Semiclassical versus quantum-mechanical vibronic approach in the analysis of the functional characteristics of molecular quantum cellular automata.

In the context of the decisive role that vibronic interactions play in the functioning of molecular quantum cellular automata, in this article we give a comparative analysis of the two alternative vibronic approaches to the evaluation of the key functional characteristics of molecular cells. Semiclassical Born-Oppenheimer approximation and quantum mechanical evaluations of the vibronic energy pattern, electronic density distributions and cell-cell response function are performed for two-electron square-planar mixed valence molecular cells subjected to the action of a molecular driver. Special emphasis is put on the description of the cell-cell response function, which describes strong non-linearity as a prerequisite for the effective action of quantum cellular automata.

Two-dimensional decomposition of H-D exchange mass spectra of multicharged ions of biopolymers and their separation into components with independent H-D substitutions.

The work is aimed at developing a numerical method for analysing mass spectra of deutero-substituted multicharged ions of biopolymers to determine contributions of components presumably corresponding to different biomolecule conformations. The two-dimensional decomposition of the H-D exchange mass spectra of two, three and four charged apamin ions with their separation suggests that the reaction of apamin ions with ND molecules in the gas phase reveals hypothetically three different structural modifications of apamin ions. Usually for H-D exchange mass spectra, the presence of many resolvable protein structures was determined from measured distributions of peak intensities of ions with the same charge state.

Persistent Organic High-Spin Trinitrenes.

The septet ground state trinitrenes 1,3,5-trichloro-2,4,6-trinitrenobenzene and 1,3,5-tribromo-2,4,6-trinitrenobenzene were isolated in inert (Ar, Ne, and Xe) as well as reactive matrices (H , O , and H O) at cryogenic temperatures. These trinitrenes were obtained in high yields by UV photolysis of the corresponding triazides and characterized by IR and UV/Vis spectroscopy. The trinitrenes, despite bearing six unpaired electrons, are remarkably unreactive towards molecular oxygen and hydrogen and are persistent in water ice up to 160 K where the water matrix starts to sublime off.

The first water-soluble polynuclear metallamacrocyclic Sr(ii)-Cu(ii) complex based on simple glycinehydroximate ligands.

Recently, aminohydroximate ligands have found wide applications in the fascinating class of polynuclear metallamacrocyclic compounds named 15-MC-5 metallacrowns. The enhanced interest in water-soluble aminohydroximate Ln(iii)-Cu(ii) complexes is largely due to their rich coordination chemistry, diverse properties and ease of synthesis. We examined glycinehydroxamic acid as a simple ligand for the preparation of the first water-soluble polynuclear metallamacrocyclic Sr(ii)-Cu(ii) compound.

Spin-crossover behavior of neutral iron(iii) complexes with salicylaldehyde thio-, seleno- and semicarbazone ligands: experiment and theoretical analysis.

The iron(iii) complex [Fe(Hsemsal)(semsal)]·3H2O (1) (H2semsal - salicylaldehyde semicarbazone) has been synthesized and characterized by powder and single crystal X-ray diffraction, and magnetic susceptibility measurements. Crystal structure analysis showed that the complex forms neat stacks stabilized by hydrogen-bonding through water molecules and π-π interactions between phenolate rings of ligands. The complex does not exhibit spin-crossover phenomena and remains in the high-spin state down to 2 K.

Phase Transitions and Formation of a Monolayer-Type Structure in Thin Oligothiophene Films: Exploration with a Combined In Situ X-ray Diffraction and Electrical Measurements.

A combination of in situ electrical and grazing-incidence X-ray diffraction (GIXD) is a powerful tool for studies of correlations between the microstructure and charge transport in thin organic films. The information provided by such experimental approach can help optimizing the performance of the films as active layers of organic electronic devices. In this work, such combination of techniques was used to investigate the phase transitions in vacuum-deposited thin films of a common organic semiconductor dihexyl-quarterthiophene (DH4T).

The First Conducting Spin-Crossover Compound Combining a Mn Cation Complex with Electroactive TCNQ Demonstrating an Abrupt Spin Transition with a Hysteresis of 50 K.

We present herein the synthesis, crystal structure, and electric and magnetic properties of the spin-crossover salt [Mn(5-Cl-sal-N-1,5,8,12)]TCNQ ⋅2 CH CN (I), where 5-Cl-sal-N-1,5,8,12=N,N'-bis(3-(2-oxy-5-chlorobenzylideneamino)propyl)-ethylenediamine, containing distinct conductive and magnetic blocks along with acetonitrile solvent molecules. The Mn complex with a Schiff-base ligand, [Mn(5-Cl-sal-N-1,5,8,12)] , acts as the magnetic unit, and the π-electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ ) is the conducting unit. The title compound (I) exhibits semiconducting behavior with room temperature conductivity σ ≈1×10  ohm  cm and activation energy Δ ≈0.

Polarized angular-dependent reflectivity and density-dependent profiles of shock-compressed xenon plasmas.

New data for the reflectivity of shock-compressed xenon plasmas at pressures of 10-12 GPa at large incident angles are presented. In addition, measurements have been performed at different densities. These data allow to analyze the free-electron density profile across the shock wave front.

Strained Bottlebrushes in Super-Soft Physical Networks.

ABA triblock copolymers composed of a poly(dimethylsiloxane) (PDMS) bottlebrush central block and linear poly(methyl methacrylate) (PMMA) terminal blocks self-assemble into a physical network of PDMS bottlebrush strands connected by PMMA spherical domains. A combination of small- and ultrasmall-angle X-ray scattering techniques was used to concurrently examine dimensions of PMMA spherical domains and PDMS bottlebrush strands both in the bulk and at the PMMA-PDMS interface. In agreement with scaling model predictions, the degrees of polymerization of the bottlebrush backbone () and PMMA block () correlate with the measured PMMA domain size and area per molecule at the PMMA-PDMS interface as ∝ () and ∝ , respectively.

Pair-delocalization in trigonal mixed-valence clusters: new insight into the vibronic origin of broken-symmetry ground states.

A new vibronic mechanism for the stabilization of pair-delocalized electronic states in trigonal trimeric mixed valence complexes (such as iron-sulfur [FeS] proteins) is proposed. Unlike the previously reported mechanism based on the Piepho-Krausz-Schatz model dealing with the local "breathing" vibrations, the present mechanism involves the multicenter vibrations of the triangular complex, which change the metal-metal distances. The former mechanism of the vibronic coupling in combination with the double exchange and Heisenberg type exchange (superexchange) interactions accounts for the existence of the pair-delocalized states of many-electron mixed valence clusters in the intermediate ground spin states.

Aqueous microgels modified with photosensitive wedge-shaped amphiphilic molecules: synthesis, structure and photochemical behaviour.

Aqueous microgels based on poly(N-vinylcaprolactam) with reversible temperature-induced volume transition are promising "smart" materials for various applications. In this work, the microgels are modified via acid-base interaction by wedge-shaped amphiphilic sulfonic acid molecules with alkyl chains of different lengths and an azobenzene group. In contrast to the pristine microgel the modified microgels retain colloidal stability in water and show different responses to the change of temperature and pH.

Nuclear spin selectivity in enzymatic catalysis: A caution for applied biophysics.

Nuclear magnetic ions Mg, Ca, and Zn suppress DNA synthesis by 3-5 times with respect to ions with nonmagnetic nuclei. This observation unambiguously evidences that the DNA synthesis occurs by radical pair mechanism, which is well known in chemistry and implies pairwise generation of radicals by electron transfer between reaction partners. This mechanism coexists with generally accepted nucleophilic one; it is switched on, when at least two ions enter into the catalytic site.

Dynamics of supernova bounce in laboratory.

We draw attention to recent high-explosive (HE) experiments which provide compression of macroscopic amount of matter to high, even record, values of pressure in comparison with other HE experiments. The observed bounce after the compression corresponds to processes in core-collapse supernova explosions after neutrino trapping. Conditions provided in the experiments resemble those in core-collapse supernovae, permitting their use for laboratory astrophysics.

EPR spectroscopy of multicomponent, multispin molecular system obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon.

Complex multicomponent, multispin molecular system, consisting of a septet trinitrene, two quintet dinitrenes, and three triplet mononitrenes, was obtained by the photolysis of 2,4,6-triazido-3-cyano-5-fluoropyridine in solid argon. To identify these paramagnetic products, electron paramagnetic resonance spectroscopy in combination with line-shape spectral simulations and density functional theory calculations was used. The products of the photolysis was found to be triplet 2,4-diazido-3-cyano-5-fluoropyridyl-6-nitrene (D  = 1.

Hydrated Sulfate Clusters SO(HO) ( n = 1-40): Charge Distribution Through Solvation Shells and Stabilization.

Investigations of inorganic anion SO interactions with water are crucial for understanding the chemistry of its aqueous solutions. It is known that the isolated SO dianion is unstable, and three HO molecules are required for its stabilization. In the current work, we report our  computational study of hydrated sulfate clusters SO(HO) ( n = 1-40) in order to understand the nature of stabilization of this important anion by water molecules.

Taxifolin tubes: crystal engineering and characteristics.

Taxifolin, also known as dihydroquercetin, is the major flavonoid in larch wood. It is well known as an antioxidant and a bioactive substance. Taxifolin as an active pharmaceutical ingredient is produced industrially in crystalline form during the processing of larch wood.

Coordination-induced metal-to-macrocycle charge transfer and effect of cations on reorientation of the CN ligand in the {SnLMac} dianions (L = CN, OCN, Im; Mac = phthalo- or naphthalocyanine).

A series of anionic coordination complexes of tin(ii) phthalocyanine (Pc) with cyanide, cyanate, and imidazolate (Im) anions (1, 3, and 4, respectively) and tin(ii) naphthalocyanine (Nc) with cyanide anions (2) has been obtained. Two anions coordinate to tin(ii) atoms in 1-4 to form the {SnL2Mac}2- dianions in salts with the general formula {crypt[2.2.

Effect of One- and Two-Electron Reduction of Terbium(III) Double-Decker Phthalocyanine on Single-Ion Magnet Behavior and NIR Absorption.

Reduction of terbium(III) double-decker phthalocyanine, TbPc (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN){Tb(Pc)}·2.5CHCl (2) containing the dianionic Pc macrocycles, whereas a stronger NaCpCo(CO) reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na)}{(Pc)Tb(Pc)} (3) containing the Pc radical trianionic macrocycle. Isolated pairs of the {Tb(Pc)} anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak π-orbitals overlapping in all three directions.

Comparative Study of Electrical Conduction and Oxygen Diffusion in the Rhombohedral and Bixbyite LnMoO (Ln = Er, Tm, Yb) Polymorphs.

Electrical conduction and oxygen diffusion mobility in the bixbyite ( Ia3̅) and rhombohedral ( R3̅) polymorphs of the LnMoO (Ln = Er, Tm, Yb; Δ = δ, δ1, δ2; δ1 > δ2) heavy lanthanide molybdates, belonging to new, previously unexplored classes of potential mixed (ionic-electronic) conductors, have been studied in the range of 200-900 °C. The oxygen self-diffusion coefficient in bixbyite ( Ia3̅) YbMoO phase estimated by the temperature-programmed heteroexchange with CO was shown to be much higher than that for rhombohedral ( R3̅) RI (with large oxygen deficiency) and ( R3̅) RII (with small oxygen deficiency) LnMoO (Ln = Tm, Yb; Δ = δ1; δ1 > δ2) oxides. According to the activation energy for total conduction in ambient air, 0.

Electronic Communication between S=1/2 Spins in Negatively-charged Double-caged Fullerene C Derivative Bonded by Two Single Bonds and Pyrrolizidine Bridge.

Radical anion salt {cryptand[2.2.2] (K )} (bispheroid) ⋅3.

FTIR spectroscopic study of the interaction between NH and DMSO in Nafion.

Nafion-NH membranes plasticized with dimethyl sulfoxide (DMSO and DMSO-d) have been investigated at room temperature using the vacuum ATR-FTIR and FTIR absorption spectroscopic technique in the range 50-4000 cm. The amount of the plasticizer corresponds to the molecular ratio n = DMSO/NH = 2.7-13.

Orientational dependencies of dynamics and relaxation of multiple quantum NMR coherences in one-dimensional systems.

Dynamics and relaxation, or decoherence, of multiple quantum (MQ) coherences are investigated experimentally and theoretically for different orientations of a single crystal of fluorapatite with respect to the external magnetic field. Dynamics of MQ coherences is studied as a function of the preparation period of the MQ NMR experiment. Their relaxation, or decoherence, during the evolution period is also investigated.

The instrument for electrochemical noise measurement of chemical power sources.

Instrumentation for the electrochemical noise measurement of chemical power sources is considered in this work. A high resolution NM-5 instrument based on a 32 bit "analog to digital" converter is tested with different objects-a passive resistor and RC-circuits as well as with several electrochemical systems-lithium batteries and hydrogen-air fuel cells. The possibility of low thermal noise measurement down to the level of 1 Ω by application of this instrument is shown.

Antioxidant Properties of Fullerene Derivatives Depend on Their Chemical Structure: A Study of Two Fullerene Derivatives on HELFs.

Oxidative stress is a major issue in a wide number of pathologies (neurodegenerative, cardiovascular, immune diseases, and cancer). Because of this, the search for new antioxidants is an important issue. One of the potential antioxidants that has been enthusiastically discussed in the past twenty years is fullerene and its derivatives.

Simulation of Field Assisted Sintering of Silicon Germanium Alloys.

We report a numerical study of the field assisted sintering of silicon germanium alloys by a finite element method, which takes into account contact resistances, thermal expansion and the thermoelectric effect. The distribution of electrical and thermal fields was analyzed numerically, based on the experimental data collected from spark plasma sintering (SPS) apparatus. The thermoelectric properties of Si-Ge used within the simulation were considered as the function of density and the sintering temperature.