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51.
A model of disordered medium is proposed to describe the monolayer adsorption isotherm on heterogeneous surfaces. The model
is based on the premise that adsorption medium consists of separate regions in each of which there is a permanent local equilibrium
constant, the character of the changes of which is determined by the disorder parameter of the medium.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 189–193, May–June, 2006. 相似文献
52.
53.
The equilibrium structures, binding energies, and vibrational spectra of the clusters CH3F(HF)1 n 3 and CH2F2(HF)1 n 3 have been investigated with the aid of large-scale ab initio calculations performed at the Møller–Plesset second-order level. In all complexes, a strong C–FH–F halogen–hydrogen bond is formed. For the cases n = 2 and n = 3, blue-shifting C–HF–H hydrogen bonds are formed additionally. Blue shifts are, however, encountered for all C–H stretching vibrations of the fluoromethanes in all complexes, whether they take part in a hydrogen bond or not, in particular also for n = 1. For the case n = 3, blue shifts of the ν(C–H) stretching vibrational modes larger than 50 cm−1 are predicted. As with the previously treated case of CHF3(HF)1 n 3 complexes (A. Karpfen, E. S. Kryachko, J. Phys. Chem. A 107 (2003) 9724), the typical blue-shifting properties are to a large degree determined by the presence of a strong C–FH–F halogen–hydrogen bond. Therefore, the term blue-shifted appears more appropriate for this class of complexes. Stretching the C–F bond of a fluoromethane by forming a halogen–hydrogen bond causes a shortening of all C–H bonds. The shortening of the C–H bonds is proportional to the stretching of the C–F bond. 相似文献
54.
Jean Bricmont Jean-Raymond Fontaine Eugene Speer 《Communications in Mathematical Physics》1982,86(3):337-362
We consider two models that are small perturbations of Gaussian or mean field models: the first one is a double well /44 — /22 perturbation of a massless Gaussian lattice field in the weak coupling limit (0, proportional to ). The other consists of a spin 1/2 Ising model with long-range Kac type interactions; the inverse range of the interaction, , is the small parameter. The second model is related to the first one via a sine-Gordon transformation. The lattice
d
has dimensiond3.In both cases we derive an asymptotic estimate to first order (in or 2) on the location of the critical point. Moreover, we prove bounds on the remainder of an expansion in or around the Gaussian or mean field critical points.The appendix, due to E. Speer, contains an extension of Weinberg's theorem on the divergence of Feynman graphs which is used in the proofs.Supported by NSF Grant # MCS 78-01885Supported by NSF Grant # PHY 78-15920 相似文献
55.
V. V. Kastron A. M. Kats G. Ya. Dubar R. M. Zolotoyabko 《Chemistry of Heterocyclic Compounds》1978,14(11):1236-1240
4,4-Disubstituted 1,4-dihydropyridines (I) are brominated with bromine in chloroform to give 2,6-bis(bromomethyl)-4,4-disubstituted 1,4-dihydropyridines (II), whereas 2,6-bis(dibromomethyl)-4,4-disubstituted 1,4-dihydropyridines (III) are obtained in the case of bromination of I in acetic acid. The bromine atoms in II and III are labile and readily undergo nucleophilic substitution.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1519–1524, November, 1978. 相似文献
56.
Eugene S. Kryachko 《International journal of quantum chemistry》1984,25(4):637-644
The relations based on an external one-electron operator V( r ) are examined from two view-points, i.e., from the Hohenberg–Kohn approach and the four-dimensional density concept introduced by Wilson and Frost, and extensively studied by Parr and Politzer. The object being to obtain, with the help of the Hellmann–Feynman theorem, new formulas for the energy of atoms and molecules, and to discuss the construction of the universal energy density functional on the basis of the four-dimensional density. 相似文献
57.
Lin JF Militzer B Struzhkin VV Gregoryanz E Hemley RJ Mao HK 《The Journal of chemical physics》2004,121(17):8423-8427
The melting curve of H(2)O has been measured by in situ Raman spectroscopy in an externally heated diamond anvil cell up to 22 GPa and 900 K. The Raman-active OH-stretching bands and the translational modes of H(2)O as well as optical observations are used to directly and reliably detect melting in ice VII. The observed melting temperatures are higher than previously reported x-ray measurements and significantly lower than recent laser-heating determinations. However, our results are in accord with earlier optical determinations. The frequencies and intensities of the OH-stretching peaks change significantly across the melting line while the translational mode disappears altogether in the liquid phase. The observed OH-stretching bands of liquid water at high pressure are very similar to those obtained in shock-wave Raman measurements. 相似文献
58.
Lindsay J. Webber Eugene Whang Edward C. De Fabo 《Photochemistry and photobiology》1997,66(4):484-492
Abstract— Ultraviolet B radiation (280-320 nm) can systemically suppress contact hypersensitivity (CHS), delayed type hypersensitivity (DTH) and tumor rejection responses in mice. Several models have been postulated for the initiation of this UVB-induced immune suppression and, although the complete mechanism is unclear, our early studies suggested that initiation is via the activation of a photoreceptor in the skin, identified as urocanic acid (UCA). Recent preliminary data from our laboratory and others indicated that UVA (320-400 nm)-emitting broadband sunlamps can also isomerize UCA but may not lead to immune suppression, in contrast to UVB-emitting sunlamps, which cause both effects. Although the reason for this inconsistency is unknown, the emission spectra of UVA lamps contain differing amounts of UVB, UVA-I (340-400 nm) and UVA-II (320-340 nm) from those of UVB sources. In this study we determined a detailed dose-response for the isomerization of UCA in mouse skin using the UVA-I, UVA-II and UVA-I+II wavelength ranges. The dose-response curves obtained were put on an equal energy basis by quantum correction and the possibility of wavelength interaction for this effect investigated. A simple additive wavelength interaction between UVA-I, UVA-II, and UVA-I+II was observed for trans-UCA photoisomerization. This result indicates that the failure of UVA-I, UVA-II or UVA-I+II radiation to induce immune suppression of the CHS response in an animal model is not due to complex wavelength interactions and/or the presence of an in vivo endogenous photosensitizer of UCA isomerization. Other factors, such as downstream blocking by UVA of the cis -UCA generated signal, may be involved. 相似文献
59.
Eugene P. Gross 《Journal of statistical physics》1981,25(4):585-604
We present a microscopic theory of the problem of finding the properties of a particle interacting with potentials located at random sites. The sites are governed by a general probability distribution. The starting point is the multiple scattering equations for the amplitude k
1|T
|k
2 in terms of the individual scattering amplitudes k
1|T
|k
2. We work with quantitiesA
defined by k
1|T
|k
2=k
1|T
|k
2exp[i(k
1–k
2)R
]. The theory is based on a splitting of the fundamental equation forA into equations for the mean A and the fluctuationsAA
. Neglect of the fluctuations yields the quasicrystalline approximation. We rearrange the equation forAA
to isolate the collective part of the fluctuations. We then make the simplest microscopic truncation which is thatAA
is a restricted two-body additive function of the site positions. With the contribution of the collective fluctuations, this yields results forA that are accurate to ordert
4.Work supported in part by the National Science Foundation under Contract No. NSF DMRWork supported in part by the National Science Foundation under Contract No. NSF DMR 相似文献
60.
Eugene L. Lawler 《Mathematical Programming》1975,9(1):31-56
LetM
1 = (E, 91),M
2 = (E, 92) be two matroids over the same set of elementsE, and with families of independent sets 91, 92. A setI 91 92 is said to be anintersection of the matroidsM
1,M
2. An important problem of combinatorial optimization is that of finding an optimal intersection ofM
1,M
2. In this paper three matroid intersection algorithms are presented. One algorithm computes an intersection containing a maximum number of elements. The other two algorithms compute intersections which are of maximum total weight, for a given weighting of the elements inE. One of these algorithms is primal-dual, being based on duality considerations of linear programming, and the other is primal. All three algorithms are based on the computation of an augmenting sequence of elements, a generalization of the notion of an augmenting path from network flow theory and matching theory. The running time of each algorithm is polynomial inm, the number of elements inE, and in the running times of subroutines for independence testing inM
1,M
2. The algorithms provide constructive proofs of various important theorems of matroid theory, such as the Matroid Intersection Duality Theorem and Edmonds' Matroid Polyhedral Intersection Theorem.Research sponsored by the Air Force Office of Scientific Research Grant 71-2076. 相似文献