2011 Vol. 24, No. 4

Content
2011, 24(4): 0-0. doi: 10.1088/1674-0068/24/4/0-0
Quasi-classical trajectory calculations have been employed to investigate the influence of collision energy on the stereodynamics of the title reaction C+CD→C2+D on the poten-tial energy surface of the 12A' state developed by Boggio-Pasqua et al. [Mol. Phys. 98, 1925 (2000)]. The product angular distributions which reflect the vector correlation have been calculated. In addition, two polarization-dependent different cross-sections are also presented in the center-of-mass frame respectively. The results indicate that the product C2 is sensitively affected by collision energy.
We explores Hamiltonian reduction in pulse-controlled finite-dimensional quantum systems with near-degenerate eigenstates. A quantum system with a non-degenerate ground state and several near-degenerate excited states is controlled by a short pulse, and the objective is to maximize the collective population on all excited states when we treat all of them as one level. Two cases of the systems are shown to be equivalent to effective two-level systems. When the pulse is weak, simple relations between the original systems and the reduced systems are obtained. When the pulse is strong, these relations are still available for pulseswith only one frequency under the first-order approximation.
The hydrolysis process of Ru(III) complex (HL)[trans-RuCl4L(dmso-S)] (L=1-methyl-1,2,4-triazole and dmso-S=S-dimethyl sulfoxide) (1), a potential antitumor complex similar to the well-known antitumor agent (Him)[trans-RuCl4L(dmso-S)(im)] (NAMI-A, im=imidazole), was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. The structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.
The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru(II) complexes [Ru(terpy)(phen)X]+(terpy=2,2',6',20'-terpyridine, phen=1,10-phenanthroline, and X=-C≡CH (1), X=Cl (2), X=CN (3)) were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com-plexes in CH3CN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for 3, while the lowest unoccupied molecular orbital were π*(terpy) type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nm are attributed to a dyz(Ru)+π/p(X)→π*(terpy) transition with MLCT/XLCT (metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer) character, whereas that of 3 at 529 nm is related to a dyz(Ru)+π(terpy)→π*(terpy) transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm (1), 913 nm (2), and 838 nm (3) have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru(II) complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.
Molecular dynamics calculation of UO2 in a wide temperature range are presented and dis-cussed. The calculated lattice parameters, mean square displacements, and dynamic prop-erty of phonon-level density of the velocity auto-correlation functions for UO2 are provided. The Morelon potential and the Basak potential are employed. It confirms that the cal-culated lattice parameters using the Basak potential are in nearly perfect agreement with the reported values. The models successfully predict mean square displacement and Bredig transition. Furthermore, the phonon-level density of uranium dioxide are discussed. The intensity of phonon-level density increases with temperature, and the properties of UO2 are characterized by large thermal vibrations rather than extensive disorder.
The electronic state and potential data of U2 molecules are performed by first principle calculations with B3LYP hybrid exchange-correlation functional, the valence electrons of U atom are treated with the (5s4p3d4f)/[3s3p2d2f] contraction basis sets, and the cores are approximated with the relativistic effective core potential. The results show that the ground electronic state is X9+g . The pair potential data are fitted with a Murrell-Sorbie analytical potential function. The U-U embedded atom method (EAM) interatomic potential is deter-mined based on the generalized gradient approximation calculation within the framework of the density functional theory using Perdew-Burke-Ernzerhof exchange-correlation functional at the spin-polarized level. The physical properties, such as the cohesive energy, the lattice constant, the bulk modulus, the shear modulus, the sc/fcc relative energy, the hcp/fcc rela-tive energy, the shear modulus and the monovacancy formation energy are used to evaluate the EAM potential parameters. The U-U pair potential determined by the first principle calculations is in agreement with that defined by the EAM potential parameters. The EAM calculated formation energy of the monovacancy in the fcc structure is also found to be in close agreement with DFT calculation.
The accurate reduced potential energies for two binary gas mixtures including benzene-methanol and methane-tetrafluoromethane at low density have been obtained by direct inversion of the viscosity collision integral equations. The kinetic theory along with the extended principle of corresponding-states has been used to calculate the viscosity and dif-fusion coefficients over a wide range of temperature and composition. Good agreements between calculated and experimental data are obtained.
Quantum chemical calculations are performed to study the reactions of OH and ozone with-out and with water to estimate whether the single water molecule can decrease the energy barrier of the OH radical reaction with ozone. The calculated results demonstrate that the single water molecule can reduce the activated barrier of the naked OH+O3 reaction with the value of about 4.18 kJ/mol. In addition, the transition state theory is carried out to determine whether the single water molecule could enhance the rate constant of the OH+O3 reaction. The computed kinetic data indicate that the rate of the ozone reaction with the formed complexes between OH and water is much slower than that of the OH+O3 reaction, whereas the rate constant of OH reaction with the formed H2O…O3 complex is 2 times greater than that of the naked OH radical with ozone reaction. However, these processes in the atmosphere are not important because the reactions can not compete well with the naked reaction of OH with ozone under atmospheric condition.
The oscillation behavior of a two-dimension lattice-gas Brusselator model was investigated. We have adopted a coarse-grained kinetic Monte Carlo (CG-KMC) procedure, where m£m microscopic lattice sites are grouped together to form a CG cell, upon which CG processes take place with well-defined CG rates. Such a CG approach almost fails if the CG rates are obtained by a simple local mean field (s-LMF) approximation, due to the ignorance of correlation among adjcent cells resulting from the trimolecular reaction in this nonlinear system. By proper incorporating such boundary effects, thus introduce the so-called b-LMF CG approach. Extensive numerical simulations demonstrate that the b-LMF method can reproduce the oscillation behavior of the system quite well, given that the diffusion constant is not too small. In addition, the deviation from the KMC results reaches a nearly zero minimum level at an intermediate cell size, which lies in between the effective diffusion length and the minimal size required to sustain a well-defined temporal oscillation.
The electronic structure of five conformers of 2-chloroethanol was studied by ab initio cal-culations at B3LYP and MP2 levels of theory with aug-cc-pVTZ basis set. The existing hydrogen bond and hyperconjugation effects on the stability of 2-chloroethanol conformers were discussed on the base of natural bond orbital analyses. The result exhibits that hyper-conjugation is the main factor to determine the stability of conformers. Such effects on the electron wavefunctions of the highest-occupied molecular orbital (HOMO) of different con-formers are demonstrated with electron momentum spectroscopy, exhibiting the obviouslydifferent symmetries of the HOMO wavefunctions in momentum space.
We present a first-principles study on the geometric, vibrational and electronic properties of a novel Y-based non-scandium mixed-metal nitride clusterfullerene (TiY2N@C80). Theoretical results indicate that the fundamental electronic properties of TiY2N@C80 are similar to that of TiSc2N@C80, but dramatically different from that of Sc3N@C80 and Y3N@C80 molecules. We find that the magnetism of TiY2N@C80 is quenched by carrier doping. The rotation energy barrier of the TiY2N cluster in C80 cage was obviously increased by exohedral chemical modification with pyrrolidine monoadduct.
A series of end-capped triply branched dendritic chromophores have been studied by means of density functional theory calculations. It is found that the second order nonlinear optical properties of the end-capped dendrimers are strongly dependent on the mutual orientations of the three chromophores, numbers of caps and the conjugation length of the chromophores. Large enhancement of the ˉrst hyperpolarizability can be obtained when dipole moments of three branches in the dendrimers are highly parallelized.
Multiple coordination modes are present in the CuII-histidine complex in solution and the copper coordination environment varies with pH. In this work, we have investigated the coordination geometry of Cu(His)2 complex using X-ray absorption fine structure (XAFS) analysis. Copper K-edge XAFS spectra were acquired on aqueous Cu2+ samples with his-tidine at different pH values. The coordination environments were further confirmed by chemically modified histidine. Results show that the caboxylate groups coordinate at acidic condition, while amino and imidazole nitrogens get coordinated at higher pH. For the co-ordination geometry of Cu(His)2 in solution at physiological pH, the sixfold coordination is preferentially formed, while the fivefold coordination can co-exist in equilibrium.
A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2crude bio-syngas into the CO-containing bio-syngas using the CuZnAlZr catalyst. After the on-line syngas conditioning at 450 oC, the CO2/CO ratio in the bio-syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/(kgcatal·h) MeOH with a methanol selectivity of 97.9% at 260 oC and 5.05 MPa using conventional CuZnAl catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.
ZnO nanoparticles were synthesized via a direct precipitation method followed by a hetero-geneous azeotropic distillation and calcination processes, and then characterized by X-ray power diffraction, scanning electron microscopy, transmission electron microscopy, and ni-trogen adsorption-desorption measurement. The effects of Pt-loading amount, calcination temperature, and sacrificial reagents on the photocatalytic H2 evolution efficiency from the present ZnO suspension were investigated. The experimental results indicate that ZnO nanoparticles calcined at 400 oC exhibit the best photoactivity for the H2 production in comparison with the samples calcined at 300 and 500 oC, and the photocatalytic H2 pro-duction efficiency from a methanol solution is much higher than that from a triethanolamine solution. It can be ascribed to the oxidization of methanol also contributes to the H2 produc-tion during the photochemical reaction process. Moreover, the photocatalytic mechanism for the H2 production from the present ZnO suspension system containing methanol solution is also discussed in detail.
CdS thin films were prepared by chemical-bath-deposited method and the effect of tempera-ture and time on the properties of CdS thin films was studied. Independent of the deposited temperature, the growth was mainly controlled by the ion-by-ion growth mechanism at the beginning of the film deposition, then the cluster-by-cluster mechanism came to be domi-nant. The growth rate increased faster with the increasing of temperature until the thickness reached the limitation, then thickness instead become thinner. The scanning electron micro-scope results revealed that the morphology of the CdS film changed from pinholes to rough,inhomogeneous surface with increasing deposition time and deposition temperature. The X-ray diffraction results showed the film structure was a mixture of two phases: hexagonal and cubic, and it was very important to controll deposition time to the film's crystal phase. All films in depth of approximate 100 nm existed above 65% transmittance, the absorption edge became 〝red-shift〞 with temperature rising. At 60 and 70 oC, with 20 min deposited-time, the energy band gap was more than 2.42 eV and decreased with time, while at 80 and 90 oC, the energy band gap was less than 2.42 eV and increased little when the time changed from 10 min to 15 min at 80 oC.
We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H2/kg dry biomass. The product gas was a mixed gas containing 72%H2, 26%CO2, 1.9%CO, and a trace amount of CH4. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H2 yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H2O. In addition, the CuZn-Al2O3 catalyst in the water-gas shift bed could also increase the absolute H2 yield via shifting CO to CO2.
Cetyltrimethylammonium bromide (CTAB)/potassium bromide (KBr) micellar system has been used as a viscosity probe to study the inclusion complexation between β-cyclodextrin (β-CD) and CTAB. Viscosity measurements show that the inclusion complexation between β-CD and CTAB may cause the breakdown of CTAB/KBr wormlike micelles, resulting in the decrease of the solution viscosity. The viscosity minimum at Cβ-CD/CCTAB=2 indicate the molecular ratio of host molecule to guest molecule is 2:1 in the β-CD/CTAB inclusion complex.
The sol-gel transition of methylcellulose (MC) solution in the presence of NaCl and hexade-cyltrimethylammonium bromide (HTAB), together with MC/NaCl solution in the presence of HTAB and MC/HATB solution in the presence of NaCl, was investigated by the rheolog-ical measurements. It has been found that the sol-gel transition temperature of MC solution decreases linearly with the concentration of NaCl in solution but increases linearly with the concentration of HTAB in solution, respectively. However, the sol-gel transition temperature of MC/NaCl solution in the presence of HTAB keeps the same value, independent of theconcentration of HTAB in solution. On the other hand, the sol-gel transition temperature of MC/HTAB solution decreases linearly with the concentration of NaCl in solution. The experimental results suggest that, for MC/NaCl solution in the presence of HTAB, the salt-induced spherical micelles of HTAB should have formed in bulk solution. For MC solution in the absence of NaCl, no spherical micelles have been formed in bulk solution, though the concentration of HTAB in our experiment is almost one order of magnitude higher than the critical micelle concentration of HTAB in polymer-free solution. In fact, due to adsorption of HTAB on MC chains, the realconcentration of HTAB in bulk solution, is much less than the apparent concentration of HTAB dissolved in MC solution.