Photodissociation dynamics of ethyl iodide in the A band has been investigated at several wavelengths between 245 and 283 nm using resonance-enhanced multiphoton ionization technique combined with velocity map ion-imaging detection. The ion images of I, I(*), and C(2)H(5) fragments are analyzed to yield corresponding speed and angular distributions. Two photodissociation channels are found: I(5p (2)P(3/2))+C(2)H(5) (hotter internal states) and I(*)(5p (2)P(1/2))+C(2)H(5) (colder). In addition, a competitive ionization dissociation channel, C(2)H(5)I(+)+h nu-->C(2)H(5)+I(+), appears at the wavelengths <266 nm. The I/I(*) branching of the dissociation channels may be obtained directly from the C(2)H(5) (+) images, yielding the quantum yield of I(*) about 0.63-0.76, comparable to the case of CH(3)I. Anisotropy parameters (beta) determined for the I(*) channel remain at 1.9+/-0.1 over the wavelength range studied, indicating that the I(*) production should originate from the (3)Q(0) state. In contrast, the beta(I) values become smaller above 266 nm, comprising two components, direct excitation of (3)Q(1) and nonadiabatic transition between the (3)Q(0) and (1)Q(1) states. The curve crossing probabilities are determined to be 0.24-0.36, increasing with the wavelength. A heavier branched ethyl group does not significantly enhance the I(5p (2)P(3/2)) production from the nonadiabatic contribution, as compared to the case of CH(3)I.

Black TiO2 has triggered worldwide research interest due to its excellent photocatalytic properties. However, the understanding of its structure–property relationships and a more effective, facile and versatile method to produce it remain great challenges. We have developed a facile approach to synthesize black TiO2 nanoparticles with significantly improved light absorption in the visible and infrared regions. The experimental results show that oxygen vacancies are the major factors responsible for black coloration. More importantly, our black TiO2 nanoparticles have no Ti3+ ions. These oxygen vacancies could introduce localized states in the bandgap and act as trap centers, significantly decreasing the electron–hole recombination. The photocatalytic decomposition of both rhodamine B and methylene blue demonstrated that, under ultraviolet light irradiation, better photocatalytic performance is achieved with our black TiO2 nanoparticles than with commercial TiO2 nanoparticles.

Oxygen vacancy defects play an important role in improving the light-capturing and photocatalytic activity of tungsten trioxide (WO3). However, the hydrogen treatment method that is commonly used to introduce oxygen vacancies is expensive and dangerous. Therefore, the introduction and control of oxygen vacancy defects in WO3 remains a challenge. Here, we demonstrated that oxygen vacancies could be successfully introduced into WO3−x while using a facile method through low temperature annealing in alcohol. The obtained WO3−x samples with optimal oxygen vacancies showed strong absorption of light, extending from the ultraviolet to the visible and near-infrared regions, and exhibits strong plasmon resonance from 400–1200 nm peaking at approximately 800 nm. When compared to pristine WO3, the photocatalytic activity of WO3−x was greatly improved in the ultraviolet and visible regions. This study provides a simple and efficient method to generate oxygen vacancies in WO3 for photocatalysis, which may be applied in the photoelectrochemical, electrochromic, and photochromic fields. Because oxygen vacancy is a common characteristic of metal oxides, the findings that are presented herein may be extended to other metal oxides.

No abstract

This paper presents the design and construction of a deep excavation for building foundations in saturated soil. This deep excavation was of particular interest because it was located above and beside the Shanghai Metro tunnels. The twin Shanghai Metro tunnels had to be in full operation during the deep excavation. Potential large deformation of the twin tunnels was one of the main concerns during the design and construction for the deep excavation. The paper discusses in detail the criteria and measures for controlling the soil and tunnel deformation. The measures included cast-in-place concrete diaphragm walls with bracing structural members, pumping consolidation, cement–soil mix pile systems, and rational excavation procedures. A simplified theoretical method was proposed to estimate the increment in undrained shear strength in a soft clay layer due to pumping consolidation. Furthermore, conventional finite element methods were used to predict the soil vertical and horizontal displacements induced by the excavation. Using the design and construction methods discussed in the paper, the settlement and horizontal displacement of the tunnels were successfully controlled within 5.0 mm and 9.0 mm, respectively. The curvature of longitudinal deformation curve of the tunnels was less than 1/15 000. The horizontal displacement of the braced diaphragm walls was less than 0.12% of the total excavation depth. Key words: Metro tunnels, saturated soft soil, deep excavation, design, construction, ground improvement, case studies.

Following photodissociation of CH2Br2 at 248 nm, Br2 molecular elimination is detected by using a tunable laser beam, as crossed perpendicular to the photolyzing laser beam in a ring-down cell, probing the Br2 fragment in the B 3Piou+ -X 1Sigmag+ transition. The nascent vibrational population is obtained, yielding a population ratio of Br2(v = 1)Br2(v = 0) to be 0.7 +/- 0.2. The quantum yield for the Br2 elimination reaction is determined to be 0.2 +/- 0.1. Nevertheless, when CH2Br2 is prepared in a supersonic molecular beam under cold temperature, photofragmentation gives no Br2 detectable in a time-of-flight mass spectrometer. With the aid of ab initio potential energy calculations, a plausible pathway is proposed. Upon excitation to the 1B1 or 3B1 state, C-Br bond elongation may change the molecular symmetry of Cs and enhance the resultant 1 1,3A'-X 1A' (or 1 1,3B1-X 1A1 as C2v is used) coupling to facilitate the process of internal conversion, followed by asynchronous concerted photodissociation. Temperature dependence measurements lend support to the proposed pathway.

No abstract

No abstract