ELECTRONIC-STRUCTURES OF THE ALKALI-CONTAINING BUCKMINSTERFULLERENES (A-DELTA-C60) (A=LI,NA,K,RB,CS) AND THE HALOGEN-CONTAINING BUCKMINSTERFULLERENES (H-DELTA-C60) (H=F,CL,BR,I)

The geometrical parameters and electronic structures of C60, (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl, Br, I) have been calculated by the EHMO/ASED (atom superposition and electron delocalization) method. When putting a central atom into the C60 cage, the frontier and subfrontier orbitals of (A partial derivative C60) (A = Li, Na, K, Rb, Cs) and (H partial derivative C60) (H = F, Cl) relative to those of C60 undergo little change and thus, from the viewpoint of charge transfer, A (A = Li, Na, K, Rb, Cs) and H (H = F, Cl) are simply electron donors and acceptors for the C60 cage resPeCtively. Br is an electron acceptor but it does influence the frontier and subfrontier MOs for the C60 cage, and although there is no charge transfer between I and the C60 cage, the frontier and subfrontier MOs for the C60 cage are obviously influenced by I. The stabilities DELTAE(X) (DELTAE(X) = (E(X) + E(C60)) - E(x partial derivative C60)) follow the sequence I < Br < None < Cl < F < Li < Na < K < Rb < Cs while the cage radii r follow the inverse sequence. The stability order and the cage radii order have been explained by means of the (exp-6-1) potential.

Photostimulated luminescence of silver clusters in zeolite-Y

Upon UV-irradiation at 254 nm, the photoluminescence of silver atoms in zeolite-Y decreases, meanwhile an absorption band shows up around 840 nm. By photostimulation at 840 nm, fluorescence of silver atoms is detected, which is called photostimulated luminescence, and the photoluminescence of silver atoms is increased slightly. These phenomena are attributed to the charge-transfer interaction between the zeolite framework and the entrapped silver atoms. (C) 1997 Published by Elsevier Science B.V.

Electrical bistability and negative differential resistance in diodes based on silver nanoparticle-poly(N-vinylcarbazole) composites

An electrically bistable device has been fabricated using nanocomposite films consisting of silver nanoparticles and a semiconducting polymer by a simple spin-coating method. The current-voltage characteristics of the as-fabricated devices exhibit an obvious electrical bistability and negative differential resistance effect. The current ratio between the high-conducting state and low-conducting state can reach more than 103 at room temperature. The electrical bistability of the device is attributed to the electric-filed-induced charge transfer between the silver nanoparticles and the polymer, and the negative differential resistance behavior is related to the charge trapping in the silver nanoparticles. The results open up a simple approach to fabricate high quality electrically bistable devices by doping metal nanoparticles into polymer.

Theoretical investigation on excitation, ionization and capture in H(1s, 2s)+H(1s, 2s) collisions

Cross sections of electron- loss in H( 1s)+ H( 1s) collisions and total collisional destruction of H( 2s) in H( 1s) + H( 2s) collisions are calculated by four- body classical- trajectory Monte Carlo ( CTMC) method and compared with previous theoretical and experimental data over the energy range of 4 - 100 keV. For the former a good agreement is obtained within di. erent four- body CTMC calculations, and for the incident energy Ep > 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approximation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H( 2p), single- and double- ionization and H- formation in H( 2s)+ H( 2s) collisions are calculated in the energy range of 4 - 100 keV for the. rst time, and compared with those in H( 1s)+ H( 1s) and H( 1s)+ H( 2s) collisions.

The many-particle scattering system He++ on He: Experiment and a complete unified description

Highly differential experimental results of the scattering system He++ on He at 30 keV are presented as well as a complete unified theoretical description where excitation, transfer and ionization are treated simultaneously on an ab initio level. The agreement even for highly differential cross sections is nearly complete although no explicit correlation besides Pauli correlation is included in the calculations.

Average energy loss measured in single and double electron capture collisions of He2 on Ar at low velocities

Employing the recoil ion momentum spectroscopy we investigate the collision between He2+ and argon atoms. By measuring the recoil longitudinal momentum the energy losses of projectile are deduced for capture reaction channels. It is found that in most cases for single- and double-electron capture, the inner electron in the target atom is removed, the recoil ion is in singly or multiply excited states (hollow ion is formed), which indicates that electron correlation plays an important role in the process. The captured electrons prefer the ground states of the projectile. It is experimentally demonstrated that the average energy losses are directly related to charge transfer and electronic configuration.

Excitation and dissociation of tungsten hexacarbonyl W(CO)(6): Statistical and nonstatistical dissociation processes

We have studied the excitation and dissociation processes of the molecule W(CO)(6) in collisions with low kinetic energy (3 keV) protons, monocharged fluorine, and chlorine ions using double charge transfer spectroscopy. By analyzing the kinetic energy loss of the projectile anions, we measured the excitation energy distribution of the produced transient dications W(CO)(6)(2+). By coincidence measurements between the anions and the stable or fragments of W(CO)(6)(2+), we determined the energy distribution for each dissociation channel. Based on the experimental data, the emission of the first CO was tentatively attributed to a nonstatistical direct dissociation process and the emission of the second or more CO ligands was attributed to the statistical dissociation processes. The dissociation energies for the successive breaking of the W-CO bond were estimated using a cascade model. The ratio between charge separation and evaporation (by the loss of CO+ and CO, respectively) channels was estimated to be 6% in the case of Cl+ impact. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3523347]

Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

An alternative approach to ascertain the rate-determining steps of TiO2 photoelectrocatalytic reaction by electrochemical impedance spectroscopy

In an attempt to ascertain the rate-determining steps (RDS) of TiO2 photoelectrocatalytic (PEC) reaction, the PEC oxidation of sulfosalicylic acid (SSA) solution in a TiO2-coated electrode reactor system was monitored by applying the electrochemical impedance spectroscopy (EIS) method. In the meantime, an EIS mathematical model was first established to theoretically simulate the PEC reaction. Based on the EIS model, the theoretical simulation indicates three typical reactions in a PEC oxidation process, which include the charge-transfer-dominated reaction, both the charge-transfer- and adsorption-dominated reaction, and the adsorption-dominated reaction. The experimental results of EIS measurement showed that there was only one arc/semicircle on the EIS plane display when the external bias applied was below 200 mV (vs SCE) in the SSA PEC degradation whereas there were two arcs/semicircles when the externally applied bias exceeded 200 mV (vs SCE). The experimental results have a good agreement with the model simulation. The EIS method in this study provides an easier way to determine the RDS in a PEC oxidation process, which would be helpful to better control the reaction in practice.

DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Rhenium(I) Pyridinybenzoimidazole Complexes

The electronic structures and spectral properties of three Re(I) complexes [Re(CO)(3)XL] (X = Br, Cl; L = 1-(4-5 '-phenyl-1.3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1), 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), and 2-(1-ethyl benzimidazol-2-yl)pyridi ne (3)) were investigated theoretically. The ground and the lowest lying triplet excited states were full optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ levels, respectively. TDDFT/PCM calculations have been employed to predict the absorption and emission spectra starting from the ground and excited state geometries, respectively.

Adsorption of 4,4 '-thiobisbenzenethiol on silver surfaces: surface-enhanced Raman scattering study

Adsorption of 4,4'-thiobisbenzenethiol (4,4'-TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface-enhanced Raman scattering (SERS) for the first time, which indicates that 4,4'-TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H-atoms of the S-H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4'-TBBT in the two systems.

Theoretical Studies on the Reaction Mechanism of Platinum-Catalyzed Diboration of Allenes

The reaction mechanism of Pt(0)-catalyzed diboration reaction of allenes is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. The electronic mechanisms of the allene insertion into the Pt-B bond are discussed in terms of the electron donation, back-donation, and d-pi interaction. During allene insertion into the Pt-B bond, the internal carbon atom of allene is preferred over the terminal one due to the stronger electron back-donation and stronger charge transfer in the former case than that in the latter one.

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.