Vector correlations in photodissociation of polarized polyatomic molecules beyond the axial recoil limit

We present the full quantum mechanical theory of the angular momentum distributions of photofragments produced in photolysis of oriented/aligned parent polyatomic molecules beyond the axial recoil limit. This paper generalizes the results of Underwood and Powis(28,29) to the case of non-axial recoil photodissociation of an arbitrary polyatomic molecule. The spherical tensor approach is used throughout this paper. We show that the recoil angular distribution of the angular momentum polarization of each of the photofragments can be presented in a universal spherical tensor form valid for photolysis in diatomic or polyatomic molecules, irrespective of the reaction mechanism. The angular distribution can be written as an expansion over the Wigner D-functions in terms of the set of the anisotropy-transforming coefficients c(K(i)q(i))(K) (k(d), K(0)) which contain all of the information about the photodissociation dynamics and can be either determined from experiment, or computed from quantum mechanical theory. An important new conservation rule is revealed through the analysis, namely that the component q(i) of the initial reagent polarization rank K(i) and the photofragment polarization rank K onto the photofragment recoil direction k is preserved in any photolysis reaction. Both laboratory and body frame expressions for the recoil angle dependence of the photofragment angular momentum polarization are presented. The parent molecule polarization is shown to lead to new terms in the obtained photofragment angular distributions compared with the isotropic case. In particular, the terms with |q(i)| > 2 can appear which are shown to manifest angular momentum helicity non-conservation in the reaction. The expressions for the coefficients c(K(i)q(i))(K) (k(d), K(0)) have been simplified using the quasiclassical approximation in the high-J limit which allows for introducing the dynamical functions and the rotation factors which describe the decreasing of the photofragment angular momentum orientation and alignment due to the rotation of the molecular axis during photodissociation. In this case, the resultant recoil angle dependence is also presented in a form where the anisotropy of the parent molecular ensemble is expressed in terms of the molecular axis distribution, rather than in terms of the molecular density matrix.     

Development of a turbulent boundary layer after a step from smooth to rough surface

The flow developing downstream of a step change from smooth to rough surface condition is studied in the light of Townsend’s wall similarity hypothesis. Previous studies seem to support the hypothesis for channel and pipe flows, but there are considerable controversies about its application to boundary layers and in particular to surface roughness formed by spanwise bars. It has been suggested that this controversy arises from insufficient separation of scales between the boundary layer thickness and the roughness length scale. An experimental investigation has therefore been undertaken where the flow evolves from a fully developed smooth wall boundary layer at high Reynolds numbers over a step in surface roughness (Re _θ = 13,400 at the step). The flow is mapped through the development of the internal layer until the flow is fully developed over the rough wall. The internal layer is found to grow as δ ∼ X ^0.73, and after about 15 boundary layer thicknesses at the step, the internal layer has reached the outer edge of the incoming layer. At the last rough wall measurement station, the Reynolds number has grown to Re _θ ≈ 32,600 and the ratio of boundary layer to roughness length scales is δ/k ≈ 140. The outer layer differences between the smooth and the rough wall data were found to be sufficiently small to conclude that for this setup the Townsend’s wall similarity hypothesis appears to hold.     

Physical processes during development of lightning flashes

The objective of this paper is to review our present understanding of the physical processes in lightning flashes during their development within or outside a cloud, following lightning initiation. This represents the ‘big picture’ of lightning development, in the scale of the cloud dimensions themselves. Since the acceptance of the bi-directional, zero-net-charge leader concept, significant changes have occurred in our understanding of the key physical processes of which a lightning flash is comprised, and in the analytical relationship between the electrical structure of a cloud and lightning parameters. These changes are discussed with an emphasis on the unifying nature of the bi-directional leader concept. To cite this article: V. Mazur, C. R. Physique 3 (2002) 1393–1409.     

Construction of fiber-optic bundle light-collection systems and calculations of collection efficiency

This paper describes the position-sensitive light-collection system that we use in our fast-beam laser experiments. The collection system consists of fiber-optic bundles whose facets are arranged to accept light emitted from a beam of fluorescent atoms. The flexibility of the fiber bundles allows their use in scanning collection systems with precise position sensitivity. We describe calculations of geometrical collection efficiency using a numerical integration scheme and compare the results with measurements. We also compare the collection efficiencies of the different fiber bundle arrangements that we used as our apparatus evolved with the implementation of various improvements.     

High-pressure clathrate hydrate of acetone

X-ray diffraction study of quenched sample of acetone clathrate hydrate synthesized at 0.8 GPa was carried out. It was shown that the host frameworks of the hydrate comprise uniform cavities which are similar to that of recently characterized structure of high-pressure tetrahydrofurane hydrate. The unique peculiarity of investigated hydrate is decrease in the crystallographic symmetry of the hydrate arising from ordering in guest subsystem.     

An exact identity for memory

It is argued that memory functions from Time-Convolution Generalized Master Equations for probabilities of finding a system interacting with a genuine bath in arbitrary state of a full system of states have, under quite general conditions for asymmetric systems, zero time integrals provided that the latter exist and that no approximations were involved.     

Effects of substituents on activation parameters in SN2 reactions at aliphatic carbon in solution

Changes of the activation parameters in aliphatic S_N2 reactions with anionic and neutral nucleophiles in various solvents, ΔH^≠ and ΔS^≠, were correlated with σ constants of the substituents. The resultant δΔH^≠ and δΔS^≠ reaction constants are linearly related for variations of substituents at the substrate, leaving group and nucleophile. Correlations of δΔH^≠ versus δΔS^≠ allow the estimation of the contribution of changes of the internal enthalpy, δΔH, to the enthalpy reaction constant, δΔH^≠, which gives a single linear dependence on the Hammett ρ reaction constants. The deviations from the dependence of δΔH versus ρ can be interpreted in terms of changes in the transition state structure in S_N2 reactions. The results obtained show that the substituent effects on the charge development in the transition state are governed by the magnitude of δΔH. Copyright © 2009 John Wiley & Sons, Ltd.     

Explicit solutions of generalized Cauchy-Riemann systems using the transplant operator

In Kravchenko (2008) [8] it was shown that the tool introduced there and called the transplant operator transforms solutions of one Vekua equation into solutions of another Vekua equation, related to the first via a Schrödinger equation. In this paper we prove a fundamental property of this operator: it preserves the order of zeros and poles of generalized analytic functions and transforms formal powers of the first Vekua equation into formal powers of the same order for the second Vekua equation. This property allows us to obtain positive formal powers and a generating sequence of a “complicated” Vekua equation from positive formal powers and a generating sequence of a “simpler” Vekua equation. Similar results are obtained regarding the construction of Cauchy kernels. Elliptic and hyperbolic pseudoanalytic function theories are considered and examples are given to illustrate the procedure.