2008 Vol. 21, No. 6

Editorial
Article
The laser-induced fluorescence excitation spectrum of CoC was recorded in the spectral region from 13500 cm-1 to 22000 cm-1, in which the CoC molecules were produced by the reaction of sputtered cobalt atoms with methanol under supersonic jet cooled conditions. Much of the visible spectrum was assigned to transitions between the X2∑+ ground state and F2∑+ state. The 11 bands assigned as (v’=3-13, 0) transitions of the F2∑+- X2∑+ band system were observed and rotationally analyzed. Equilibrium constants for the F2∑+ state were Te=1362 cm-1, ωe=669 cm-1 ,ωe?e=4.3 cm-1, Be=0.546 cm-1, and Re=1.758A. Some new bands were observed.
White organic light-emitting diodes were fabricated by using a novel phosphorescence bis(1,2-dipheny1-1H-benzoimidazole)iridium(acetylacetonate)[(pbi)2Ir(acac)] as sensitizer and a fluorescent dye of 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran(DCJTB) codoped into a car-bazole polymer of poly(N-vinylcarbazole) (PVK). Through characterizing the UV-Vis absorption spectra,the photoluminescence spectra of (pbi)2Ir(acac) and DCJTB, and the electroluminescence spectral properties of the WOLEDs, the energy transfer mechanisms of the codoped polymer system were deduced. The results demonstrate that the luminescent spectra with different intensity of (pbi)2Ir(acac) and DCJTB were co-existent in the EL spectra of the blended system, which is ascribed to an incomplete energy transfer process in the EL process. The effcient F?rster and Dexter energy transfer between the host and the guests.
The binding energy spectra and electron momentum distributions for the complete valence orbitals of ethanethiol were measured for the first time by binary (e, 2e) electron momentum spectroscopy employing non-coplanar symmetric kinematics at an impact energy of 1200 eV plus binding energy. The experimental results are generally consistent with the theoretical calculations using density functional theory and Hartree-Fock methods with various basis sets. A possible satellite line at 17.8 eV in binding energy spectrum was observed and studied by electron momentum spectroscopy.
The influence of internal noise on the calcium oscillations is studied. It is found that stochastic calcium oscillations occur when the internal noise is considered, while the corresponding deterministic dynamics only yields a steady state. Also, the performance of such oscillations shows two maxima with the variation of the system size, indicating the occurrence of system size resonance. This behavior is found to be intimately connected with the canard phenomenon. Interestingly, it is also found that one of the optimal system sizes matches well with the real cell size, and such a match is robust to the variation of the control parameters.
Density functional theory method was employed to study the effect of the nitroamino group as a substituent in cyclopentane and cyclohexane, which usually construct polycyclic or caged nitramines. Based on the optimized molecular structures of two groups of monocyclic nitramines at the B3LYP/6-31G** level, the infrared (IR) spectra were obtained and assigned by harmonic vibrational analysis. The calculated results agree reasonably with the available experimental data. According to the principles of statistic thermodynamics, thermodynamic properties were derived from the IR spectra, which were linearly correlated with the number of nitroamino groups as well as the temperature. The.
During the measurement of atmospheric nitrate radical by long-path differential optical absorption spectroscopy, water vapor strong absorption could affect the measurement of nitrate radical and detection limits of system. Under the tropospheric condition, the optical density of water vapor absorption is non-linearly dependent on column density. An effective method was developed to eliminate the effect of water vapor absorption. Reference spectra of water vapor based on the daytime atmospheric absorption spectra, when fitted together with change of cross section with water vapor column densities, gave a more accurate fitting of water vapor absorptions, thus its effect on the measurements of nitrate radical could be restricted to a minimum and detection limits of system reached 3.6 ppt. The modified method was applied during an intensive field campaign in the Pearl River Delta, China. The NO3 concentration in polluted air masses varied from 3.6 ppt to 82.5 ppt with an average level of 23.6±1.8 ppt.
The structures and isomerization of magnesium fluorosilylenoid H2SiFMgF were investigated by ab initio molecular orbital theory. Four equilibrium structures and three isomeric transition states were located and fully optimized at the B3LYP/6-31G(d,p) and G3MP2B3 levels, respectively. Based on the B3LYP/6-31G(d,p) optimized geometries, harmonic frequencies of various structures were obtained and 29Si chemical shifts were calculated. The solvent effects were investigated by means of the polarizable continuum model using THF as a solvent at B3LYP/6-31G(d,p) level. Isomerization paths for isomers were confirmed by intrinsic reaction coordinate calculations. The calculated results show that tetrahedral structure has the lowest energy and is the most stable; tetrahedral, three-membered ring, and p-complex structures are suggested to be the experimentally detectable ones; and σ-complex structure has the highest energy and will not exist.
The AlEt3-promoted tandem reductive rearrangement reactions of epoxides was studied at B3LYP/6-31G(d,p) level. For the model compound σ-hydroxy epoxides, two possible reaction pathways I and II were calculated. The main difference is the order of ethylene release and six- to five-member ring rearrangement.The ring contraction rearrangement in pathway I is the first step and this step is the rate controlling step with a free energy barrier of 116.62 kJ/mol. For pathway II, the ethylene release occurs first, and is followed by a six-member ring opening reaction which is the rate controlling step, and the barrier is 251.38 kJ/mol.The reason for such high barrier is that the ethylene release results in the following reaction being moredifficult. The results show that pathway I (C-C rearrangement and then ethylene release) is more favorable,which is consistent with experimental results.
The elastic behavior of a single chain transporting through complex channel which can be seen as the combination of three different channels (left channel, middle channel, and right channel, respectively) is investigated using the new pruned-enriched Rosenbluth method with importance sampling. The elastic force during the translocation process is calculated. At the entrance into the middle channel, there is the first plateau in the curve of the elastic force f(f>0) versus x, here x represents the position of the first monomer along the x-axis direction. When the first monomer moves to a certain position, a second plateau is observedwith the elastic force f<0, which represents spontaneous translocation. The free energy difference between the subchain in the right channel and the subchain in the left channel may drive the translocation. The influence of chain length and width of the left and right channels on the translocation process are also investigated. From the simulation results, more detailed explanations for the reason why the componenttranslocation time is not the same for different channels can be presented.
UV-Vis absorption spectra of the molecular complex formed by imidazole (Im) and chloranil (CA) were measured in chloroform. The stoichiometry of the imidazole-chloranil (Im-CA) complex was determined as 1:1 by applying Benesi-Hildebrand's equation and Job's continuous variation method. Density function theory (DFT) and MP2 calculations were performed to study the structures and the binding energies of the Im-CA complex. The calculations located four conformations (denoted as S1-S4) for the Im-CA complex, two edge(Im)-to-face(CA) linked and two edge(Im)-to-edge(CA) linked. It was found that the edge-to-face conformers are more stable than the edge-to-edge ones. The bonding characteristics of these conformers were investigated with natural population analysis (NPA), topological analysis of electron density, and natural bond orbital (NBO) analysis. It was revealed that the edge-to-face conformers are charge-transfer (CT) complexes whereas the edge-to-edge conformers are the hydrogen bond complexes. For the most stable conformation of the Im-CA complex (S1), the charge transfer interaction of the imidazole n(N15) lone pair orbital with the chloranil ∏*(C1=O7) orbital plays a crucial role in the Im-CA binding, and the binding is further strengthened by the O7… H20 hydrogen bond. The electronic excitation energies of the complex (S1) were calculated with time-dependent DFT (TDDFT), and the observed UV-Visible spectrum of the complex was analyzed based on the computed results.
A modified Miedema model, using interrelationship among the basic properties of elements Ti and H, is employed to calculate the standard enthalpy of formation of titanium hydride TiHx (1≤x≤2). Based on Debye theories of solid thermal capacity, the vibrational entropy, as well as electronic entropy, is acquired by quantum mechanics and statistic thermodynamics methods, and a new approach is presented to calculate the standard entropy of formation of TiH2. The values of standard enthalpy of formation of TiHx decrease linearly with increase of x. The calculated results of standard enthalpy, entropy, and free energy of formation of TiH2 at 298.16 K are -142.39 kJ/mol, -143.0 J/(mol?K) and -99.75 kJ/mol, respectively, which is consistent with the previously-reported data obtained by either experimental or theoretic
Anti-spiral waves are controlled in an oscillatory system by using a local inhomogeneity. The inhomogeneity acts as a wave source, and gives rise to the propagating plane waves. It is found that there is a critical pacemaking domain size below which no wave will be created at all. Two types of ordered waves (target waves and traveling waves) are created depending on the geometry of the local inhomogeneity. The competition between the anti-spiral waves and the ordered waves is discussed. Two different competition mechanisms were observed, which are related to the ordered waves obtained from different local inhomogeneities. It is found that traveling waves with either lower frequency or higher frequency can both eliminate the anti-spiral waves, while only the target waves with lower absolute value of frequency can eliminate the anti-spiral waves.This method also applies to outwardly rotating spiral waves. The control mechanism is intuitively explained and the control method is easily operative.
The damping property of magnetorheological (MR) elastomers is characterized by a modified dynamic mechanical-magnetic coupled analyzer. The influences of the external magnetic flux density, damping of the matrix, content of iron particles, dynamic strain, and driving frequency on the damping properties of MR elastomers were investigated experimentally. The experimental results indicate that the damping properties of MR elastomers greatly depend on the interfacial slipping between the inner particles and the matrix. Different from general composite materials, the interfacial slipping in MR elastomers is affected bythe external applied magnetic field.
Aluminum nitride (AlN) nanobelts were successfully synthesized in high yield through a chloride assisted vapor-solid process. X-ray diffraction, transmission electron microscopy, and selected area electronic diffraction demonstrate that the as-prepared nanobelts are pure, structurally uniform and single crystalline, and can be indexed to hexagonal wurtzite structure. The micro observations show that there exist no defects in the obtained nanobelts. The growth direction of the nanobelts is along [0001]. The frequency spectra of the relative dielectric constant and of the dielectric loss were measured in the frequency range of 50 Hz to 5 MHz. Analysis of these spectra indicates that the interface in samples has great influence on the dielectric behavior of samples. As compared with AlN micropowders, AlN nanobelts have much higher relative dielectric constant, especially at low frequencies at room temperature.
Chemical effects on the Kβ/Kα intensity ratios and ¢E energy differences for Co, Ni, Cu, and Zn complexes were investigated. The samples were excited by 59.5 keV γ-rays from a 241Am annular radioactive source. K X-rays emitted by samples were counted by an Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV. We observed the effects of different ligands on the Kβ/Kα intensity ratios and ⊿E energy differences for Co, Ni, Cu, and Zn complexes. We tried to investigate chemical effects on central atoms using the behaviors of different ligands in these complexes. The experimental values of Kβ/Kα were compared with the theoretical and other experimental values of pure Co, Ni, Cu, and Zn.
Mesoporous silica materials were synthesized via a sol-gel method employing a room temperature ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4]) as a new solvent medium and further modified with surfactant (hexadecyl-trimethyl-ammonium bromide, CTAB) as a pore templating material. The synthesized samples were characterized by the transmission electron microscopy, X-ray diffraction, and N2 adsorption-desorption techniques. The results indicated that the mesoporous silica synthesized by using [bmim][BF4] and CTAB as mixed templates showed better mesostructural order and smaller pore size, compared with mesoporous silica materials synthesized by using single [bmim][BF4] as template under the same conditions. This indicates that the presence of surfactant can affect the microstructures of silica prepared by the present synthesis method.