Vapor phase modification of sol-gel derived titania (TiO2) surfaces

Chemical vapor deposition (CVD) method was used in titania surface modification. Titania layers were obtained in sol-gel process and prepared as thin films on silicon wafers in dip-coating method. In order to define the influence of modification on titania surface properties (e.g., friction), various types of fluoroalkylsilanes were used. The effectiveness of the modification was monitored by FT-IR spectroscopy. The topography and frictional measurements were investigated with the use of atomic force microscopy (AFM).     

Symmetry of the pentacene molecule and classification of electron states studied in the frame of group action on a set

Pentacene have recently become the subject of intense studies due to their physical properties which follow from the states of their outer-shell electrons that are able to take part in molecule bonding. The symmetry of these molecules provides the classification of quantum states according to the group theory method. In this paper, we apply a molecular state-space factorization scheme for the classification of pentacene molecules based on the structure of their electron states.     

A compromise procedure for the multiple objective linear fractional programming problem

A generalization of a well-known multiple objective linear fractional programming (MOLFP) problem, the multiple objective fractional programming (MOFP) problem, is formulated. A concept of multiple objective programming (MOP) problem corresponding to MOFP is introduced and some relations between those problems are examined. Based on these results, a compromise procedure for MOLFP problem is proposed. A numerical example is given to show how the procedure works.     

Fractional Dynamics Identification via Intelligent Unpacking of the Sample Autocovariance Function by Neural Networks

Many single-particle tracking data related to the motion in crowded environments exhibit anomalous diffusion behavior. This phenomenon can be described by different theoretical models. In this paper, fractional Brownian motion (FBM) was examined as the exemplary Gaussian process with fractional dynamics. The autocovariance function (ACVF) is a function that determines completely the Gaussian process. In the case of experimental data with anomalous dynamics, the main problem is first to recognize the type of anomaly and then to reconstruct properly the physical rules governing such a phenomenon. The challenge is to identify the process from short trajectory inputs. Various approaches to address this problem can be found in the literature, e.g., theoretical properties of the sample ACVF for a given process. This method is effective; however, it does not utilize all of the information contained in the sample ACVF for a given trajectory, i.e., only values of statistics for selected lags are used for identification. An evolution of this approach is proposed in this paper, where the process is determined based on the knowledge extracted from the ACVF. The designed method is intuitive and it uses information directly available in a new fashion. Moreover, the knowledge retrieval from the sample ACVF vector is enhanced with a learning-based scheme operating on the most informative subset of available lags, which is proven to be an effective encoder of the properties inherited in complex data. Finally, the robustness of the proposed algorithm for FBM is demonstrated with the use of Monte Carlo simulations.     

Regiospecific and highly stereoselective coupling of 6-(substituted-imidazol-1-yl)purines with 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-erythro-pentofuranosyl chloride. Sodium-salt glycosylation in binary solvent mixtures: improved synthesis of cladribine

Glycosylation of 6-(substituted-imidazol-1-yl)purine sodium salts with 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-erythro-pentofuranosyl chloride proceeds with regiospecific formation of the N9 isomers. Base substrates with lipophilic substituents on the C6-linked imidazole moiety are more soluble in organic solvents, and the solubility is further increased with binary solvent mixtures. Selective solvation also diminishes the extent of anomerization of the chlorosugar. Stirred reaction mixtures of the modified-purine sodium salts generated in a polar solvent and cooled solutions of the protected 2-deoxysugar chloride in a nonpolar solvent give 2'-deoxynucleoside derivatives with N9 regiochemistry and enhanced beta/alpha configuration ratios. Application of the binary-solvent methodology with 2-chloro-6-(substituted-imidazol-1-yl)purine salts in cold acetonitrile and the chlorosugar in cold dichloromethane gives essentially quantitative yields of the N9 isomers of beta-anomeric 2'-deoxynucleoside intermediates. Direct ammonolysis (NH(3)/MeOH) of such intermediates or benzylation of the imidazole ring followed by milder ammonolysis of the imidazolium salt gives high yields of the clinical anticancer drug cladribine (2-chloro-2'-deoxyadenosine).     

The exchange-correlation potential in ab initio density functional theory

From coupled-cluster theory and many-body perturbation theory we derive the local exchange-correlation potential of density functional theory in an orbital dependent form. We show the relationship between the coupled-cluster approach and density functional theory, and connections and comparisons with our previous second-order correlation potential [OEP-MBPT(2) (OEP-optimized effective potential)] [I. Grabowski, S. Hirata, S. Ivanov, and R. J. Bartlett, J. Chem. Phys. 116, 4415 (2002)]. Starting from a general theoretical framework based on the density condition in Kohn-Sham theory, we define a rigorous exchange-correlation functional, potential and orbitals. Specifying initially to second-order terms, we show that our ab initio correlation potential provides the correct shape compared to those from reference quantum Monte Carlo calculations, and we demonstrate the superiority of using Fock matrix elements or more general infinite-order semicanonical transformations. This enables us to introduce a method that is guaranteed to converge to the right answer in the correlation and basis set limit, just as does ab initio wave function theory. We also demonstrate that the energies obtained from this generalized second-order method [OEP-MBPT2-f] and [OEP-MBPT2-sc] are often of coupled-cluster accuracy and substantially better than ordinary Hartree-Fock based second-order MBPT=MP2.     

Point vortex dynamics: recent results and open problems

he concept of point vortex motion, a classical model in the theory of two-dimensional, incompressible fluid mechanics, was introduced by Helmholtz in 1858. Exploration of the solutions to these equations has made fitful progress since that time as the point vortex model has been brought to bear on various physical situations: atomic structure, large scale weather patterns, “vortex street” wakes, vortex lattices in superfluids and superconductors, etc. The point vortex equations also provide an interesting example of transition to chaotic behavior. We give a brief historical introduction to these topics and develop two of them in particular to the point of current understanding: (i) Steadily moving configurations of point vortices; and (ii) Collision dynamics of vortex pairs.     

Dissociative electron attachment to triflates

Gas phase studies of dissociative electron attachment to simple alkyl (CF(3)SO(3)CH(3)) and aryl (C(6)H(5)SO(3)CF(3) and CF(3)SO(3)C(6)H(4)CH(3)) triflates, model molecules of nonionic photoacid generators for modern lithographic applications, were performed. The fragmentation pathways under electron impact below 10 eV were identified by means of crossed electron-molecular beam mass spectrometry. Major dissociation channels involved C-O, S-O, or C-S bond scissions in the triflate moiety leading to the formation of triflate (OTf(-)), triflyl (Tf(-)), or sulfonate (RSO(3)(-)) anions, respectively. A resonance leading to C-O bond breakage and OTf(-) formation in alkyl triflates occurred at electron energies about 0.5 eV lower than the corresponding resonance in aryl triflates. A resonance leading to S-O bond breakage and Tf(-) formation in aryl triflates occurred surprisingly at the same electron energies as C-O bond breakage. In case of alkyl triflates S-O bond breakage required 1.4 eV higher electron energies to occur and proceeded with substantially lower yields than in aryl triflates. C-S bond scission occurred for all presently studied triflates at energies close to 3 eV.     

Interplay of the Kondo effect and spin-polarized transport in magnetic molecules, adatoms, and quantum dots

We study the interplay of the Kondo effect and spin-polarized tunneling in a class of systems exhibiting uniaxial magnetic anisotropy. Using the numerical renormalization group method we calculate the spectral functions and linear conductance in the Kondo regime. We show that the exchange coupling between conducting electrons and localized magnetic core generally leads to suppression of the Kondo effect. We also predict a nontrivial dependence of the tunnel magnetoresistance on the strength of exchange coupling and on the anisotropy constant.