The submersion of sodium clusters in helium nanodroplets: identification of the surface → interior transition

The submersion of sodium clusters beyond a critical size in helium nanodroplets, which has recently been predicted on theoretical grounds, is demonstrated for the first time. Confirmation of a clear transition from a surface location, which occurs for alkali atoms and small clusters, to full immersion for larger clusters, is provided by identifying the threshold electron energy required to initiate Na(n) cluster ionization. On the basis of these measurements, a lower limit for the cluster size required for submersion, n ≥ 21, has been determined. This finding is consistent with the recent theoretical prediction.     

Site-Selectivity in the Fe+-Mediated C?H/C?C Bond Activation of Aldimines Short Communication

It is demonstrated for the first time that the site-selectivity for the Fe⁺-mediated C? H bond activation of aldimines R¹N?CHR² (R¹, R² = alkyl) involves the alkyl chain R¹ by a factor ≥ 12 in comparison to the alkenyl part R². This finding explains previous observations that dehydrogenation of intermediates formed by alkene loss from either R¹ or R² of R¹N?CHR²/Fe⁺ preferentially involves the alkyl part.     

Dissociative electron attachment to furan, tetrahydrofuran, and fructose

We study dissociative electron attachment to furan (FN) (C(4)H(4)O), tetrahydrofuran (THF) (C(4)H(8)O), and fructose (FRU) (C(6)H(12)O(6)) using crossed electron/molecular beams experiments with mass spectrometric detection of the anions. We find that FN and THF are weak electron scavengers and subjected to dissociative electron attachment essentially in the energy range above 5.5 eV via core excited resonances. In striking contrast to that, FRU is very sensitive towards low energy electrons generating a variety of fragment ions via a pronounced low energy feature close to 0 eV. These reactions are associated with the degradation of the ring structure and demonstrate that THF cannot be used as surrogate to model deoxyribose in DNA with respect to the attack of electrons at subexcitation energies (<3 eV). The results support the picture that in DNA the sugar moiety itself is an active part in the initial molecular processes leading to single strand breaks.     

Sulfur- and Selenium-Containing Compounds Potentially Exhibiting Al Ion Conductivity

We have created a set of crystalline model structures exhibiting straight lines of Al³⁺ connected to chalcogenides (O²⁻, S²⁻, and Se²⁻) connected to metal cations of varying valence (Sr²⁺, Y³⁺, Zr⁴⁺, Nb⁵⁺, and Mo⁶⁺). They were relaxed with density functional theory computations and analysed by Bader partitioning. As Al³⁺ ions are supposed to strongly interact with their atomic environment, we studied the electron density topology induced by higher-valent cations in the extended chemical neighbourhood of Al. In fact, we found a general decrease of ionic charges and an increasing displacement of the chalcogenides towards higher-valent ions for the heavier chalcogens. Therefore, we comprehensively screened S- and Se-containing compounds for candidates theoretically exhibiting low migration barriers for Al³⁺ ions by using Voronoi–Dirichlet partitioning and bond valence site energy calculations. The basis for this search is the Inorganic Crystal Structure Database. Indeed, we could extract six promising candidates with low Al³⁺ migration barriers. which are even lower than the barriers for any other element inside of these materials. This will encourage efforts towards preparing suitable Al³⁺ conductors.     

Implicit large-eddy simulation applied to turbulent channel flow with periodic constrictions

The subgrid-scale (SGS) model in a large-eddy simulation (LES) operates on a range of scales which is marginally resolved by discretization schemes. Accordingly, the discretization scheme and the subgrid-scale model are linked. One can exploit this link by developing discretization methods from subgrid-scale models, or the converse. Approaches where SGS models and numerical discretizations are fully merged are called implicit LES (ILES). Recently, we have proposed a systematic framework for the design, analysis, and optimization of nonlinear discretization schemes for implicit LES. In this framework parameters inherent to the discretization scheme are determined in such a way that the numerical truncation error acts as a physically motivated SGS model. The resulting so-called adaptive local deconvolution method (ALDM) for implicit LES allows for reliable predictions of isotropic forced and decaying turbulence and of unbounded transitional flows for a wide range of Reynolds numbers. In the present paper, ALDM is evaluated for the separated flow through a channel with streamwise-periodic constrictions at two Reynolds numbers Re = 2,808 and Re = 10,595. We demonstrate that, although model parameters of ALDM have been determined for isotropic turbulence at infinite Reynolds number, it successfully predicts mean flow and turbulence statistics in the considered physically complex, anisotropic, and inhomogeneous flow regime. It is shown that the implicit model performs at least as well as an established explicit model.      

Compactly Supported Correlation Functions

This article proposes compactly supported correlation functions, which parameterize the smoothness of the associated stationary and isotropic random field. The constructions are straightforward, and compact support is relevant for various ends: computationally efficient spatial prediction, fast and exact simulation, and appeal among practicioners.     

REACTIVITY OF EXCITED STATES OF FLAVIN AND 5-DEAZAFLAVIN IN ELECTRON TRANSFER REACTIONS

Abstract— Quenching of the excited states of lumiflavin and 3-methyl-5-deazalumiflavin by methyl-and methoxy-substituted benzenes and naphthalenes in methanol was investigated. The observed difference in the reactivity of acid and neutral lumiflavin triplets is explained thermodynamically by applying the Michaelis cycle, as being due to the higher reduction potential of the acid triplet. In this connection the p K values of lumiflavin triplet (p K ^M= 6.5) and semiquinone (p K ^M= 11.3) have also been determined in methanol. The difference in the reactivity between the singlet and triplet states of lumiflavin is found to be greater as predicted by the difference in excitation energy. The reactivities of the excited states of flavin and 5-deazaflavin differ only slightly in contrast to the marked difference in the ground state reactivities of electron transfer reactions. This is explained in terms of the model of Rehm and Weller. The pH dependence of the electron transfer quenching of 5-deazaflavin triplet was investigated in water, yielding a triplet p K of 2.5. In contrast to the flavin, this triplet p K does not significantly differ from the p K of the 5-deazaflavin ground state. From this, different sites of protonation are deduced for the photoexcited triplet states of flavin and 5-deazaflavin.     

Letter to the Editor: On the evolution of dissipation rate and resolved kinetic energy in ALDM simulations of the Taylor–Green flow

We correct a data processing error in the article “Construction of explicit and implicit dynamic finite difference schemes and application to the large-eddy simulation of the Taylor–Green vortex” by Dieter Fauconnier, Chris De Langhe and Erik Dick published in the Journal of Computational Physics 228 (2009), pp. 8053–8084.     

Fuzzy complex Grassmannians and quantization of line bundles

We construct by purely representation-theoretic methods fuzzy versions of an arbitrary complex Grassmannian M=Gr _n (ℂ ^n+m ), i.e., a sequence of matrix algebras tending SU(n+m)-equivariantly to the algebra of smooth functions on M. We also show that this approximation can be interpreted in terms of the Berezin-Toeplitz quantization of M. Furthermore, we use branching rules to prove that the quantization of every complex line bundle over M is given by a SU(n+m)-equivariant truncation of the space of its L ²-sections.