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81.
Reactions are described that employ 90°-1,3-butadiene as a reference structure for the evaluation of the stabilization energyof the benzenoid and other cyclic conjugated hydrocarbons. The unique benefits of this rotamer of butadiene as a reference molecule within the homodesmotic conceptual framework are discussed. Experimental stabilization energies are presented for a number of cyclic hydrocarbons. 相似文献
82.
Mui C Senosiain JP Musgrave CB 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7604-7609
We use density functional theory to investigate the surface chemistry of initial oxidation and hydroxylation of the Ge(100)-2 x 1 surface by water and hydrogen peroxide. Comparison of the reaction of water on the Si(100)-2 x 1 and Ge(100)-2 x 1 surfaces shows that the kinetics of oxidation of the Ge(100)-2 x 1 surface with water is slower. Our calculations also show that oxidation products on the Ge(100)-2 x 1 surface are less thermodynamically stable than on Si. We also investigate two competing dissociation reactions of H2O2 on the Ge(100)-2 x 1 surface. We find that dissociative adsorption via cleavage of the OH bond is less exothermic than OO dissociation. Furthermore, interdimer OO dissociation has a lower activation barrier than interdimer or intradimer OH dissociation, although interdimer dissociation products are found to be less stable compared than those formed from intradimer dissociation reactions. Finally, we find that the oxidation products formed from hydrogen peroxide are more stable than those formed from water. 相似文献
83.
Donald R. Dimmel Charles A. Wilkie Paul J. Lamothe 《Journal of mass spectrometry : JMS》1975,10(1):18-25
The mass spectra of (Me3Sn)nCH4?n, where n varies from 1 to 4, (Me3Sn)2CClX, where X equals H, Cl, Br or I, together with some tetraalkyltin compounds and Me3SnCCl3, are presented. Comparisons with mass spectra of the silicon analogs1 show a large number of similarities, including the appearance of allylic ions which require Group IV metal to carbon π-bonding. Multiple rearrangements are observed with the halogenated tin compounds which bring the α-halogen into direct bonding with the tin atom. 相似文献
84.
Richard J. Wiener Philip W. Hammer Charles E. Swanson David C. Samuels Russell J. Donnelly 《Journal of statistical physics》1991,64(5-6):913-926
Taylor-Couette flow subject to a Coriolis force is studied experimentally and numerically. In the experiment, the Couette apparatus is mounted on a turntable with the axis of the cylinders orthogonal to the rotation vector of the turntable. The Coriolis force stabilizes the fluid against the onset of Taylor vortices and alters the velocity fields, both above and below the transition from the initial flow. At small dimensionless turntable frequencies, the transition yields time-independent Taylor vortices which are tilted with respect to the cylinder axis. At larger there is a direct transition to turbulence. We determine the first-order correction to the classical Couette initial flow, to account for the effects of the Coriolis force, by expanding in powers of. We present numerical results for the axial velocity (the only nonvanishing correction term to order) in the infinite-cylinder approximation. 相似文献
85.
Chu-In Charles Lee 《Annals of the Institute of Statistical Mathematics》1992,44(1):107-120
The Laplace continued fraction is derived through a power series. It provides both upper bounds and lower bounds of the normal tail probability % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiqbfA6agzaaraaaaa!3DC0!\[\bar \Phi\](x), it is simple, it converges for x>0, and it is by far the best approximation for x3. The Laplace continued fraction is rederived as an extreme case of admissible bounds of the Mills' ratio, % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiqbfA6agzaaraaaaa!3DC0!\[\bar \Phi\](x)/(x), in the family of ratios of two polynomials subject to a monotone decreasing absolute error. However, it is not optimal at any finite x. Convergence at the origin and local optimality of a subclass of admissible bounds are investigated. A modified continued fraction is proposed. It is the sharpest tail bound of the Mills' ratio, it has a satisfactory convergence rate for x1 and it is recommended for the entire range of x if a maximum absolute error of 10-4 is required.The efforts of the author were supported by the NSERC of Canada. 相似文献
86.
87.
Tae-Kyu Ha Urs P. Wild Ren O. Kühne Charles Loesch Thierry Schaffhauser Johanna Stachel Alexander Wokaun 《Helvetica chimica acta》1978,61(3):1193-1199
Ab initio SCF and CI calculations on the cationic and neutral complexes of formaldehyde and lithium are reported. For the cationic complex CH2O/Li+, the stabilization energy of 41.7 kcal/mol obtained from the SCF calculation increases to 51.6 kcal/mol if a configuration interaction is introduced. For the neutral complex CH2O?/Li+, the C2v-conformer of the 2A1-state with the equilibrium bond distances of d(C? O) = 1.23 Å and d (O? Li) = 1.90 Å is calculated to be more stable than the 2B1-state with d (C? O) = 1.34 Å, and d (O? Li) = 1.65 Å. Charge transfer and polarization effects upon complex formation are discussed. 相似文献
88.
Trina M. Arola William H. Ojala Nell Herrera Barjeta Balidemaj Charles R. Ojala 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):o207-o211
Two isomeric pairs of Schiff bases, N,N′‐bis(2‐methoxybenzylidene)‐p‐phenylenediamine, C22H20N2O2, (I), and 2,2′‐dimethoxy‐N,N‐(p‐phenylenedimethylene)dianiline, C22H20N2O2, (II), and (E,E)‐1,4‐bis(3‐iodophenyl)‐2,3‐diazabuta‐1,3‐diene (alternative name: 3‐iodobenzaldehyde azine), C14H10I2N2, (III), and N,N′‐bis(3‐iodophenyl)ethylenediimine, C14H10I2N2 [JAYFEV; Cho, Moore & Wilson (2005). Acta Cryst. E 61 , o3773–o3774], differ pairwise only in the orientation of their imino linkages and in all four individual cases occupy inversion centers in the crystal, yet all four compounds are found to assume unique packing arrangements. Compounds (I) and (II) differ substantially in molecular conformation, possessing angles between their ring planes of 12.10 (15) and 46.29 (9)°, respectively. Compound (III) and JAYFEV are similar to each other in conformation, with angles between their imino linkages and benzene rings of 11.57 (15) and 7.4 (3)°, respectively. The crystal structures are distinguished from each other by different packing motifs involving the functional groups. Intermolecular contacts between methoxy groups define an R22(6) motif in (I) but a C(3) motif in (II). Intermolecular contacts are of the I⋯I type in (III), but they are of the N⋯I type in JAYFEV. 相似文献
89.
L. Allen Kindman Charles E. Cohen Michael H. Zeldin Yehuda Ben-Shaul Jerome A. Schiff 《Photochemistry and photobiology》1978,27(6):787-794
Abstract— Absorption measurements in the 600–720 nm region of dark-grown cells of Euglena gracilis Klebs var. bacillaris Cori were made in vivo at room temperature using computer-assisted spectrophotometry. Dark-grown wild-type cells have a prominent absorption maximum at 634 nm due to protochlorophyll(ide) absorption. Upon illumination, the absorption at 634nm decreases and a peak appears at 674nm, representing the phototransformation of protochlorophyll(ide) to chlorophyll(ide). Using difference spectroscopy, the resynthesis in the dark of protochlorophyll(ide) by previously-illuminated wild-type dark-grown cells was found to begin at about 10min after illumination and reached completion by about 25 min, the amount of protochlorophyll(ide) resynthesized being equivalent to that of dark-grown cells. Resynthesis of protochlorophyll(ide) following a second illumination follows the same kinetics, indicating that protochlorophyll(ide) resynthesis is under tight regulation, possibly via feedback control. Cells of dark-grown wild-type and W3BUL, a mutant lacking protochlorophyll(ide) contain a component absorbing at 658 nm which does not undergo phototransformation when examined by difference spectroscopy at room and liquid N2 temperatures. Following the phototransformation of protochlorophyll(ide) 634 to chlorophyll(ide) 674, the chlorophyll(ide) 674 shifts to shorter wavelengths, ultimately to 671 nm. Possible relationships among the various spectroscopic forms of protochlorophyll(ide) and chlorophyll(ide) at room temperature and liquid N2 temperature in Euglena and higher plants are presented. It is concluded that Euglena, unlike older, etiolated higher plants, contains only protochlorophyll(ide) 634, making it an excellent system in which to examine the phototransformation of this pigment species in the absence of other forms. 相似文献
90.
Thep-state pairing idea proposed recently to explain the ferromagnetism of ZrZn2 is described in more detail, and the underlying soft-mode hypothesis is examined in relation with experiments, in particular the discovery of antiferromagnetism in TiBe2. The key result, namely an electron-phonon contribution to the Stoner factor given essentially by the mass enhancement factor, is used to explain the behaviour of the Curie pointT
m
and to predict an isotope effect.p-state superconductivity with a transition temperature determined by is predicted in TiBe2 and, above the critical pressure whereT
m
=0, also in ZrZn2.Work in La Jolla supported by NSF/DMR 77-08469. 相似文献