Three-dimensional Molecular Geometry of PEG Hydrogels by an “Expansion-Contraction” Method through Monte Carlo Simulations

Three-dimensional（3-D） coarse-grained Monte Carlo algorithms were used to simulate the conformations of swollen hydrogels formed by copper（I）-catalyzed azide-alkyne cycloaddition（Cu AAC）. The simulation consists of three successive steps including diffusion, cross-linking and relaxation. The cross-linking of multifunctional reaction sites is simulated instantly followed by fast crosslinking. In order to explore the validity of this approach pristine poly（ethylene glycol）（PEG） hydrogels with tri- and tetra-functional reaction sites（G3 and G4 respectively） were prepared and characterized. The data from the simulations were found to be in good agreement with experimental results such as PEG lengths between crosslinks, pore volume and pore radius distribution, indicating the validity of the modeling algorithm. The calculated PEG lengths in G3 and G4 networks are close（≈ 4.6 nm）. The 3-D visual topological structure of the hydrogel network suggests that the ＂ideal＂ hydrogel is far from cubic, diamond or any well defined structures of regular repeating cells.

Structural and spectroscopic properties of small Pu_n(n=2-5) molecules

The equilibrium structures and the electronic, spectroscopic and thermodynamic properties of small Pun （n = 2- 5） molecules are systematically investigated using the methods of general gradient approximation （GGA） of density functional theory （DFT）. The results show that the bond length of the lowest-energy structure of Pu2 is 2.578 A. The ground state structure of Pu3 is a triangle with D3h symmetry, whereas for Pu4, the ground state structure is a square （D4h） and the spin polarization of 16 for molecule Pu5 with square geometry （D_4h） is the most stable structure. For the ground state structures, the vibrational spectra as well as thermodynamic parameters are worked out. In addition, the values for the highest occupied molecular orbital （HOMO） and the lowest unoccupied molecular orbital （LUMO） along with the energy gap of all the Pu_2-5 structures are presented. The relevant structural and chemical stabilities are predicted.

Theoretical Studies on Property and Structure of Silacyclohexane-based Liquid Crystal Compounds

SCF-MO-AM1 calculations have been per formed on 10 silacyclohex-ane-based liquid crystal compounds by energy gradient completed optimization. The stable configurations, electronic structures, heats of formation, dipole moments and ionization potentials of titled comPounds are first reported. The calculated results are.discussed relating to the classical organic electronic theory.

Geometric structure of N_(2)O^(q+)(q=5,6)studied by Ne^(8+)ion-induced Coulomb explosion imaging

We report the study on the complete three-body Coulomb explosion(CE)of N_(2)O^(q+)(q=5,6)induced by 56-keV/u Ne8+ion collision with N2O gaseous molecule.Six CE channels for N_(2)O^(5+)and seven for N_(2)O^(6+)are identified by measuring three ionic fragments and the charge-changed projectile in quadruple coincidence.Correspondingly the kinetic energy release(KER)and momentum correlation angle(MCA)distributions of three ionic fragments for each of the CE channels are also deduced.Numerical computation is presented to reconstruct the geometric structure of N_(2)O^(q+0prior to dissociation based on the measured KER and MCA.The N–N and N–O bond lengths and the N–N–O bond angles of N_(2)O^(q+)for each of the channels are determined.

The structural and spectroscopic properties for uranium oxides

The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO2, UO3, and U2O3 molecules are systematically investigated using the density functional theory （DFT） with the method of generalized gradient approximation （GGA）. The bond lengths and the vibrational frequencies of the ground states of UO, UO2, and UO3 molecules are all in agreement with available experimental data. For U2O3 molecules, our calculations indicate that the ground state of the U203 molecule is an XTA1 state with Dah （trigonal bipyramid） symmetry （R1 （U O）=0.2113 nm, R2（U1 U2）=0.2921 nm, ZU1OU2 = 87.5° , dihedral angle O（U,O1,O2,O3）=62.40°）. The harmonic frequency, the IR intensity and the spin density of the U2Oa molecule are all obtained for the first time in theory. For the ground state of U203 molecules, the vibrational frequencies are 178.46 （Ai）, 276.79 （E1＇＇）, 310.77 （EL）, 396.63 （AS＇）, 579.15 （El）, and 614.98 （A1＇） cm-1. The vibrational modes corresponding to the IR maximum peaks are worked out for UO3 and U203 molecules. Besides, the results of Gophinatan-Jng bond order indicate that UO, UO2, and UO3 molecules possess U=O double bonds and that the U203 molecule possesses U O single bonds and a U-U single bond.

Bonding Energies and Structural Study of Alkylaluminium

Neutral aluminium alkyls are well known to act as ethylene oligomerization and polymerization catalysts and cocatalysts.On the basis of the full optimization of alkylaluminium compounds with Gaussian 98 program package at the B3LYP/6-31G＊＊ level,the selected structures and bonding energies were investigated extensively.The geometries and bonding energies of AlR3（R = H,CH3,C2H5,C3H7,C4H9） and Al（C2H5）2R＇（R＇ = C2H5,C3H7,C4H9,C5H11,C6H13） were investigated extensively,and we found that,along with the prolongation of carbon chains the terminal C-C bond is shortened gradually until to a constant value of about 0.1532 nm in C4H9;and the bonding energy almost remains constant.The dative bonding of C2H4 to Al（C2H5）3,whose bonding energy is only 15.30 kJ/mol,is very weak.

Novel Donor-Acceptor Copolymers Based on Dithienosilole and Ketone Modified Thieno[3,4-b]thiophene for Photovoltaic Application

Two novel donor-acceptor （D-A） copolymers containing dithienosilole （DTS） donor unit and ketone modified thieno[3,4-b]thiophene （TT） acceptor unit, namely, poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2-b：2＇,Y-d]silole-5,5＇-diyl- alt-l-（thieno[3,4-b]thiophen-2-yl）-2-ethylhexan-l-one} （PDTSTT） and poly{4,4＇-bis（2-ethylhexyl）dithieno[3,2- b：2＇,3＇-d]silole-5,5＇-diyl-alt- 1-（4,6-bis（4-ethylhexylthien-2-yl）thieno[3,4-b]thiophen-2-yl）-2-ethylhexan- 1-one} （PD- TSDTTT）, were synthesized for the application in polymer solar cells （PSCs）, and the effects of thiophene bridge on the structural geometry and photovoiltaie performance have been investigated. The polymer PDTSTT and PDTSDTTT have the electrochemical bandgaps of 1.54 and 2.02 eV, together with low-lying HOMO energy levels of-5.47 and -5.37 eV, respectively. Molecular geometry simulation result shows that compared with PDTSTT, the insertion of thiophene bridge in PDTSDTTT can well relieve the steric hindrance between the TT and DTS unit, as confirmed by the reduced dihedral angle between DTS and DTTT unit. Under the illumination of AM 1.5G, 100 mW/cm2, the PSC based on PDTSDTTT/PC61BM （1 ： 1, w ： w） demonstrates a power conversion efficiency of 1.0%, which is significantly improved in comparison with the device based on PDTSTT/PC61BM （1 ： 2, w ： w） under the same experimental condition. This is because the enhanced planarity and increased effective conjugation of the main chain in PDTSDTTT promote the more favorable morphology for charge transportation, although PDTSTT possesses the broader absorption band than PDTSDTTT.

Theoretical study on tetrazole and its derivatives (3) MP2 and thermodynamic calculations of amino derivatives of tetrazole

Fully optimized geometries and electronic structures of amino derivatives of tetrazole are obtained at MP2/6-31G* level. The tetrazole rings are planar and aromatic for all the amino derivatives of tetrazole. The amino group is not co-planar with the ring and its conformation is mainly determined by the lone pair electronic repulsion between the substituents and the ring. N(4) atom is more negatively charged and is the most probable coordination site. The energy gaps between LUMOs and HOMOs of 2H-aminotetrazoles and C-aminotetrazole neutrals are smaller than those of the corresponding 1H-isomers and N-aminotetrazole neutrals respectively. The IR frequencies, thermodynamic properties and temperature-dependent functions for heat capacities in the fom (a + bT + cT2) in the 300–1000K range are reported.