitzki E. Schacht A. Stolz M. 《Journal of Thermal Analysis and Calorimetry》2004,77(2):471-481
Microcalorimetric titrations allow to recognize and investigate high-affinity ligand binding to Na,K-ATPase. Titrations with
the cardiac glycoside Ouabain, which acts as a specific inhibitor of the enzyme, have provided not only the thermodynamic
parameters of high-affinity binding with a stoichiometric coefficient of about 0.6 but also evidence for low-affinity binding
to the lipid. The marked enthalpic contribution of -95 kJ mol-1 at 298.2 K is partially compensated by a large negative entropy change, attributed to an increased interaction between water
and the protein. The calorimetric ADP and ATP titrations at 298.2 K are indicative of high-affinity nucleotide binding either
in 3 mM NaCl, 3 mM MgCl2 or at high ionic strength such as 120 mM choline chloride. However, no binding is detected in the buffer solution alone at
low ionic strength. The affinities for ADP and ATP are similar, around 106 M-1 and the stoichiometric coefficients are close to that of Ouabain binding. The exothermic binding of ADP is characterized
by a ΔH and ΔS value of -65 kJ mol-1 and -100 J mol-1 K-1, respectively. TheΔH value for ATP binding is larger than for ADP and is compensated by a larger, unfavorable ΔS value. This
leads to an enthalpy/entropy compensation, which could express that H-bond formation represents the major type of interaction.
As for Ouabain, the negative ΔS values that are also characteristic of nucleotide binding can indicate an increase of solvate
interaction with the protein due to a conformational transition occurring subsequent to the binding process. The resulting
binding constants are discussed with regard to the results of other studies employing different techniques. A molecular interaction
model for nucleotide binding is suggested.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献