Survey of ligand field parameters of strong field d complexes obtained from the g matrix

Using a newly proposed approach involving an internally consistent set of equations, the ligand field parameters Δ/ξ, V/ξ and k are obtained from literature values of the g matrix for strong field d⁵ systems of various conformations in which |Δ/ξ|≤10. Qualitative analysis of the observed results is done using the Angular Overlap Model, AOM.     

New analytical expressions,symmetry relations and numerical solutions for the rotational overlap integrals

In this article, extremely simple analytical formulas are obtained for rotational overlap integrals which occur in integrals over two reduced rotation matrix elements. The analytical derivations are based on the properties of the Jacobi polynomials and beta functions. Numerical results and special values for rotational overlap integrals are obtained by using symmetry properties and recurrence relationships for reduced rotation matrix elements. The final results are of surprisingly simple structures and very useful for practical applications. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Effective medium representation and complex modes in 3D periodic metamaterials made of cubic resonators with large permittivity at mid-infrared frequencies

We review some of the techniques that lead to the effective medium representation of a three-dimensional (3D) periodic metamaterial. We consider a 3D lattice of lead telluride cubic resonators at mid-infrared (MIR) frequencies. Each cubic resonator is modeled with both an electric and a magnetic dipole, through a method called the dual dipole approximation. The electric and magnetic polarizabilities of a cubic resonator are computed via full-wave simulations by mapping the resonator's scattered field under electric/magnetic excitation only to the field radiated by an equivalent electric/magnetic dipole. We then analyze the allowed modes in the lattice, with transverse polarization and complex wavenumber, highlighting the attenuation that each mode experiences after one free space wavelength. We observe the presence of two modes with low attenuation constant, dominant in different frequency ranges, able to propagate inside the lattice: this allows the treatment of the metamaterial as a homogeneous material with effective parameters, evaluated by using various techniques. We then show that the metamaterial under analysis allows for the generation of artificial magnetism (i.e., relative effective permeability different than unity, including negative permeability with low losses) at MIR frequencies.     

Relation between structure and enthalpy for stacking interactions of aromatic molecules

An approximately linear correlation has been found between the enthalpy of complexation and the area of overlap of the chromophores using published structural and thermodynamical data on the self- and hetero-association of aromatic molecules measured under similar solution conditions. This finding is consistent with the assumption that short-range van-der-Waals forces dominate over other contributions to the enthalpy of stacking of aromatic molecules. It provides a ‘model-independent’ approach for a priori estimation of the enthalpy of aromatic–aromatic stacking interactions from knowledge of the structural properties or vice versa.     

Investigation of a UV-laser generated waveguide in a planar polymer chip using an improved interferometric method

Polymeric integrated-optical waveguides are prepared in a planar polymer chip by UV-laser lithographic methods. The waveguide samples are irradiated by an excimer laser at a wavelength Λ=248 nm with various irradiation parameters (different fluencies and irradiation doses). Mach-Zehnder interferometer is employed and the refractive index depth profiles of the waveguide samples are obtained. This profile covers two regions having exponential and Gaussian shapes. The model field distributions strongly depend on the refractive index of each region. The mode field distribution and the effective mode indices for each region have been calculated on the basis of a theoretical model and the experimentally measured data.     

An evaluation method for measuring SPL and mode shape of tire cavity resonance by using multi-microphone system

This paper presents an evaluation method for measuring the sound pressure level and mode shapes of tire cavity resonance by using a multi-microphone system. Two commercial tires were evaluated to compare abilities of noise suppression by means of this method in the range of the first resonance from 200 to 260 Hz. One tire was a special tire that suppresses tire cavity resonance with polyurethane foam mounted on the tire’s inner liner. The other tire was a normal tire with no polyurethane foam. The mode shape change from vertical to horizontal direction in both tires. However, the sound pressure level of the special tire was lower than the normal tire at all frequencies.     

Dynamics of the rotational degrees of freedom in an undercooled crystal of cyanoadamantane

Results of molecular dynamics are presented for a simple model of cyanoadamantane crystal. Rotator cubic phase was simulated over a wide range of temperatures. In this system, glass formation is not induced by quenched diluted disorder, but it occurs similarly to conventional glasses. Simulations have shown that the system evolves from free small-step rotational diffusion to jump like motion. The results obtained with this model are used to discuss the validity of the Mode Coupling Theory (MCT) predictions.     

联吡啶[3,2-a：2’,3-c]-7-氮杂-吩嗪铜(I)配合物的合成、表征及其与DNA的相互作用

合成了邻菲罗啉衍生物联吡啶[3,2-a:2',3'-c]-7-氮杂-吩嗪(dpapz)及其铜(I)配合物[Cu(dpapz)₂]PF₆, 利用核磁共振氢谱(¹H NMR), 傅里叶变换红外(FTIR)光谱, 高分辨质谱(HR ESI-MS)等对合成的化合物进行了表征.采用紫外-可见吸收光谱,荧光光谱, DNA熔解温度实验和循环伏安方法研究了dpapz和[Cu(dpapz)₂]PF₆与小牛胸腺DNA(CT DNA)的相互作用. 配体dpapz与小牛胸腺DNA(CT DNA)作用时未观察到吸收峰红移并且减色效应较小(<30%), 且DNA熔解温度也上升较小(ΔT_m=7.8 ℃), 说明dpapz以沟槽结合的方式与CT DNA相互作用. 而[Cu(dpapz)₂]PF₆与CT DNA作用时, 可观测到较小的吸收峰红移(2-3 nm)和较大的减色效应(>50%), 同时DNA熔解温度上升较大(ΔT_m=11.1 ℃), 表明[Cu(dpapz)₂]PF₆以静电相互作用和部分扦插的方式与DNA结合. 溴乙锭(EB)荧光竞争实验和循环伏安实验进一步证实了这一结论. 配体dpapz和[Cu(dpapz)₂]PF₆与DNA的结合常数分别为2.88×10⁵和5.32×10⁵ mol·L^-1. 光照条件下, [Cu(dpapz)₂]PF₆产生单重态氧的能力与dpapz相当, 但产生超氧负离子自由基的能力要弱于dpapz. 活性氧猝灭实验表明, 超氧负离子自由基、单重态氧和羟基自由基均参与了dpapz和[Cu(dpapz)₂]PF₆对DNA的光损伤作用. [Cu(dpapz)₂]PF₆对DNA的亲和性要高于对dpapz的, 使得[Cu(dpapz)₂]PF₆对质粒DNA的光损伤效率明显强于dpapz.     

石墨烯能带中的重叠矩阵效应:Tight-Binding方法在模拟中的研究

采用紧束缚方法计算了石墨烯的价带(π)和导带(π*),考虑了非正交基矢下重叠矩阵效应,重叠积分参量s越小,导带越靠近费米面,而价带越远离费米面.在重叠积分参量s≤0.1时,基本保持了原子在实际空间中重叠所引起的能带的改变,太大(s=0.4)则会导致物理上失效.计算了石墨烯的能态密度,在费米面ε=0处(对应Dirac点)的能态密度为零,并且在Dirac点附近呈线性变化.