2H NMR spectra of 2-(p-heptylbenzoyloxy)-5-(p-heptylbenzenazo)tropone. A new sigmatropic liquid crystal

Liquid crystals incorporating in their molecular framework a seven-membered ring are still relatively rare [1]. Recently the synthesis and thermal behaviour of a series of liquid crystal materials having a tropone moiety in their mesogenic core have been reported [2-4]. These mesogens, based on a 2-(acyloxy)tropone core structure, show intramolecular migration of the acyl substituents between the two oxygen atoms at C-1 and C-2, an effect already known for simple 2-(acyloxy)tropones in their isotropic solutions [5]. This migration involves a concerted [1, 9]-sigmatropic rearrangement [2]. This rearrangement could play a major role in determining the properties of the mesophases: it has been suggested in fact that, because of this rearrangement, the mesogenic molecules acquire a mean rod-like shape which can sustain the mesophase formation [2].     

Cylindrical spike model for the formation of diamondlike thin films by ion deposition

T /n_S of n_T rearrangements and n_S atoms in the spike volume as the crucial parameter characterizing the ability of a given ion–target combination to achieve complete rearrangement of the spike volume. n_T/n_S>1 is the optimum condition for diamondlike film growth. For aC films the ion energy dependence of n_T/n_S agrees well with the measured sp³ bond fraction. For Ar⁺-ion-assisted deposition of aC we find n_T/n_S>1 above 50 eV with no pronounced ion energy dependence. Furthermore, our model predicts optimum conditions for the formation of cubic boron nitride between 50 eV and 3 keV. Accepted: 14 October 1997     

Critical thickness and stress relaxation in YBaCuO (123) strained epitaxial layers and YBaCuO based strained superlattices

An energy model has been used to calculate the critical thickness h _c of YBaCuO thin films and YBaCuO based superlattices within an isotropic or anisotropic approximation. The critical thickness of single layers calculated from the anisotropic model (16 nm) is in good agreement with the previously published experimental values which are spread out from 4 to 20 nm. In the case of superlattices, relaxation appears to be governed by the critical thickness of the elementary sub-layers and is then better evaluated through the calculation performed for YBaCuO single layers. XRD measurements on YBa₂Cu₃O₇/PrBa₂Cu_3?xGa_xO₇ superlattices grown on {100{ SrTiO₃ have evidenced a tetragonal stress in the YBaCuO ab plane which remains expanded when the YBaCuO elementary layer thickness is lower than 4.8 nm (4 YBaCuO cells). However the critical temperature of the shortest period superlattices is only slightly affected by this expanded stress in contrast to the effect of an elastic stress externally applied along the ab plane of YBaCuO thin films.     

Theory of surface spin-exchange recombination of spin-polarized hydrogen

Calculations of the two-atom surface recombination rate for spinpolarized atomic hydrogen are carried out. Both the plane-wave Born approximation (PWBA) and the -dimensional distorted-wave model are employed. The field dependence forB=4 to 10 Tesla, and the temperature dependence for 0.2<T<1 K are examined for systems initially consisting of equal numbers ofa- andb-state atoms. The rates are analyzed with respect to para- and ortho-H₂ production, and to recombination to various vibrational and rotational states of H₂. The PWBA gives reasonable agreement with experiment with respect to the field-dependence and ortho-para production, but predicts an overall rate a factor of 40 above experiment. The -dimensional model underestimates the rate by a factor of 10³ and yields poorer agreement with experiment than the PWBA for the field-dependence and ortho-para production ratio. These results point out the need for a proper many-body treatment.     

Markov type properties for mixtures of probability measures

Summary We show that, given a general Markov type property M, and a finite dimensional set of probability measures , the set of elements of having M can be described by finitely many quadratic equations. We apply the result to the problem of the global Markov property for nonextremal Gibbs states.This work was prepared during the author's stay at the University of Hull, England, and supported by the Science and Engineering Research Council of Great Britatin     

A method to account for acoustic microstreaming when predicting bubble growth rates produced by rectified diffusion

A reinterpretation of existing theory for rectified diffusion, the process by which bubbles in a sound field may grow in radius, is presented in order to quantitate the effect of acoustic microstreaming on bubble growth rates. The 1/t term in the growth rate equation is defined as the "decay term" and t as the "decay time," the time required for the gas concentration in the liquid contacting the bubble to rise (or fall) from its initial to its final value. In the absence of microstreaming, t is the duration of sonification. In the presence of microstreaming, t may be calculated from the streaming velocity and the bubble radius. A comparison between theory and the experimental results of Eller [A. Eller, J. Acoust. Soc. Am. 46, 1246-1250 (1969)] and of Gould [R.K. Gould, J. Acoust. Soc. Am. 56, 1740-1746 (1974)] shows reasonable agreement in the low kHz range. Theoretical results in the frequency range of 1-10 MHz at 1 and 4 bar are also presented.     

Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element)

Keggin heteropolyanions [XM(12)O(40)](n-) have various isomeric structures, alpha and beta being the most common. Conventionally, the alpha structure appears to be the most stable, but calculations carried out at the DFT level for X = P(V), Si(IV), Al(III), As(V), Ge(IV), and Ga(III) and M = W(VI) and Mo(VI) show that this stability depends on several factors, particularly on the nature of the heteroatom (X) and the total charge of the cluster. In this paper, we apply the clathrate model to the Keggin molecule to carry out a fragment-interaction study to elucidate when and why the traditional relative stability of various isomers can be inverted. The fully oxidized anions that have inverted the traditional stability trend in this series are [AlW(12)O(40)](5-) and [GaW(12)O(40)](5-), both of which contain a third-group heteroatom and an overall charge of -5. beta-isomers are always more easily reduced than alpha-isomers. This experimental observation suggests that reduction favors the stability of beta-isomers and one of the most important results of this study is that the alpha/beta inversion is achieved in most cases after the second reduction. The alpha- and beta-isomers may have different properties because the energy of the LUMO, a symmetry-adapted d(xy)-metal orbital, is different.