In situ determination of orientational distributions in Langmuir monolayers by total internal reflection fluorescence

A new application of the polarized total internal reflection fluorescence (PTIRF) technique to study the orientation distribution of a fluorophore within a Langmuir monolayer in situ on an aqueous subphase is described. The technique utilizes the measurement of polarized fluorescence, excited by the evanescent field appearing upon total internal reflection. The excitation by the evanescent field is achieved by launching the beam into a prism that is brought into contact with the monolayer from above. We also show here that a combination of PTIRF of monolayers on water and those freshly deposited onto the prism by horizontal lift in the same experiment provide enough data to determine the dielectric constant of the actual local environment of the fluorophore in the monolayer to eliminate the ambiguity of the orientation determination, arising from uncertainty in the normal component of excitation field. The new technique was applied to several model systems: fatty acid monolayers containing amphiphilic dyes DiI or BODIPY and also a monolayer of a synthetic amphiphilic porphyrin-binding peptide AP0. This technique is more accurate than polarized epifluorescence (PEF) in determining the fluorophore orientation distribution due to the much higher normal component of the excitation, achievable in the evanescent field, and to the lack of surface vibrations caused by capillary waves. Comparison of the new PTIRF approach with PEF shows that the monolayer structure is not disturbed by weak van der Waals attachment to the hydrophobic substrate.     

脉冲激光沉积的金属原子团簇的电子状态及生长的研究

 介绍了采用X射线光电子谱(XPS)等技术研究脉冲激光沉积在Ni、Mo、C、NaCl(100)表面的Cu、Au原子团簇的电子状态;结合Cu₂p_3/2 X射线光电子谱峰和Cu L₃M_4,5M_4,5俄歇跃迁分离了电子结合能的初态和终态贡献,得出了它们随Cu表面浓度变化的关系,并对之作出了解释。使用XPS、RBS、TEM三项技术研究了Au在NaCl(100)表面的生长过程,通过计算得出了在不同表面浓度下Au原子团簇的平均高度和表面覆盖率。     

Ordering in an ensemble of nanometer-size Au clusters on a NaCl(100) surface at high deposition rates

The results of experimental studies on pulsed laser deposition of the Au atoms on the NaCl(100) surface are reported. Under the conditions far from thermodynamic equilibrium, the spatial ordering was observed in an ensemble of gold clusters at the initial deposition stage. A mechanism based on the idea of fractal structure decomposition caused by the development of unstable concentration modes in the condensed substance is proposed.     

The percolation transition in filling a nanoporous body by a nonwetting liquid

The paper presents the results of an experimental study of the percolation transition in filling by nonwetting liquids of nanoporous bodies of various natures with different specific surface areas and mean pore and granule sizes. The liquid that we used was an aqueous solution of ethylene glycol. The hysteresis and non-outflow phenomena observed in this transition at various (known) surface energies of liquids were studied by varying the concentration of ethylene glycol. This helped us explain the mechanism of the percolation transition in filling nanoporous bodies with nonwetting liquids. It was shown that, to quantitatively describe the observed dependences in terms of percolation theory taking into account energy barriers to filling, we must use a non-scaling distribution function of clusters of accessible and filled pores that admits the formation of pore clusters of arbitrary dimensions.     

Correlation effects in Auger spectra of Ni and Cu nanoclusters

Results of experimental research of exciton-like two-hole states in nanoclusters of narrow-band metals (Ni, Cu) on surface of high-oriented pyrolitic graphite by X-ray photoelectron and Auger electron spectroscopy are presented. It was found that the evolution of the electronic structure in Ni nanoclusters with the decreasing of their sizes can lead to appearance of long-living two-hole states in the valence band. One-particle and two-particle density of states are analyzed, and the Auger-electron spectra confirming the presence of the bound and localized states are obtained.     

Natural multitransformations of multifunctors

We continue to develop the theory of multicategories over verbal categories. This theory includes both the usual category theory and the theory of operads, as well as a significant part of classical universal algebra. We introduce the notion of a natural multitransformation of multifunctors, owing to which categories of multifunctors from a multicategory to some other one turn into multicategories. In particular, any algebraic variety over a multicategory possesses a natural structure of a multicategory. Furthermore, we construct a multicategory analog of commacategories with properties similar to those in the category case. We define the notion of the center of a multicategory and show that centers of multicategories are commutative operads (introduced by us earlier) and only they. We prove that commutative FSet-operads coincide with commutative algebraic theories.     

A study of many-body phenomena in metal nanoclusters (Au, Cu) close to their transition to the nonmetallic state

The results of a study of many-body phenomena in gold and copper nanoclusters are presented. The measured conductivity as a function of nanocluster height h was found to have a minimum at h ≈ 0.6 nm. Conductivity was local in character at nanocluster sizes l ≤ l _c ≈ 2.5 nm. Changes in core hole screening and an anomalous increase in the Anderson singularity index α in gold and copper nanoclusters could be caused by changes in permittivity from metallic (? → ∞) to nonmetallic (? ∝ l ²). The many-body phenomenon characteristics observed in the X-ray photoelectron and tunnel spectra of gold and copper nanoclusters as the size of the nanoclusters changed led us to suggest changes in the band structure of the nanoclusters and, therefore, their possible transition from the metallic to nonmetallic state.     

Formation of an ensemble of nanoclusters under rapid deposition of atoms on a surface

The results of an experimental study of the formation of nanometer-size Au clusters on NaCl(100) and HOPG(0001) surfaces under pulsed laser deposition are presented. No clusters of small sizes (d ≤ 1 nm) have been found in the cluster size distribution. The distribution itself at d < 5 nm has the form of a percolation distribution. It has been established that the perimeter of clusters with sizes d < 5 nm has a fractal structure. The fractal dimension of clusters is different for NaCl(100) and HOPG(0001) surfaces with different symmetries; it decreases with increasing cluster size from D _f ≈ 1.2–1.4 at d ≈ 1.5 nm to D _f ≈ 1 at d ≈ 5 nm. A physical mechanism of nanocluster formation is suggested. Under pulsed laser deposition, the attainable densities of adatoms are close to the percolation threshold in the region of thermodynamically unstable states and many-particle correlation regions are formed in a spatially inhomogeneous adsorbate. Clusters are formed on the surface from many-particle correlation regions in several diffusion jumps. The suggested mechanism allows the fractal dimension of the clusters forming on surfaces with different symmetries, its dependence on cluster size, and the cluster size distribution functions to be calculated.     

On the melting of gold nanoclusters formed by pulsed laser deposition on different substrates

The experimental results are presented for the backscattering of 500-eV electrons on Au nanoclusters formed on the surface of highly oriented pyrolytic graphite HOPG(0001) and amorphous SiO₂. It has been found that the measured intensity of the elastically backscattered electrons nonmonotonically depends on the size of nanoclusters. It has been shown that the observed features can be explained by an increase in the rms deviation of the atoms of the Au nanocluster with a decrease in its size. The difference in the dependence of the rms deviation of atoms on the size of the nanoclusters formed on the surfaces of HOPG(0001) and amorphous SiO₂ is qualitatively explained by an increase in the roughness of the nanocluster surface accompanying their formation under the strongly nonequilibrium conditions of pulsed laser deposition.