Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.     

极化子导电到能带导电的转变

采用交流法测量大功率商用钛酸钡(BT)陶瓷加热器的电阻和加热功率随温度的变化关系.结果显示,BT陶瓷的电导特性在80℃附近出现了明显的转变,从低温时的极化子跳跃导电转变为高温时的能带导电,此时,电阻出现极小值,而加热功率出现极大值.     

Assignment of conformation-sensitive near-infrared bands in high-spin ferrous haemoproteins. Low-temperature magnetic circular dichroism data

An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD) spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand (i.e. myoglobin, haemoglobin and horseradish peroxidase). Received: 4 February 1997 / Accepted: 1 May 1997     

Tunable properties of light propagation in photonic liquid crystal fibers

Tunable properties of light propagation in photonic crystal fibers filled with liquid crystals, called photonic liquid crystal fibers (PLCFs) are presented. The propagation properties of PLCFs strongly depend on contrast between refractive indices of the solid core (pure silica glass) and liquid crystals (LCs) filing the holes of the fiber. Due to relatively strong thermo-optical effect, we can change the refractive index of the LC by changing its temperature. Numerical analysis of light propagation in PLCF, based on two simulation methods, such as finite difference (FD) and multipole method (MM) is presented. The numerical results obtained are in good agreement with our earlier experimental results presented elsewhere [1].     

Tight-binding method modelling of photonic crystal waveguides

We present here a tight-binding-like modelling of two-dimensional (2D) photonic crystals (PCs). Adopted from solid-state physics, the concept of generalized Wannier functions is used to construct a localized state basis that allows a parameter-free ab initio study of defects in PCs. We demonstrate here for a 2D triangular lattice of dielectric rods in air, the existence of this localized basis and the possibility to study large scale complex dielectric structures deviating from periodicity. Specific numerical simulations on a split waveguide embedded in this triangular lattice are performed, and they demonstrate the superiority of this method over plane wave based techniques.     

About the Notion of Semiring of Sets

We introduce a generalized notion of semiring and prove that all known properties that semirings have according to the old definition are preserved.     

A method for determining optical constants, dimensions, and concentrations of “soft” absorbing particles in the brightening band region

We investigate the possibilities of creating a method for estimating the optical constants, dimensions, and concentrations of “soft” absorbing particles by applying a theoretical analysis of the angular dependence of the intergrated indicatrix, overall characteristics of light scattering, and absorption on the phase shift and diffraction parameter of particles in the brightening band region. We show that using the investigated optical characteristics, it is possible to determine the unknown parameters of a suspension from experimental data. Institute of Biophysics, Siberian Branch of the Russian Academy of Sciences, Akademgorodok, Krasnoyarsk, 660036, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 807–812, November–December, 1997.     

Asymptotic behavior of energy band associated with a negative energy level

The mathematical foundation of the tight binding approximation is given. If ₀ is a negative energy level of a real potentialq, then there exists an energy band for a one-dimensional chain with period 2T of the same atoms which lies near ₀. We study this band whenT tends to infinity.On leave of absence from the Department of Physics, Leningrad State University, Leningrad, USSR.     

Conformations, Energy and Spectral Characteristics of 2,3-Trimethylene- and 2,3-Pentamethylene-3,4-dihydro-4-quinazolinones

Quantum-chemical calculations and IR spectroscopy were used to study the conformations as well as the energy and spectral characteristics of 2,3-trimethylene- and 2,3-pentamethylene-3,4-dihydro-4-quinazolinones. The shift of -electron density from the heterocyclic system to the carbonyl group and, thus, the proton affinity of the oxygen atom of this group increase with expansion of the bond angle at the nitrogen atom in going from a five-membered to seven-membered ring.