π-Electron Densities in Molecules ΦCHX1X2 and Correlation with the Intensity of the 00 Band of the Secondary Transition

In molecules such as ΦX₁X₂X₃the intensity of the secondary transition of the benzene chromophore, strongly depends on long range interactions involving a σ·π coupling between orbitals belonging to the C_α-X bonds, and the πΦ system. Such a coupling distorts the symmetry of the π_Φ system(1–5). The secondary transition (towards 260 nm) which is forbidden when the symmetry is D_6h - as in the benzene molecule itself where only the low intensity progression A isobserved - becomes all the more allowed as the substituent is able to distort the πΦ cloud towards a C_2V symmetry. A new progression called B is observed. Its intensity is usually evaluated by the measure of its 00 band. The distorsion of symmetry arises because of the π donating or π withdrawing electronic effects of the substituent(1–7). These phenomena have been explained on the ground of a V shaped function(l) : ε₀₀ = f(σ), where σ is a parameter linked to the electronic effects of the substituents. When the whole substituent is a π donating one, its π donating effect is lowered by an increase of the electron attracting power of the groups X : the perturbation of the D_6h symmetry is lessened and ε₀₀ decreases. On the contrary, when the whole substituent is a π withdrawing one, an increase of the withdrawing power of the groups X increases the withdrawing power of the whole substituent, the distorsion of the D6h symmetry increases and ε₀₀ increases too. The minimum of the V shaped curve correspond to the species for which the π donating tendency of the aliphatic part of the substituent is quenched by the electron withdrawing tendency of the groups X. The D_6h symmetry of the πΦ cloud is restored. The transition is forbidden and the system A only is observed.     

Influence of ro-vibrational and isotope effects on the dynamics of the C(3 P)+ OD(X 2Π) → CO(X 1 Σ+) + D(2 S) reaction

The C(³ P)+OD(X ²Π) reaction has been studied by means of quantum mechanical real wave packet (RWP) and quasiclassical trajectory (QCT) methodologies on the ground potential energy surface of Zanchet et al. [J. Phys. Chem. A 110, 12017 (2006)]. Initial state selected total reaction probabilities at J?=?0 total angular momentum have been calculated for a wide range of collision energies. Product state-resolved integral cross-sections at selected collision energies and excitation functions have been determined from the RWP calculations using the J-shifting approximation and from QCT calculations. State-specific and thermal rate coefficients have been calculated using both methodologies up to 500 K. The effect of reagent rotational excitation on the dynamics for the C(³ P)+OH(X ²Π) and C(³ P)+OD(X ²Π) reactions has been investigated and interesting discrepancies between the QCT and RWP results have been found. The RWP results are found to be in an overall good agreement with the corresponding QCT results, although the QCT integral cross-section and rate coefficients are slightly smaller than those obtained from the RWP calculations.     

Effect of the a 1(1260) resonance on the ρ → 4π and ω,ø → 5 π decay widths

The contribution of the a ₁(1260) meson to the ρ(770) → 4π,ω(782) → 5π, and ø(1020) → 5π decay amplitudes is analyzed on the basis of the chiral model of pseudoscalar, vector, and axial-vector mesons that is based on generalized hidden local symmetry and which is supplemented with terms induced by the Wess-Zumino anomaly. It is shown that the intensities of the above decays are enhanced upon taking into account the a ₁ meson in intermediate states. For the a ₁-meson mass $m_{a_1 } $ varying from 1.23 GeV to $m_p \sqrt 2 = 1.09 GeV$ , the enhancement factor grows from 1.3 to 1.9.     

Influence of γ-irradiation on the optical and electrical properties of Se(0.85) Te(0.15) films

Abstract

Se_(0.85) Te_(0.15) films were prepared by thermal evaporation under vacuum on glass substrate. The optical and electrical properties of as deposited and irradiated Se_(0.85) Te_(0.15) films with different γ-doses are reported.

The optical constants (absorption coefficient (α), extinction coefficient (k), refractive index (n) and dielectric constants (?, ?) of unirradiated and irradiated films were calculated. The value of allowed direct optical energy gap of Se_(0.85) Te_(0.15) films increased from 1.47 eV. to 1.72 eV. with increasing the γ-doses to 2.5 Mrad. The irradiated films have lower resistivity than those as deposited films (unirradiated). The activation energy (ΔE) increases from 0.72 eV. to 0.86 eV. with increasing γ-doses to 2.5 Mrad.     

Influence of structure disorders and temperaturesof systems on the bio-energy transport in proteinmolecules (Ⅱ)

The influence of molecular structure disorders and physiological temperature on the states and properties of solitons as transporters of bio-energy are numerically studied through the fourth-order Runge-Kutta method and a new theory based on my paper [Front. Phys. China, 2007, 2(4): 469]. The structure disorders include fluctuations in the characteristic parameters of the spring constant, dipole-dipole interaction constant and exciton-phonon coupling constant, as well as the chain-chain interaction coefficient among the three channels and ground state energy resulting from the disorder distributions of masses of amino acid residues and impurities. In this paper, we investigate the behaviors and states of solitons in a single protein molecular chain, and in α-Helix protein molecules with three channels. In the former we prove first that the new solitons can move without dispersion, retaining its shape, velocity and energy in a uniform and periodic protein molecule. In this case of structure disorder, the fluctuations of the spring constant, dipole-dipole interaction constant and exciton-phonon coupling constant, as well as the ground state energy and the disorder distributions of masses of amino acid residues of the proteins influence the states and properties of motion of solitons. However, they are still quite stable and are very robust against these structure disorders, even in the presence of larger disorders in the sequence of masses, spring constants and coupling constants. Still, the solitons may disperse or be destroyed when the disorder distribution of the masses and fluctuations of structure parameters are quite great. If the effect of thermal perturbation of the environment on the soliton in nonuniform proteins is considered again, it is still thermally stable at the biological temperature of 300 K, and at the longer time period of 300 ps and larger spacing of 400 amino acids. The new soliton is also thermally stable in the case of motion over a long time period of 300 ps in the region of 300–320 K under the influence of the above structure disorders. However, the soliton disperses in the case of a higher temperature of 325 K and in larger structure disorders. Thus, we determine that the soliton’s lifetime and critical temperature are 300 ps and 300–320 K, respectively. These results are also consistent with analytical data obtained via quantum perturbed theory. In α-Helix protein molecules with three channels, results obtained show that these structure disorders and quantum fluctuations can change the states and features of solitons, decrease their amplitudes, energies and velocities, but they still cannot destroy the solitons, which can still transport steadily along the molecular chains while retaining energy and momentum when the quantum fluctuations are small, such as in structure disorders and quantum fluctuations of and and . Therefore, the solitons in the improved model are quite robust against these disorder effects. However, the solitons may be dispersed or disrupted in cases of very large structure disorders. When the influence of temperature on solitons is considered, we find that the new solitons can transport steadily over 333 amino acid residues in the case of motion over a long time period of 120 ps, and can retain their shapes and energies to travel forward along protein molecules after mutual collision of the solitons at the biological temperature of 300 K. Therefore, the soliton is also very robust against thermal perturbation of the α-helix protein molecules at 300 K. However, the soliton disperses in cases of higher temperatures at 325 K and in larger structure disorders. Thus, their critical temperature is about 320 K. When the effects of structure disorder and temperature are considered simultaneously, the soliton has high thermal stability and can transport for a long time along the protein molecular chains while retaining its amplitude, energy and velocity, even though the fluctuations of the structure parameters and temperature of the medium increase continually. However, the soliton disperses in the larger fluctuations of and at T=300 K, and at temperatures higher than 315 K when the fluctuations are and . This means that the critical temperature of the soliton is only 315 K in this condition. In a word, we can conclude from the above investigations that the soliton in the improved model is very robust against the structure disorders and thermal perturbation of proteins at the biological temperature of 300 K in α-helix protein molecules, and is a possible bio-energy transport carrier; the improved model is a possible candidate for the mechanism of this transport.      

Atomic and electronic properties of tert-butanol on the Si(001)-(2×1) surface

The atomic and electronic properties of the adsorption of tert-butanol [(CH₃)₃OH] molecule on the Si(001)-(2×1) surface have been studied by using the ab-initio density functional theory (DFT) based on pseudopotential approach. We have found that tert-butanol bonded the Si(001) surface by oxygen atom, cleaving a O–H bond and producing a Si-H bond and tert-butoxy surface species. We have also investigated the influence of chemisorption of tert-butanol on the electronic structure of the clean Si(001)-(2×1) surface. Two occupied surface states situated entirely below the bulk valence band maximum have been identified, which means that the clean Si(001)-(2×1)surface was passivated by the chemisorption of tert-butanol. In order to explain the nature of the surface components we have also plotted the total and partial charge densities at the [`(K)]\bar{K} point of the surface Brillouin zone (SBZ).     

Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

The contributions of Co²⁺ and Nb⁴⁺ ions to the high-frequency dynamic magnetic susceptibility of the Co₂[Nb(CN)₈] · 8H₂O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.     

Confirmation of the X(1835) and observation of the resonances X(2120) and X(2370) in J/ψ→γπ+π-η'

With a sample of (225.2±2.8)×10(6) J/ψ events registered in the BESIII detector, J/ψ→γπ(+)π(-)η(') is studied using two η(') decay modes: η(')→π(+)π(-)η and η(')→γρ(0). The X(1835), which was previously observed by BESII, is confirmed with a statistical significance that is larger than 20σ. In addition, in the π(+)π(-)η(') invariant-mass spectrum, the X(2120) and the X(2370), are observed with statistical significances larger than 7.2σ and 6.4σ, respectively. For the X(1835), the angular distribution of the radiative photon is consistent with expectations for a pseudoscalar.     

Influence of silver on the galvanomagnetic properties and energy spectrum of mixed (Bi1− x Sbx)2Te3 crystals

An investigation is made of the temperature dependences of the resistivity in the range 4.2–300 K, the Hall effect, and the Shubnikov-de Haas effect in magnetic fields up to 40 T in (Bi_{1? x} Sb_x)₂Te₃Ag_y single crystals (0 ≤ x ≤ 0.75). Doping (Bi_{1? x} Sb_x)₂Te₃ crystals with silver showed that in Sb₂Te₃ and (Bi_{1? x} Sb_x)₂Te₃ crystals unlike Bi₂Te₃ silver exhibits acceptor properties. The angular and concentration dependences of the Shubnikov-de Haas effect were studied in (Bi_{1? x} Sb_x)₂Te₃Ag_y. It was established that the anisotropy of the ellipsoids of the upper valence band in Bi_0.5Sb_1.5Te₃ remains unchanged as a result of silver doping.     

Fundamental Role of the H-Bond Interaction in the Dissociation of NH_{3} on Si(001)-(2×1)

Further insight into the dissociative adsorption of NH_{3} on Si(001) has been obtained using a combined computational and experimental approach. A novel route leading to the dissociation of the chemisorbed NH_{3} is proposed, based on H-bonding interactions between the gas phase and the chemisorbed NH_{3} molecules. Our model, complemented by synchrotron radiation photoelectron spectroscopy measurements, demonstrates that the low temperature dissociation of molecular chemisorbed NH_{3} is driven by the continuous flux of ammonia molecules from the gas phase.     

Determination of the electron phonon coupling and the superconducting gap in β-(BEDT-TTF)2X crystals (X=I3, IAuI)

We performed point-contact and tunneling measurements on the organic superconductors -(BEDT-TTF)₂I₃ and -(BEDT-TTF)₂IAuI, in the normal and superconducting states. The point-contact measurement in the normal state provides the Eliashberg function ²()F (). This function has maxima at 4 and 15 mV, as well as a sharp peak at 1 mV which seems to indicate a very soft phonon strongly coupled to the electrons. The measurements in the superconducting state provide the superconducting gap, which for the tunneling measurements has a value 2/k_B T_c4, just slightly above the BCS value.     

A Comparative Study of the Growth of Cr on (110)TiO2 Rutile, (0001) α-Al2O3 and (100)SrTiO3 Surfaces

Thin Cr films were deposited on single crystal -Al₂O₃, SrTiO₃ and TiO₂ (rutile) substrates under ultrahigh vacuum conditions using molecular beam epitaxy (MBE). The growth behavior and thermal stability of the films were investigated with scanning tunneling microscopy (STM), X-ray phototelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and transmission electron microscopy (TEM). Cr grew as 3D clusters on all substrates. For all three Cr/oxide systems a strong temperature dependent interfacial reaction was observed. The results suggested that these reactions depended greatly on thermodynamics and on transport properties in the oxide substrates.     

Effect of the Oxygen Content on the Metal‒Insulator Transition and on the Spin State of Co3+ Ions in the Layered NdBaCo2O5 + δ Cobaltite (0.37 ≤ δ ≤ 0.65)

JETP Letters - The effect of the oxygen content δ in layered NdBaCo2O5 + δ cobaltite, where 0.37 ≤ δ ≤ 0.65, on the metal?insulator transition, as well as on the...     

Adsorption and diffusion of an Au atom and dimer on a θ-Al2O3 (001) surface

With density-functional calculations we have investigated adsorption and diffusion of an Au atom and an Au₂ dimer on a θ-Al₂O₃(001) surface. The surface structure of θ-Al₂O₃(001) has an armchair-like configuration containing flat and trench areas and the Au_n (n = 1 or 2) cluster prefers to adsorb on the flat area. A single Au atom adsorbs on an O–Al bridge site with adsorption energy 0.35 eV, whereas an Au₂ dimer bonds to the oxide with adsorption energy 0.78 eV, with one Au coordinated singly to a surface O. Formation of Au₂ from Au₁ is favored, with a negligible energy barrier. The calculated energy barriers for diffusion indicate that an Au atom diffuses more rapidly than an Au₂ dimer but both prefer to diffuse anisotropically, along the flat area of the θ-Al₂O₃(001) surface.     

Influence of Pressure on the Annealing Process of β-Ca_2SiO_4(C_2S) in Portland Cement

Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-speciality grout. Dicalcium silicate(Ca_2SiO_4) is the primary constituent of a number of different types of cement. The β-Ca_2SiO_4 phase is metastable at room temperature and will transform into γ-Ca_2SiO_4 at 663 K. In this work, Portland cement is annealed at a temperature of 950 K under pressures in the range of 0–5.5 GPa. The high pressure experiments are carried out in an apparatus with six anvil tops. The effect of high pressure on the obtaining nano-size β-Ca_2SiO_4(C_2 S) process is investigated by x-ray diffraction and transmission electron microscopy. Experimental results show that the grain size of the C_2 S decreases with the increase of pressure. The volume fraction of the C_2 S phase increases with the pressure as the pressure is below3 GPa, and then decreases(P 3 GPa). The nano-effect is very important to the stabilization of β-Ca_2SiO_4. The mechanism for the effects of the high pressure on the annealing process of the Portland cement is also discussed.     

Determination of Ofloxacin using a Highly Selective Photo Probe Based on the Enhancement of the Luminescence Intensity of Eu3+—Ofloxacin Complex in Pharmaceutical and Serum Samples

A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of ofloxacin was developed. At pH 5.1 the ofloxacin enhances the luminescence intensity of the Eu³⁺ ion in Eu³⁺- ofloxacin complex at λ_ex = 365 nm. The produced luminescence intensity of Eu³⁺-ofloxacin complex was in proportional to the concentration of ofloxacin. The working range for the determination of ofloxacin was 5.0 × 10^-9–5.0 × 10^-6 mol L^-1 with lower detection limit (LOD) and quantitative detection limit (QDL) of 3 × 10^-9 and 9 × 10^-9 mol L^-1, respectively. The enhancement mechanism of the luminescence intensity in the Eu³⁺-ofloxacin system has been also explained. The method revealed good selectivity for ofloxacin in the presence of coexisting substances and used successfully for the assay of ofloxacin in pharmaceutical preparations and serum. A comparison with other standard methods was also discussed.     

Influence of pulse duration on the doping quality in laser chemical processing (LCP)—a simulative approach

The laser chemical processing (LCP) technique for the local doping of crystalline silicon solar cells is investigated. Here, a liquid jet containing a dopant source acts as a waveguide for pulsed laser light, which results in the melting and subsequent doping of the silicon surface. Typical LCP pulse durations are in the 15 ns range, giving satisfactory results for specific parameter settings. While great potential is assumed to exist, optimization of the pulse duration has until now not been deeply investigated, because it is hard to change this parameter in laser systems. Therefore, this paper accesses the influence of the pulse duration by a simulative approach. The model includes optics, thermodynamics, and melt dynamics induced by the liquid jet and dopant diffusion into the silicon melt. It is solved by coupling our existing finite differences Matlab-code LCPSim with the commercial fluid flow solver Ansys Fluent. Simulations of axial symmetric single pulses were performed for pulse durations ranging from 15 ns to 500 ns. Detailed results are given, which show that for longer pulse durations lateral heat conduction significantly homogenizes the inhomogeneous dopant distribution caused by the speckled intensity profile within the liquid jet cross section. The melt expulsion by the liquid jet is low enough that a sufficiently doped layer remains after full resolidification for all pulse durations. Last, temperature gradients are evaluated to give an indication on the amount of laser damage induced by thermal stress.     

Influence of dehydration on the electron spin resonance in the Cu3[W(CN)8]2(Pyrimidine)2 · 8H2O molecular magnet

The influence of dehydration on the electron spin resonance spectra in the Cu₃[W(CN)₈]₂(pyrimidine)₂ · 8H₂O molecular magnet has been found. It has been established that two ferromagnetic phases with the Curie temperatures of ～12–17 and ～50 K, which correspond to two different lines of the ferromagnetic resonance, are present in crystals. Dehydration leads to increasing the Curie temperature of the low-temperature phase from 12 to 17 K and to varying the temperature dependences of the spectrum parameters of the high-temperature phase (the resonant field and the width line).     

Analysis of the high-resolution 5-μm spectra of the ν4(E) and 2ν2(A1) bands of 12CD3F

The infrared spectrum of the ν₄(E) and 2ν₂(A₁) bands of ¹²CD₃F have been recorded and deconvolved to ∼0.005 cm⁻¹ resolution. More than 1890 transitions have been assigned to one of the 37 subbands (−18≤KΔK≤+18) comprising the spectrum of the ν₄ band with a maximum assigned J value of 41. The weak 2ν₂(A₁) band has never been reported in the infrared prior to this work. A total of 358 transitions in K ≤ 8 subbands have been assigned to the 2ν₂ band. The two bands are members of the 24 interacting state complex of ¹²CD₃F spectra in the 5-μm region. The ν₄ and 2ν₂ spectra are highly perturbed, exhibiting local and global resonances. Effective parameters of the two bands were obtained by fitting the data in a restricted manner leaving out the obviously perturbed transitions. The effective parameters, the identification of the different resonances affecting the bands, and estimates of some of the coupling constants are reported.