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.

Long lifetime plasma channel in air generated by multiple femtosecond laser pulses and an external electrical field

The lifetime of a plasma channel produced by self-guiding intense femtosecond laser pulses in air is largely prolonged by adding a high voltage electrical field in the plasma and by introducing a series of femtosecond laser pulses. An optimal lifetime value is realized through adjusting the delay among these laser pulses. The lifetime of a plasma channel is greatly enhanced to 350 ns by using four sequential intense 100fs( FWHM) laser pulses with an external electrical field of about 350kV/m, which proves the feasibility of prolonging the lifetime of plasma by adding an external electrical field and employing multiple laser pulses. (c) 2006 Optical Society of America.

Formation of X-waves at fundamental and harmonics by infrared femtosecond pulse filamentation in air

We experimentally observe the formation of X-waves at fundamental, third harmonic, and fifth harmonic wavelengths by infrared (central wavelength at similar to 1500 nm) femtosecond laser pulse filamentation in air. By fitting the angularly resolved spectra of the fundamental and harmonic waves using X-wave relations, we confirm that all the X-waves have nearly the same group velocity, indicating that they are locked in space and time during their propagation in filament.

Spectral evolution of angularly resolved third-order harmonic generation by infrared femtosecond laser-pulse filamentation in air

We experimentally investigate the evolution of an angularly resolved spectrum of third harmonic generated by infrared femtosecond laser pulse filamentation in air. We show that at low pump intensity, phase matching between the fundamental and third-harmonic waves dominates the nonlinear optical effect and induces a ring structure of the third-harmonic beam, whereas at high pump intensity, the dispersion properties of air begin to affect the angular spectrum, leading to the formation of a nonlinear X wave at third harmonic.

X-shaped third harmonic generated by ultrashort infrared pulse filamentation in air

The authors report the measurement of the angularly resolved spectrum of the third harmonic generated in a femtosecond filament in air and its evolution with increasing pump power. Pumped by a focused infrared ultrashort pulse with a carrier wavelength of 1270 nm, a pulse duration of similar to 20 fs, and pulse energy up to 487 mu J, the generated third harmonic is composed of an on-axis emission and a conical ring emission. When the pump power is sufficiently high, angularly resolved spectra with significant X-like feature could be observed, indicating the formation of nonlinear X wave at third harmonic. (c) 2008 American Institute of Physics.

Transverse evolution of a plasma channel in air induced by a femtosecond laser

We investigate the evolution of filamentation in air by using a longitudinal diffraction method and a plasma fluorescence imaging technique. The diameter of a single filament in which the intensity is clamped increases as the energy of the pump light pulse increases, until multiple filaments appear. (c) 2006 Optical Society of America.

ZnSe nanowires grown on the crystal surface by femtosecond laser ablation in air

Uniform ZnSe nanowires are observed on the ablation crater on ZnSe crystal surface irradiated by femtosecond lasers in air, while other parts of the sample surface are not polluted. The nanowire growth rate is about 5 mu m/s, it is higher than that fabricated by chemical vapor deposition method by a factor of 10(4). The nanowire length and diameter can be controlled by varying laser pulse energy and pulse number. The formation mechanism is studied and found to be self-catalyzed vapor-liquid-solid process. (c) 2006 American Institute of Physics.

Control of filamentation induced by femtosecond laser pulses propagating in air

Filamentation formed by self-focusing of intense laser pulses propagating in air is investigated. It is found that the position of filamentation can be controlled continuously by changing the laser power and divergence angle of the laser beam. An analytical model for the process is given.

Polarization-dependent supercontinuum generation from light filaments in air

We investigate polarization-dependent properties of the supercontinuum emission generated from filaments produced by intense femtosecond laser pulses propagating through air over a long distance. The conversion efficiency from the 800-nm fundamental to white light is observed to be higher for circular polarization than for linear polarization when the laser intensity exceeds the threshold of the breakdown of air. (C) 2005 Optical Society of America.

The Uniform World Model: A Methodology for Predicting the Health Impacts of Air Pollution

47 p.

Local air pollution and global climate change taxes: a distributional analysis

25 p.