Spectroscopic studies of gas-phase molecular clusters

Spectroscopic investigations of hydrogen-bonding and van der Waals' interactions m molecular clusters were studied by the techniques of infrared predissociation and resonance-enhanced multiphoton ionization spectroscopies (REMPI). Ab initio calculations were applied in conjunction for data interpretation.

The infrared predissociation spectroscopy of CN^-•(H_2O)_n (n = 2 - 6) clusters was reported in the region of 2950 - 3850 cm^(-1). The hydrogen bondings for the C-site and N-site binding, and among the water molecules were identified for n = 2 to 4. A spectral transition was observed for n = 5 and 6, implying that the anion was surface-bound onto the water aggregates in larger clusters.

The infrared predissociation spectroscopy of Br^-•(NH_3) and I^-•(NH_3)_n (n =1-3) clusters was reported in the region of 3050-3450 cm^(-1). For the Br^-•(NH_3) complex, a dominating ionic NH stretch appeared at 3175 cm^(-1), and the weaker free NH stretch appeared at 3348 cm^(-1). The observed spectrum was consistent to the structure in which there was one nearly linear hydrogen bond between Br^- and the NH_3 moiety. For the I^- •(NH_3) complex, five distinct IR absorption bands were observed in the spectrum. The spectrum was not consistent with basic frequency patterns of three geometries considered in the ab initio calculations - complex with one, two and three hydrogen bondings between I^- and the NH_3 moiety. Substantial inhomogenous broadening were displayed in the spectra for I^-•(NH_3)_n (n =2-3), suggesting the presence of multiple isomers.

The REMPI spectroscopy of the bound 4p ^2П 1/2 and ^2П 3/2 states, and the dissociative 3d ^2Σ^+ 1/2 state in the Al•Ar complex was reported. The dissociative spectrum at Al^+ channel suggested the coupling of the 4p ^2П 1/2,3/2 states to the repulsive 3d ^2Σ^+ 1/2 state. The spin-electronic coupling was further manifested in the dissociative Al^+ spectrum of the 3d ^2Σ^+ 1/2 state. Using the potential energy curves obtained from ab initio calculations, a bound → continuum Franck-Condon-intensity simulation was performed and compared with the one-photon 3d ^2Σ^+ 1/2 profile. The agreement provided evidence for the petturbation above the Al(3d)Ar dissociation limit, and the repulsive character of the 3d ^2Σ^+ 1/2 state.

Effects on the proton production from explosions of hydrogen clusters subjected to intense femtosecond laser fields

The dependence of the maximum and average energies of protons, which were produced in the interaction of an intense laser pulse (similar to 1 x 10(16) W cm(-2), 65 fs) with hydrogen clusters in a gas jet backed up to 80 bar at liquid nitrogen temperature (similar to 80 K), on the backing pressure has been studied. The general trend of the proton energy dependence on the square of the average cluster radius, which is determined by a calibrated Rayleigh scattering measurement, is similar to that described by theory under the single size approximation. Calculations are made to fit the experimental results under a simplified model by taking into account both a log-normal cluster size distribution and the laser intensity attenuation in the interaction volume. A very good agreement between the experimental proton energy spectra and the calculations is obtained in the high- energy part of the proton energy distributions, but a discrepancy of the fits is revealed in the low-energy part at higher backing pressures which are associated with denser flows. A possible mechanism which would be responsible for this discrepancy is discussed. Finally, from the fits, a variation of the cluster size distributions was revealed to be dependent on the gas backing pressure as well as on the evolving time of the gas flow of clusters.

Embodied energy and gas emission of geotechnical infrastructure

Construction of geotechnical structures produces various environmental impacts. These include depletion of limited natural resources, generation of wastes and harmful substances during material productions and construction, ineffective usage of energy during processing of raw materials into construction materials, and emissions of unwanted gasses during transportation of materials and usage of equipments. With increasing interests in sustainability at the global scale, there is a need to develop a methodology that can assess environmental impacts at such scale for geotechnical construction. Using embodied energy and gas emission, quantitative measures of environmental impact are evaluated using a case study of a new high speed railway line construction in the UK. Based on the results, the keys to energy savings are (a) to optimise the usage of materials with high embodied energy intensity value (b) to optimise the transportation network and logistics for processes using primarily low embodied energy intensity materials and (c) to reuse as much materials on-site as possible to minimise the quantity of spoils or distance to disposal sites. The evaluated embodied energy and embodied carbon values are compared to those of other types of structures and of other activities and carbon tax values. Such comparisons can be used to discuss among various interested parties (clients, contractors, consultants, policy makers, etc) to make the construction industry more energy efficient. © Springer Science+Business Media B.V. 2011.

A Novel System for Reducing Turbo-Lag by Injection of Compressed Gas into the Exhaust Manifold

A key challenge in achieving good transient performance of highly boosted engines is the difficulty of accelerating the turbocharger from low air flow conditions (“turbo lag”). Multi-stage turbocharging, electric turbocharger assistance, electric compressors and hybrid powertrains are helpful in the mitigation of this deficit, but these technologies add significant cost and integration effort. Air-assist systems have the potential to be more cost-effective. Injecting compressed air into the intake manifold has received considerable attention, but the performance improvement offered by this concept is severely constrained by the compressor surge limit. The literature describes many schemes for generating the compressed gas, often involving significant mechanical complexity and/or cost. In this paper we demonstrate a novel exhaust assist system in which a reservoir is charged during braking. Experiments have been conducted using a 2.0 litre light-duty Diesel engine equipped with exhaust gas recirculation (EGR) and variable geometry turbine (VGT) coupled to an AC transient dynamometer, which was controlled to mimic engine load during in-gear braking and acceleration. The experimental results confirm that the proposed system reduces the time to torque during the 3rd gear tip-in by around 60%. Such a significant improvement was possible due to the increased acceleration of turbocharger immediately after the tip-in. Injecting the compressed gas into the exhaust manifold circumvents the problem of compressor surge and is the key enabler of the superior performance of the proposed concept.

Spontaneous emission from radiative chiral nematic liquid crystals at the photonic band-gap edge: An investigation into the role of the density of photon states near resonance

In this article, we investigate the spontaneous emission properties of radiating molecules embedded in a chiral nematic liquid crystal, under the assumption that the electronic transition frequency is close to the photonic edge mode of the structure, i.e., at resonance. We take into account the transition broadening and the decay of electromagnetic field modes supported by the so-called "mirrorless"cavity. We employ the Jaynes-Cummings Hamiltonian to describe the electron interaction with the electromagnetic field, focusing on the mode with the diffracting polarization in the chiral nematic layer. As known in these structures, the density of photon states, calculated via the Wigner method, has distinct peaks on either side of the photonic band gap, which manifests itself as a considerable modification of the emission spectrum. We demonstrate that, near resonance, there are notable differences between the behavior of the density of states and the spontaneous emission profile of these structures. In addition, we examine in some detail the case of the logarithmic peak exhibited in the density of states in two-dimensional photonic structures and obtain analytic relations for the Lamb shift and the broadening of the atomic transition in the emission spectrum. The dynamical behavior of the atom-field system is described by a system of two first-order differential equations, solved using the Green's-function method and the Fourier transform. The emission spectra are then calculated and compared with experimental data. © 2013 American Physical Society.

Spontaneous emission from radiative chiral nematic liquid crystals at the photonic band-gap edge: an investigation into the role of the density of photon states near resonance.

In this article, we investigate the spontaneous emission properties of radiating molecules embedded in a chiral nematic liquid crystal, under the assumption that the electronic transition frequency is close to the photonic edge mode of the structure, i.e., at resonance. We take into account the transition broadening and the decay of electromagnetic field modes supported by the so-called "mirrorless"cavity. We employ the Jaynes-Cummings Hamiltonian to describe the electron interaction with the electromagnetic field, focusing on the mode with the diffracting polarization in the chiral nematic layer. As known in these structures, the density of photon states, calculated via the Wigner method, has distinct peaks on either side of the photonic band gap, which manifests itself as a considerable modification of the emission spectrum. We demonstrate that, near resonance, there are notable differences between the behavior of the density of states and the spontaneous emission profile of these structures. In addition, we examine in some detail the case of the logarithmic peak exhibited in the density of states in two-dimensional photonic structures and obtain analytic relations for the Lamb shift and the broadening of the atomic transition in the emission spectrum. The dynamical behavior of the atom-field system is described by a system of two first-order differential equations, solved using the Green's-function method and the Fourier transform. The emission spectra are then calculated and compared with experimental data.

A novel system for reducing turbo-lag by injection of compressed gas into the exhaust manifold

A key challenge in achieving good transient performance of highly boosted engines is the difficulty of accelerating the turbocharger from low air flow conditions (turbo lag). Multi-stage turbocharging, electric turbocharger assistance, electric compressors and hybrid powertrains are helpful in the mitigation of this deficit, but these technologies add significant cost and integration effort. Air-assist systems have the potential to be more cost-effective. Injecting compressed air into the intake manifold has received considerable attention, but the performance improvement offered by this concept is severely constrained by the compressor surge limit. The literature describes many schemes for generating the compressed gas, often involving significant mechanical complexity and/or cost. In this paper we demonstrate a novel exhaust assist system in which a reservoir is charged during braking. Experiments have been conducted using a 2.0 litre light-duty Diesel engine equipped with exhaust gas recirculation (EGR) and variable geometry turbine (VGT) coupled to an AC transient dynamometer, which was controlled to mimic engine load during in-gear braking and acceleration. The experimental results confirm that the proposed system reduces the time to torque during the 3rd gear tip-in by around 60%. Such a significant improvement was possible due to the increased acceleration of turbocharger immediately after the tip-in. Injecting the compressed gas into the exhaust manifold circumvents the problem of compressor surge and is the key enabler of the superior performance of the proposed concept. Copyright © 2013 SAE International.

Enhancement of field emission of the ZnO film by the reduced work function and the increased conductivity via hydrogen plasma treatment

The ZnO films deposited by magnetron sputtering were treated by H/O plasma. It is found that the field emission (FE) characteristics of the ZnO film are considerably improved after H-plasma treatment and slightly deteriorated after O-plasma treatment. The improvement of FE characteristics is attributed to the reduced work function and the increased conductivity of the ZnO H films. Conductive atomic force microscopy was employed to investigate the effect of the plasma treatment on the nanoscale conductivity of ZnO, these findings correlate well with the FE data and facilitate a clearer description of electron emission from the ZnO H films.

Molecular Dynamics Simulation on Characteristics of Decomposition of Methane Hydrate in the Presence of Hydrogen Peroxide Solution

In this work, the characteristics of the decomposition of methane hydrate Structure I (SI) in the presence of hydrogen peroxide solution is investigated using the molecular dynamics simulation. The mechanism of the transformation process from the solid hydrate to the liquid is analyzed with the effect of hydrogen peroxide (HP) solution. In addition, the effect of ethylene glycol (EG) with the same molar concentration with HP on the methane hydrate dissociation is also studied. The results illustrate that both HP and EG promote well the hydrate dissociation. The work provides the important reference value for the experimental investigation into the promotion effect of HP on the hydrate dissociation.

Research on the mechanics of underwater supersonic gas jets

An experimental research was carried out to study the fluid mechanics of underwater supersonic gas jets. High pressure air was injected into a water tank through converging-diverging nozzles (Laval nozzles). The jets were operated at different conditions of over-, full-and under-expansions. The jet sequences were visualized using a CCD camera. It was found that the injection of supersonic air jets into water is always accompanied by strong flow oscillation, which is related to the phenomenon of shock waves feedback in the gas phase. The shock wave feedback is different from the acoustic feedback when a supersonic gas jet discharges into open air, which causes screech tone. It is a process that the shock waves enclosed in the gas pocket induce a periodic pressure with large amplitude variation in the gas jet. Consequently, the periodic pressure causes the jet oscillation including the large amplitude expansion. Detailed pressure measurements were also conducted to verify the shock wave feedback phenomenon. Three kinds of measuring methods were used, i.e., pressure probe submerged in water, pressure measurements from the side and front walls of the nozzle devices respectively. The results measured by these methods are in a good agreement. They show that every oscillation of the jets causes a sudden increase of pressure and the average frequency of the shock wave feedback is about 5-10 Hz.

Studies on the adduct reaction of disubstituted benzenes with ion system of acetone in gas phase

Ion - molecule reactions of disubstituted benzene with ion system of acetone and deuterium - labelled acetone under chemical ionization conditions were examined and the fragmentation reactions of the adduct ions formed by the ion - molecule reactions were studied using collision - induced dissociation (CID) technique. It was found that the electron - releasing groups favored the adduct reactions, whereas the electron - withdrawing groups did not. The position and properties of substituted groups affected the relative abundance of the adduct ions. The fragmentation reaction of the adduct ion formed by ortho - phenylenediamine with acetyl ion was similar to the reductive alkylation reaction of amine in condensed phase.

Studies on the product of ion-molecule reaction of halogeno-benzene in gas phase by MS/MS

The fragmentations of the product ions produced by the ion-molecule reaction of the halogeno-benzene (chlorobenzene, bromobenzene and iodobenzene) were studied using the collision-induced dissociation, The main product ions of the ion-molecule reaction of three kinds of halogeno-beneze include the dimeric ions, m/z(2M-X) ions and m/z(2M-2X) ions, The CID spectra of these ions were compared with that of the protonated bromodiphenyl and biphenyl, The formation mechanism and the structure of the product ions were obtained.