Concerted Interaction between Pnicogen and Halogen Bonds in XCl?FH2P?NH3 (X=F,OH, CN,NC, and FCC)

We analyze the interplay between pnicogen‐bonding and halogen‐bonding interactions in the XCl? FH₂P? NH₃ (X=F, OH, CN, NC, and FCC) complex at the MP2/aug‐cc‐pVTZ level. Synergetic effects are observed when pnicogen and halogen bonds coexist in the same complex. These effects are studied in terms of geometric and energetic features of the complexes. Natural bond orbital theory and Bader’s theory of “atoms in molecules” are used to characterize the interactions and analyze their enhancement with varying electron density at critical points and orbital interactions. The physical nature of the interactions and the mechanism of the synergetic effects are studied using symmetry‐adapted perturbation theory. By taking advantage of all the aforementioned computational methods, the present study examines how both interactions mutually influence each other.     

Process design for the shape control of crystals grown by Kyropoulos or SAPMAC method

A mathematical model has been proposed to design the process for growing a shaped crystals by Kyropoulos method or SAPMAC method. Crystal shape evolution behaviours under various processes were analysed. The results show that the crystal would go through a transitory shoulder‐expanding stage after which the crystal diameter rapidly decreases under a constant pulling rate and a constant heater temperature. Reducing pulling rate and heater temperature could depress the decrease of crystal diameter after the shoulder‐expanding stage so that enhance the length of crystal. However, the crystal diameter is more sensitive to pulling rate than to heater temperature, and an equal‐diameter crystal can not be grown in non‐undercooled melt by soley reducing the heater temperature. That means that adjusting the pulling rate is the most effective and convenient approach for controlling crystal diameter evolution and simultaneously decreasing both the pulling rate and the heater temperature is the optimal process for growing an equal‐diameter crystal. Moreover, a numerical approach for quantifactional designing crystal shape and corresponding growth processes was proposed according to the model, an example of crystal shape design was given out. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tb3N@C84: an improbable, egg-shaped endohedral fullerene that violates the isolated pentagon rule

The structure of isomer 2 of Tb3N@C84 has been determined through single-crystal X-ray diffraction on Tb3N@C84.NiII(OEP).2(C6H6). The carbon cage has a distinct egg shape due to the presence of a single pair of fused pentagons at one apex of the molecule. Thus, although 24 IPR structures are available to the C84 cage, Nature utilizes one of the 51 568 isomeric structures that do not conform to the IPR for this unusual molecule. The Tb3N portion of isomer 2 of Tb3N@C84 is strictly planar. One Tb atom is nestled within the fold of the fused pentagons, while the other Tb atoms are disordered over four pairs of sites.     

Preparation and structure of CeSc2N@C80: an icosahedral carbon cage enclosing an acentric CeSc2N unit with buried f electron spin

Herein, we report the preparation, purification, and characterization of a mixed trimetallic nitride endohedral metallofullerene, CeSc(2)N@C(80). Single-crystal X-ray diffraction shows that CeSc(2)N@C(80) consists of a four-atom asymmetric top (CeSc(2)N) inside a C(80) (I(h)()) carbon cage. Unlike the situation in most endohedrals of the M(3)N@C(2)(n)() type, the nitride ion is not located at the center of the carbon cage but is offset by 0.36 A in order to accommodate the large Ce(III) ion. The cage carbon atoms near the endohedral Ce and Sc atoms exhibit significantly larger pyramidal angles than the other carbon atoms on the C(80) cage. Surprisingly, at ambient temperature, the (13)C NMR spectrum exhibits isotropic motional averaging yielding only two signals (3 to 1 intensity ratio) for the icosahedral C(80) cage carbons. At the same temperature, the (45)Sc NMR exhibits a relatively narrow, symmetric signal (2700 Hz) with a small temperature-dependent Curie shift. A rotation energy barrier (E(a) = 79 meV) was derived from the (45)Sc NMR line-width analysis. Finally, the XPS spectrum for CeSc(2)N@C(80) confirms a +3 oxidation state for cerium, Ce(3+)(4f(1)5d(0)).This oxidation state and the Curie shift are consistent with a weakly paramagnetic system with a single buried f electron spin.     

Lewis acid promoted preparation of isomerically pure fullerenols from fullerene peroxides C60(OOt-Bu)6 and C60(O)(OOt-Bu)6

Fullerene mixed peroxides C60(t-BuOO)6 and C60(O)(t-BuOO)6 react with Lewis acids to form various fullerenols through the partial fragmentation of t-BuOO groups. Two monohydroxyl fullerenols with the general formula C60(OH)(t-BuOO)5 and six monohydroxyl fullerenols with the general formula C60(O)(OH)(t-BuOO)5 were prepared, which are essentially the same except the location of the OH group. An additional reaction of the monohydroxyl fullerenols gave bis- and trishydroxyl fullerenols. Single-crystal X-ray structures have been obtained for the two monohydroxyl fullerenols. Other compounds are characterized by chemical correlation and their spectroscopic data. Cuprous bromide could protect the most reactive t-BuOO group from being attacked by stronger Lewis acids. The proposed mechanism mainly involves Lewis acid induced heterolysis of the peroxo O-O bond.     

Syntheses,structure, and electrochemical properties of unsymmetrical crown‐annelated TTF derivatives

A series of new crown‐ether annelated TTF derivatives 2a, 2b, 2c, 3 and 5 have been synthesized and characterized by melting points, NMR, IR and ESI‐MS. The crystal structure of compound 3 , 2, 3‐dithia‐(5′,8′‐dioxaoctyl)‐6,7‐ethylenedithiatetrathiafulvalene, has been determined by X‐ray crystallography. Redox properties of all these compounds have been investigated by cyclic voltammetry and each compound shows two reversible single‐electron redox couples. The results indicate that 3 is responsive for Li⁺, but not to other alkali metal cations, such as Na⁺ and K⁺. Although with the same cavity, compounds 2c and 5 show marked changes upon the addition of sodium perchlorate, while there is no significant response for 2a and 2b at the same condition.     

Charge separation and surface reconstruction: a Mn2+ doping study

Hydrothermal synthesis of Mn doped anatase (TiO2) nanoparticles using scrolled nanotubes of TiO2 and MnCl2 as the starting materials is described. Incorporation of Mn2+ ions on the substitutional sites was confirmed using X-ray absorption fine structure (FT-XAFS) while the oxidation state Mn(II) and coordination environment were determined using both electron paramagnetic resonance (EPR) and X-ray absorption near edge spectroscopy (XANES). Two different hyperfine couplings of 96 and 86 G were found using high-field (130 GHz) EPR reporting that Mn atoms occupy two distinct sites: one undercoordinated (reconstructed surface) and the other octahedral crystalline geometry (nanoparticle core), respectively. It was found that Mn atoms that occupy surface layers are weakly bound to the anatase lattice and can be easily leached using simple dialysis, while those incorporated in the nanoparticle core are bound more strongly and cannot be removed by dialysis. Light excitation EPR reveals that Mn ions incorporated in the surface layers participate in the charge separation, while those trapped deeply in the nanoparticle core do not show any photoactivity. Doping of the core of nanoparticles with Mn2+ ions, on the other hand, enables synthesis of optically transparent films having superparamagnetic behavior at room temperatures with a saturation magnetic moment of 1.23 microB per Mn atom.     

Effect of the structural order of all‐trans‐β‐carotene on the Raman scattering cross section at low concentrations

Using the technique of liquid‐core optical fiber (LCOF), we measured the Raman scattering cross sections (RSCSs) of the carbon–carbon (C C) stretching vibrational modes of all‐trans‐β‐carotene in carbon disulfide (CS₂) at concentrations ranging from 10⁻⁶ to 10⁻¹¹ M . It was found that the RSCSs of all‐trans‐β‐carotene were extremely high with decreasing concentration, and the absolute RSCS of C stretching modes of all‐trans‐β‐carotene reached the value of 2.6 × 10⁻²⁰ cm² molecule⁻¹ Sr⁻¹ at 8 × 10⁻¹¹ M , which is larger than at 8 × 10⁻⁶ Mby 4 orders of magnitude. A theoretical interpretation of the anomalous experimental results is given, which introduces a qualitative nonlinear model of coherent weakly damped electron‐lattice vibrations in structural order of all‐trans‐β‐carotene. Copyright © 2010 John Wiley & Sons, Ltd.     

Intracavity optical parametric oscillator based on GTR-KTP pumped by diode-side-pumped acousto-optically Q-switched Nd:YAG laser

With a non-critically phase-matched high gray-trace resistance KTP (GTR-KTP) crystal, a high-power intracavity optical parametric oscillator (IOPO) emitting at the wavelength of 1.5 μm and pumped by a diode-side-pumped acousto-optically Q-switched Nd:YAG laser is experimentally demonstrated. At the frequency repetition rate of 6 kHz, the maximum average power of 6.36 W at signal wavelength 1570 nm with a pulse width of 9.94 ns is obtained from IOPO based on GTR-KTP, corresponding to a peak power of 107 kW and a single-pulse energy of 1.06 mJ, respectively. We have compared the GTR-KTP IOPO with common KTP IOPO using the same scheme. At the same cavity design, frequency repetition rate and pump condition, only 5.42 W average output power with pulse width 13.82 ns is obtained from IOPO based on common KTP. Besides the higher output power, the output stability of GTR-KTP IOPO is much better than that of common KTP OPO. The output instability of GTR-KTP IOPO is 0.83% versus 6.7% of the common KTP IOPO.     

基于元胞自动机模型的道路突发瓶颈现象研究

针对特殊交通事件诱发的道路突发瓶颈现象,结合驾驶员在瓶颈现象发生前后的行为变化,提出了一个考虑驾驶员在瓶颈处驾驶特性的元胞自动机模型,并利用该模型分析了瓶颈现象对驾驶特性的影响.结果发现,该模型可以刻画不对称换道和瓶颈处抢道行为所产生的一些复杂的交通现象.研究表明,在瓶颈处实行不对称交替通行可以提高系统流量.