Self-organized generation of transverse waves in diverging cylindrical detonations

Self-organized generation of transverse waves associated with the transverse wave instabilities at a diverging cylindrical detonation front was numerically studied by solving two-dimensional Euler equations implemented with an improved two-step chemical kinetic model. After solution validation, four mechanisms of the transverse wave generation were identified from numerical simulations, and referred to as the concave front focusing, the kinked front evolution, the wrinkled front evolution and the transverse wave merging, respectively. The propagation of the cylindrical detonation is maintained by the growth of the transverse waves that match the rate of increase in surface area of the detonation front to asymptotically approach a constant average number of transverse waves per unit length along the circumference of the detonation front. This cell bifurcation phenomenon of cellular detonations is discussed in detail to gain better understanding on detonation physics.

Single attosecond pulse generation using two-color polarized time-gating technique

It is proposed that single attosecond pulses be generated via high-order harmonic generation by using a two-color pump pulse with time dependent ellipticity. The two-color pump pulse is created by the fundamental field and its second harmonic: the fundamental field is left-circularly polarized and the second harmonic is right-circularly polarized. Numerical simulations show that single attosecond pulses can be produced in the cut-off region by using the synthesis of 20 fs left-hand and right-hand circularly polarized pulses with a pulse delay of 20 fs. The attosecond pulses produced this way are much stronger than that produced by a few-cycle linear polarized pulse of comparable intensity. (c) 2005 Optical Society of America

Proton transfers at the air-water interface

Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H₃O⁺(g), can protonate most (non-alkane) organic species, whereas H₃O⁺(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

Nonlinear propagation of fs laser pulses in liquids and evolution of supercontinuum generation

Nonlinear propagation of fs laser pulses in liquids and the dynamic processes of filamentation such as self-focusing, intensity clamping, and evolution of white light production have been analyzed by using one- and two-photon fluorescence. The energy losses of laser pulses caused by multiphoton absorption and conical emission have been measured respectively by z-scan technique. Numerical simulations of fs laser propagation in water have been made to explain the evolution of white light production as well as the small-scale filaments in liquids we have observed by a nonlinear fluorescence technique. (c) 2005 Optical Society of America.

Enhanced dispersive wave generation by using chirped pulses in a microstructured fiber

A theoretical investigation on the nonlinear pulse propagation and dispersive wave generation in the anomalous dispersion region of a microstructured fiber is presented. By simulating the dispersive wave generation under different conditions. it is found that the generation mechanism of the dispersive wave is mainly due to the pulse trapping across the zero-dispersion wavelength. By varying the initial pulse chirp, the output spectrum can be broadened and the intensity of the dispersive wave can be obviously enhanced. In particular, there exists an optimal positive chirp which maximizes the intensity of the dispersive wave. This effect can be explained by the energy transfer from the Raman soliton to the dispersive wave due to the effect of the pulse trapping and the effect of the higher-order dispersion. From the phase aspect, the explanation of this effect is also included. (C) 2004 Elsevier B.V. All rights reserved.

Electrical, electrochemical, and optical characterization of ceria films

Acceptor-doped ceria has been recognized as a promising intermediate temperature solid oxide fuel cell electrode/electrolyte material. For practical implementation of ceria as a fuel cell electrolyte and for designing model experiments for electrochemical activity, it is necessary to fabricate thin films of ceria. Here, metal-organic chemical vapor deposition was carried out in a homemade reactor to grow ceria films for further electrical, electrochemical, and optical characterization. Doped/undoped ceria films are grown on single crystalline oxide wafers with/without Pt line pattern or Pt solid layer. Deposition conditions were varied to see the effect on the resultant film property. Recently, proton conduction in nanograined polycrystalline pellets of ceria drew much interest. Thickness-mode (through-plane, z-direction) electrical measurements were made to confirm the existence of proton conductivity and investigate the nature of the conduction pathway: exposed grain surfaces and parallel grain boundaries. Columnar structure presumably favors proton conduction, and we have found measurable proton conductivity enhancement. Electrochemical property of gas-columnar ceria interface on the hydrogen electrooxidation is studied by AC impedance spectroscopy. Isothermal gas composition dependence of the electrode resistance was studied to elucidate Sm doping level effect and microstructure effect. Significantly, preferred orientation is shown to affect the gas dependence and performance of the fuel cell anode. A hypothesis is proposed to explain the origin of this behavior. Lastly, an optical transmittance based methodology was developed to obtain reference refractive index and microstructural parameters (thickness, roughness, porosity) of ceria films via subsequent fitting procedure.

Earth-abundant materials for solar hydrogen generation

A critical challenge for the 21st century is shifting from the predominant use of fossil fuels to renewables for energy. Among many options, sunlight is the only single renewable resource with sufficient abundance to replace most or all of our current fossil energy use. However, existing photovoltaic and solar thermal technologies cannot be scaled infinitely due to the temporal and geographic intermittency of sunlight. Therefore efficient and inexpensive methods for storage of solar energy in a dense medium are needed in order to greatly increase utilization of the sun as a primary resource. For this purpose we have proposed an artificial photosynthetic system consisting of semiconductors, electrocatalysts, and polymer membranes to carry out photoelectrochemical water splitting as a method for solar fuel generation.

This dissertation describes efforts over the last five years to develop critical semiconductor and catalyst components for efficient and scalable photoelectrochemical hydrogen evolution, one of the half reactions for water splitting. We identified and developed Ni–Mo alloy and Ni₂P nanoparticles as promising earth-abundant electrocatalysts for hydrogen evolution. We thoroughly characterized Ni–Mo alloys alongside Ni and Pt catalysts deposited onto planar and structured Si light absorbers for solar hydrogen generation. We sought to address several key challenges that emerged in the use of non-noble catalysts for solar fuels generation, resulting in the synthesis and characterization of Ni–Mo nanopowder for use in a new photocathode device architecture. To address the mismatch in stability between non-noble metal alloys and Si absorbers, we also synthesized and characterized p-type WSe₂ as a candidate light absorber alternative to Si that is stable under acidic and alkaline conditions.

Optimization of multi-cycle two-color laser fields for the generation of an isolated attosecond pulse

The effect of the mixing of pulsed two color fields on the generation of an isolated attosecond pulse has been systematically investigated. One main color is 800 nm and the other color (or secondary color) is varied from 1.2 to 2.4 mu m. This work shows that the continuum length behaves in a similar way to the behavior of the difference in the square of the amplitude of the strongest and next strongest cycle. As the mixing ratio is increased, the optimal wavelength for the extended continuum shifts toward shorter wavelength side. There is a certain mixing ratio of intensities at which the continuum length bifurcates, i.e., the existence of two optimal wavelengths. As the mixing ratio is further increased, each branch bifurcates again into two sub-branches. This 2D map analysis of the mixing ratio and the wavelength of the secondary field easily allows one to select a proper wavelength and the mixing ratio for a given pulse duration of the primary field. The study shows that an isolated sub-100 attosecond pulse can be generated mixing an 11 fs full-width-half-maximum (FWHM), 800 laser pulse with an 1840 nm FWHM pulse. Furthermore the result reveals that a 33 fs FWHM, 800 nm pulse can produce an isolated pulse below 200 as, when properly mixed. (c) 2008 Optical Society of America.

Control of single attosecond pulse generation from the reflection of a synthesized relativistic laser pulse on a solid surface

The influence of the carrier-envelope phase (CEP) of the driving laser pulse on the generation of single attosecond (as) pulses from surface harmonics by using the polarization gating technique is investigated in detail. It is found that the modulation depth of the high-order harmonic spectrum depends on the CEP, and a strong single 68 as pulse can be generated when the CEP is stable and has the proper value. The physical origin of the influence of the CEP is explained in terms of the oscillating mirror model. (C) 2008 American Institute of Physics. [DOI: 10.1063/1.2997342]

Generation of intense extreme supercontinuum radiation via resonant propagation effects

Confinement of electromagnetic energy into a single well-controlled oscillation of light is very important for generation of intense supercontinuum radiation. We find that the pulse breakup of few-cycle ultrashort laser pulses via resonant propagation effects can achieve this aim. By extracting such pulses and then focusing them to drive the He atoms, about 200 eV intense supercontinuum radiation can be generated, which is capable of supporting similar to 20 attosecond isolated pulse generation.