Relationships between geometrical and electronic structures and optical properties of 1,8-naphthosultam substituents and derivatives: TDDFT study

Geometrical and electronic structure and optical properties of several substituents and derivatives of 1,8-naphthosultam are studied by quantum-chemical DFT and TDDFT. It is found that the substituents –NO₂, –CF₃, and –N(CH₃)₂ affect the geometrical and electronic structure the most. It is shown that the Stokes shift is greatest (≈260 nm) for compounds with the strong donor substituent –N(CH₃)₂, while strong acceptor substituents provide a quite small Stokes shift. The dependence of the Stokes shift on the difference in energies of the frontier orbitals of the ground and excited states of molecules is found. Of the 1,8-naphthosultam substituents considered, compounds with –N(CH₃)₂ substituent, which emit in the biological window region, can be advised for use in optical bioimaging. The results can be used as a basis for the development and creation of new functional materials and biologically active compounds.     

Computational design and screening of promising energetic materials: Novel azobis(tetrazoles) with ten catenated nitrogen atoms chain

Density functional theory methods were used to study on 2 N10 compounds, 1,1′‐azobis(tetrazole) and 1,1′‐azobis(5‐methyltetrazole). We systematically investigated 10 novel substituted azobis(tetrazoles) with 10 catenated nitrogen atoms and various energetic groups (–CF₃ 1 , –C(NO₂)₃ 3 , –N₃ 5 , –NH₂ 6 , –NHNH₂ 7 , –NHNO₂ 8 , –NO₂ 9 , –OCH₃ 10 , –OH 11 , –ONO₂ 12 ). The optimized geometry, frontier molecular orbitals, electrostatic potential, Infrared and nuclear magnetic resonance spectrum were calculated for inspecting the molecular structure and stability as well as chemical reactivity. The effects of different substituents on the density, enthalpy of formation, heat of explosion, detonation velocity and pressure, and sensitivity of the azobis(tetrazole) derivatives have been investigated. Compound 9 with nitro was found to have remarkable detonation performances (D = 9.61 km/s, P = 42.14 GPa), which are close to the excellent explosive CL‐20. Results show that compounds 1 , 3 , 4 , 7 , 9 , 11, and 12 have high potential to replace RDX. It is surprising that compounds 1 , 3 , 9, and 12 possess better energetic properties than HMX. These novel substituted azobis(tetrazoles) with unique N10 structure may be promising candidates of HEDMs with outstanding performance and acceptable sensitivities.     

Theoretical study on the electronic structures and phosphorescent properties of four Ir(III) complexes with different substituents on the ancillary ligand

The geometry structures, electronic structures, absorption and phosphorescent properties of four Ir(III) complexes {[(F₂-ppy)₂Ir(pta-X)], where F₂-ppy = (2,4-difluoro)phenylpyridine; pta = pyridine-1,2,4-triazole; X = –CF₃; –H; –CH₃; –N(CH₃)₂}, are investigated using the density functional method. The results reveal that the electron-accepting group –CF₃ has no obvious effect on absorption and emission properties, while the substitutive group –N(CH₃)₂ with strong electron-donating ability has obvious effect on the emission properties. The mobility of hole and electron were studied computationally based on the Marcus–Hush theory. Calculations of ionisation potential and electron affinity were used to evaluate the injection abilities of holes and electrons into these complexes. We hope that this theoretical work can provide a suitable guide to the future design and synthesis of novel phosphorescent materials for use in the organic light-emitting diodes.     

Theoretical investigation of a series of bis(1H-tetrazol-5-yl)furazan and bis(1H-tetrazol) derivatives as high-energy-density materials

Using density functional theory (DFT), a series of bis(1H-tetrazol-5-yl)furazan and bis(1H-tetrazol) derivatives with different linkages and substituents are investigated theoretically as potential high-energy-density materials (HEDMs). The heat of formation (HOF), detonation properties, natural bond orbital (NBO) and thermal stabilities are calculated and reported. The introduction of a furazan ring, an –N=N– bridge group and an –N₃ substituent is beneficial to increase the HOF of the title compounds. NBO analysis shows that there are electronic delocalisation effects among the bridge groups, furazan and tetrazole rings, and substituted groups. The conjugation effects and electronic transitions are influenced by the different linkages and substituents. The estimated detonation velocities and pressures indicate that the –ONO₂ and –NO₂ groups and the –N=N– linkage play important roles in enhancing the detonation properties. The bond dissociation energy (BDE) calculations reveal that the –NO₂ group is the substituent group which causes the least thermal stability. The bond between the substituent group and the tetrazole ring is the weakest bond in the title molecules. Considering the detonation performance and the thermal stability, 17 compounds may be promising candidates for HEDMs with good performance. Eight of them (A3, A4, C3, C4, D3, F3, G1 and G3) have better detonation properties than HMX.     

Theoretical studies on 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) and its derivatives

In this work, a set of derivatives of 2‐(5‐amino‐3‐nitro‐1,2,4‐triazolyl)‐3,5‐dinitropyridine (PRAN) with different energetic substituents (?N₃, –NO₂, –NH₂, –NF₂) have been studied at the Becke, three‐parameter, Lee–Yang–Parr/aug‐cc‐pvdz, Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d), Becke, three‐parameter, Perdew 86/6‐31G(d), and Becke three‐parameter, Perdew–Wang 91/6‐31G(d,p) levels of density functional theory. The gas‐phase heats of formation were predicted with isodesmic reactions and the condensed‐phase HOFs were estimated with the Politzer approach. The effects of different functionals and basis sets were analyzed. –N₃ and –NO₂ greatly increase while –NH₂ and –NF₂ slightly decrease heats of formation. An analysis of the bond dissociation energies and impact sensitivity shows that all compounds have good stability. The crystal densities (1.82–2.00 g/cm³) computed from molecular packing calculations are big for all compounds and that of the –NF₂ derivative is the largest. All derivatives have higher detonation velocity and detonation pressure than PRAN. Compounds 3 and 4 (R = NO₂ and NF₂) have better performance than hexahydro‐1,3,5‐trinitro‐1,3,5‐trizine and the performance of 4 is quite close to that of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane, they are promising candidates of high energy compounds and worth further investigations. Copyright © 2012 John Wiley & Sons, Ltd.     

Kinetics and mechanism for the oxidation of anilines by ClO2: a combined experimental and computational study

The oxidation of para‐substituted anilines (X–C₆H₄NH₂, X = –CH₃, –H, –Cl, –NO₂) with chlorine dioxide was studied as a means of eliminating these pollutants. The oxidation rate decreases from that for 4‐methylaniline to that for 4‐nitroanilinem in agreement with the Hammett plot; the oxidation kinetics is second order in aniline and first order in ClO₂, for which a possible mechanism is proposed. Liquid chromatography and gas chromatography mass spectrometry results show that benzoquinone is formed as the major intermediate in aniline/ClO₂ oxidation, and the reaction is pH‐dependent as the rate constant increases with increasing pH. To further support our proposed mechanism, Density Functional Theory (DFT) computations at both B3LYP/6‐311 + G(d,p) level with the polarizable continuum model with an integral equation formalism solvation model (i.e., with water) were carried out, showing that activation energy barriers predict the same reactivity trend as shown by the kinetics experiments. Copyright © 2014 John Wiley & Sons, Ltd.     

Barium isotope fractionation during the experimental transformation of aragonite to witherite and of gypsum to barite,and the effect of ion (de)solvation

In this study, we present the experimental results for stable barium (Ba) isotope fractionation (¹³⁷Ba/¹³⁴Ba) during the transformation of aragonite (CaCO₃) and gypsum (CaSO₄·2H₂O) in Ba-bearing aqueous solution to witherite (BaCO₃) and barite (BaSO₄), respectively. The process was studied at three temperatures between 4 and 60?°C. In all cases, the transformation leads to a relative enrichment of the lighter ¹³⁴Ba isotope in the solid compared to the aqueous solution, with ^137/134Ba enrichment factors between –0.11 and ?0.17?‰ for BaCO₃, and –0.21 and –0.26?‰ for BaSO₄. The corresponding mass-dependent ^138/134Ba enrichment factors are ?0.15 to –0.23?‰ for BaCO₃, and –0.28 to –0.35?‰ for BaSO₄. The magnitude of isotope fractionation is within the range of recent reports for witherite and barite formation, as well as trace Ba incorporation into orthorhombic aragonite, and no substantial impact of temperature can be found between 4 and 80?°C. In previous studies, ion (de)solvation has been suggested to impact both the crystallization process of Ba-bearing solids and associated Ba isotope fractionation. Precipitation experiments of BaSO₄ and BaCO₃ using an methanol-containing aqueous solution indicate only a minor effect of ion and crystal surface (de)solvation on the overall Ba isotope fractionation process.     

2H-solid-state-NMR study of hydrogen adsorbed on catalytically active ruthenium coated mesoporous silica materials

²H solid-state NMR measurements were performed on three samples of ruthenium nanoparticles synthesized inside two different kinds of mesoporous silica, namely SBA-3 silica materials and SBA-15 functionalized with –COOH groups and loaded with deuterium gas. The line-shape analyses of the spectra reveal the different deuteron species. In all samples a strong –OD signal is found, which shows the catalytic activity of the metal, which activates the D–D bond and deuterates the –SiOH groups through the gas phase, corroborating their usability as catalysts for hydrogenation reactions. At room temperature the mobility of the –Si–OD groups depends on the sample preparation. In addition to the –Si–OD deuterons, the presence of different types of deuterons bound to the metal is revealed. The singly coordinated –Ru–D species exhibit several different quadrupolar couplings, which indicate the presence of several non-equivalent binding sites with differing binding strength. In addition to the dissociated hydrogen species there is also a dihydrogen species –Ru–D₂, which is attributed to defect sites on the surface. It exhibits a fast rotational dynamics at all temperatures. Finally there are also indications of three-fold coordinated surface deuterons and octahedrally coordinated deuterons inside the metal.     

The influence of the nature of a substituent on the parameters of the intra- and intermolecular interactions in molecules of cross-conjugated ketones

We have quantitatively analyzed the vibronic parameters of two cross-conjugated δ-dimethylaminoketones. The presence of the –N(CH₃)₂, C=O, and –NO₂ groups in the benzene ring has been shown to affect the manifestation of the vibronic parameters of characteristic bands that describe the state (vibrations, types of deformation upon excitation) of polyene systems with aromatic rings. Data on the influence of the nature of the substituent on the parameters of intra- and intermolecular interactions in the examined compounds have been presented.     

Unusual case of desmotropy. Combined spectroscopy (1H-14N NQDR) and quantum chemistry (periodic hybrid DFT/QTAIM and Hirshfeld surface-based) study of solid dacarbazine (anti-neoplastic)

Antineoplastic chemo-therapeutic drug 5-(3,3-dimethyl-1-triazenyl)imidazole-4-carboxamide (Dacarbazine, DTIC), has been studied experimentally in solid state by ¹H-¹⁴N NQDR double resonance at 295 K and theoretically by the Density Functional Theory (DFT)/Quantum Theory of Atoms in Molecules (QTAIM) and Hirshfeld surfaces analysis. Only one set of eighteen resonance frequencies was found in the experiment. This indicates the presence of six inequivalent nitrogen sites: –N(CH₃), –NH₂, –NH- and three –N= (of which one is a ring, two are from triazene) in the DTIC molecule. This contradicts the X-ray data which revealed the multiplication of nitrogen sites due to unusual desmotropism. The averaging of NQR frequencies caused by the fast in NQR time-scale exchange of protons in a double-well potential combined with the oscillations of twisted supramolecular synthons was proposed as a potential mechanism responsible for this apparent contradiction. An effective improvement in the quality of the spectrum reproduction was achieved when the calculations were performed assuming the periodic boundary conditions, BLYP functional, the DNP basis set and taking the 3×3×3 k-point separation. The ordering of the nitrogen sites according to the increasing quadrupole coupling constant (QCC): N(3)<N(2)<N(6)<N(1)<N(4)<N(5) reflects the metabolic pathway of DTIC. Two sites N(5) and N(4) with the highest QCC are responsible for the first step – conversion to MTIC (5-[3-methyl-triazen-1-yl]-imidazole-4-carboxamide) required for effective processes of binding dacarbazine to DNA (demethylation of N(5)), and the second step – fast conversion of MTIC to 5-amino-1H-imidazole-4-carboxamide (AIC; remove –N(4)–N(5)HCH₃). N(5) does not participate in any, while N(4) participates in weak C(2)H⋯N(4) interaction which can be readily broken. The four remaining nitrogen atoms N(1), N(2), N(3) and N(6) participate in strong intermolecular N(1)H⋯N(2) and intramolecular N(3)–H⋯N(6) bonds, which stiffen the crystalline structure.     

IR Photodetectors Based on Isoperiodic Epitaxial Layers of Lead Tin Chalcogenides

Technical Physics - IR photodetectors have been made on Pb/δ-layer/p-Pb1 –xSnxTe1 –ySey/p+-Pb0.8Sn0.2Te/Au and Au/δ-layer/n-Pb1 –xSnxTe1 –ySey(BaF2)/Pb...     

Ceramic Solid Solutions of Li0.17Na0.83TayNb1 –yO3: Thermobaric Synthesis,Microstructure, and Properties

Technical Physics - Ferroelectric ceramic LixNa1 –xTayNb1 –yO3 (x = 0.17, y = 0–0.5) solid solutions with perovskite structure are synthesized for the first time by the...     

Competition of Concentration Narrowing and Power Broadening of a Dark Resonance in a Ladder System of Rubidium Atoms: Specificities of Its Occurrence in Thin Spectroscopic Cells

Optics and Spectroscopy - The effect of electromagnetically induced transparency (EIT) in a three-level ladder system 5S1/2‒5P3/2 –5D5/2 of Rb atoms is investigated. The effect of...     

Aging effect of SiO2 xerogel film on its microstructure and dielectric properties

The properties of porous SiO₂ xerogel film strongly depend on the aging process. The morphology of the surface modified SiO₂ xerogel film pre-aged for 1 hr at 70°C showed a two-dimensional structure. Aging for 12 h at 70°C and successive modification of the film induced some particle growth and a three-dimensional network structure. The microstructure of the modified SiO₂ xerogel films reflects the preformed structure during aging. The surface modification induced the changes of surface coverage from –OC₂H₅ and –OH bonds to –CH₃. However the content of surface chemical species was almost same regardless of aging time. The porosity of the modified sample pre-aged for 12 h at 70°C was 89%. The calculated/measured dielectric constants were 1.31/1.42, respectively     

新型超快探测器性能研究

 为提高强g 场超快辐射探测器抗信号堆积的性能，可采用BaF₂（La）与快的光电器件组合的技术途径。用同步辐射闪烁荧光衰减谱仪和X光激发发射谱仪测量了国产不同掺La浓度的BaF₂晶体抑制快慢成分之比，探讨掺La对抑制慢成分的机理，研究了BaF₂（La）抗辐照性能。并用同步辐射测量BaF₂（La）与GD40Z光电管组成超快辐射探测器的快慢成分抑制比。     

无箔二极管结构设计研究

用数值计算方法研究了无箔二极管中几何结构参量对束流的影响，得出了无箔二极管结构参数选择的部分规律，同时又结合实际给出了一个无箱二级管模型的最佳组合参数．     

Optimisation of stability and charge transferability of ferrocene-encapsulated carbon nanotubes

Ferrocene-encapsulated carbon nanotubes (Fc@CNTs) became promising nanocomposite materials for a wide range of applications due to their superior catalytic, mechanical and electronic properties. To open up new windows of applications, the highly stable and charge transferable encapsulation complexes are required. In this work, we designed the new encapsulation complexes formed from ferrocene derivatives (FcR, where R = –CHO, –CH₂OH, –CON₃ and -PCl₂) and single-walled carbon nanotubes (SWCNTs). The influence of diameter and chirality of the nanotubes on the stability, charge transferability and electronic properties of such complexes has been investigated using density functional theory. The calculations suggest that the encapsulation stability and charge transferability of the encapsulation complexes depend on the size and chirality of the nanotubes. FcR@SWCNTs are more stable than Fc@SWCNTs at the optimum tube diameter. The greatest charge transfer was observed for FcCH₂OH@SWCNTs and Fc@SWCNTs since the Fe d levels of FcCH₂OH and Fc are nearly equal and close to the Fermi energy level of the nanotubes. The obtained results pave the way to the design of new encapsulated ferrocene derivatives which can give rise to higher stability and charge transferability of the encapsulation complexes.     

复合X光激光中复合阶段拉氏点的特性

 给出了拉氏点在进入Ne/Te增益目标区域后，其电子密度、电子温度、裸核布居概率、类H离子2–1线逃逸概率和增益随时间变化的近似估计式，以及拉氏点进入Ne/Te增益目标区域的时间tg与电子温度Teg必须满足的关系。     

Temperature dependence of the Raman spectra of Bi2Te3 and Bi0.5Sb1.5Te3 thermoelectric films

The temperature dependence of the Raman spectra of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ thermoelectric films was investigated. The temperature coefficients of the E_g(2) peak positions were determined as –0.0137 cm^–1/°C and –0.0156 cm^–1/°C, respectively. The thermal expansion of the crystal caused a linear shift of the Raman peak induced by the temperature change. Based on the linear relation, a reliable and noninvasive micro‐Raman scattering method was shown to measure the thermal conductivity of the thermoelectric films. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermally activated ionic conduction and local structure in solid LiPON thin films

Compact lithium phosphorous oxynitride (LiPON) thin films, as a solid-state electrolyte for all solid-state Li batteries and electrochromic (EC) devices, with the high ratio of the triply coordinated –N< (N_t) over the doubly coordinated –N= (N_d) structural units was deposited by a conventional reactive RF magnetron sputtering of a Li₃PO₄ target at a low pure N₂ pressure. The effect of heat treatment from 200 to 500 °C on the ionic conductivity and local structure of LiPON thin films were investigated by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) core level analysis. A dramatical improvement of ionic conductivity from 1.1 to 3.28 μS/cm and microstructure changes were happened on the LiPON thin films while annealed for 1 h at 300 °C, which was linked to structural differences with a highest ratio of –N< over –N= structural units. The work proves that a proper heat treatment on LiPON thin film can effectively improve its ionic conductivity and change its microstructure.