Electron quantum path tuning and isolated attosecond pulse emission driven by a waveform-controlled multi-cycle laser field

We investigate high-order harmonic emission and isolated attosecond pulse (IAP) generation in atoms driven by a two-colour multi-cycle laser field consisting of an 800 nm pulse and an infrared laser pulse at an arbitrary wavelength. With moderate laser intensity, an IAP of similar to 220 as can be generated in helium atoms by using two-colour laser pulses of 35 fs/800 nm and 46 fs/1150 nm. The discussion based on the three-step semiclassical model, and time-frequency analysis shows a clear picture of the high-order harmonic generation in the waveform-controlled laser field which is of benefit to the generation of XUV IAP and attosecond electron pulses. When the propagation effect is included, the duration of the IAP can be shorter than 200 as, when the driving laser pulses are focused 1 mm before the gas medium with a length between 1.5 mm and 2 mm.

Constraints on the carbon cycle and climate during the early evolution of animals

One of the greatest challenges in science lies in disentangling causality in complex, coupled systems. This is illustrated no better than in the dynamic interplay between the Earth and life. The early evolution and diversification of animals occurred within a backdrop of global change, yet reconstructing the potential role of the environment in this evolutionary transition is challenging. In the 200 million years from the end-Cryogenian to the Ordovician, enigmatic Ediacaran fauna explored body plans, animals diversified and began to biomineralize, forever changing the ocean's chemical cycles, and the biological community in shallow marine ecosystems transitioned from a microbial one to an animal one.

In the following dissertation, a multi-faceted approach combining macro- and micro-scale analyses is presented that draws on the sedimentology, geochemistry and paleontology of the rocks that span this transition to better constrain the potential environmental changes during this interval.

In Chapter 1, the potential of clumped isotope thermometry in deep time is explored by assessing the importance of burial and diagenesis on the thermometer. Eocene- to Precambrian-aged carbonates from the Sultanate of Oman were analyzed from current burial depths of 350-5850 meters. Two end-member styles of diagenesis independent of burial depth were observed.

Chapters 2, 3 and 4 explore the fallibility of the Ediacaran carbon isotope record and aspects of the sedimentology and geochemistry of the rocks preserving the largest negative carbon isotope excursion on record---the Shuram Excursion. Chapter 2 documents the importance of temperature, fluid composition and mineralogy on the delta 18-O min record and interrogates the bulk trace metal signal. Chapter 3 explores the spatial variability in delta 13-C recorded in the transgressive Johnnie Oolite and finds a north-to-south trend recording the onset of the excursion. Chapter 4 investigates the nature of seafloor precipitation during this excursion and more broadly. We document the potential importance of microbial respiratory reactions on the carbonate chemistry of the sediment-water interface through time.

Chapter 5 investigates the latest Precambrian sedimentary record in carbonates from the Sultanate of Oman, including how delta 13-C and delta 34-S CAS vary across depositional and depth gradients. A new model for the correlation of the Buah and Ara formations across Oman is presented. Isotopic results indicate delta 13-C varies with relative eustatic change and delta 34-S CAS may vary in absolute magnitude across Oman.

Chapter 6 investigates the secular rise in delta 18-Omin in the early Paleozoic by using clumped isotope geochemistry on calcitic and phosphatic fossils from the Cambrian and Ordovician. Results do not indicate extreme delta 18-O seawater depletion and instead suggest warmer equatorial temperatures across the early Paleozoic.

Intensity-dependent asymmetric photoionization in few-cycle laser pulses

The asymmetric photoionization of atoms irradiated by intense, few-cycle laser pulses is studied numerically. The results show that the pulse intensity affects the asymmetric photoionization in three aspects. First, at higher intensities, the asymmetry becomes distinctive for few-cycle pulses of longer durations. Second, as the laser intensity increases, the maximal asymmetry first decreases then increases after it has reached a minimal value. Last, the value of the carrier-envelope phase corresponding to the maximal asymmetry varies with the pulse intensity. This study reveals that the increasing of pulse intensity is helpful for observing the asymmetric photoionization.

Photoionization of H atoms in few-cycle laser pulses

Photoionization of hydrogen atoms in few-cycle laser pulses is studied numerically. The total ionization probability, the. instantaneous ionization probability; and the partial ionization probabilities in a pair of opposite directions are obtained. The partial ionization probabilities are not always equal to each other which is termed as inversion asymmetry. The variation of asymmetry degree with the CE phase, the pulse duration and the pulse intensity is studied. It is found that the pulse intensity affects the asymmetry degree in many aspects. Firstly, the asymmetry is more distinct at higher intensities than that at lower intensities when the pulse duration exceeds 4 cycles; secondly, the maximal asymmetry in lower intensities varies with the CE phase visibly while at higher intensities riot; thirdly, the partial ionization probabilities equal to each other for some special CE phases. For lower pulse intensities, the corresponding value of CE phase is always 0.5 pi and 1.5 pi, while for higher pulse intensities, the corresponding value varies with the pulse intensity. Similar phenomena were observed in a recent experiment using few-cycle radio-frequency (RF) pulses.

Propagation of an arbitrary elliptically polarized few-cycle ultrashort laser pulse in resonant two-level quantum systems

We investigate the propagation of an arbitrary elliptically polarized few-cycle ultrashort laser pulse in resonant two-level quantum systems using an iterative predictor-corrector finite-difference time-domain method. It is shown that when the initial effective area is equal to 2 pi, the effective area will remain invariant during the course of propagation, and a complete Rabi oscillation can be achieved. However, for an elliptically polarized few-cycle ultrashort laser pulse, polarization conversion can occur. Eventually, the laser pulse will evolve into two separate circularly polarized laser pulses with opposite helicities.

Duration-dependent asymmetry in photoionization of H atoms in few-cycle laser pulses

The photoionization of H atoms irradiated by few-cycle laser pulses is studied numerically. The variations of the total ionization, the partial ionizations in opposite directions, and the corresponding asymmetry with the carrier-envelope phase in several pulse durations are obtained. We find that besides a stronger modulation on the partial ionizations, the change of pulse duration leads to a shift along carrier-envelope (CE) phase in the calculated signals. The phase shift arises from the nonlinear property of ionization and relates closely to the Coulomb attraction of the parent ion to the ionized electron. Our calculations show good agreement with the experimental observation under similar conditions.

Propagation of a few-cycle laser pulse in a V-type three-level system

Propagation of a few-cycle laser pulse in a V-type three-level system (fine structure levels of rubidium) is investigated numerically. The full three-level Maxwell-Bloch equations without the rotating wave approximation and the standing slowly varying envelope approximation are solved by using a finite-difference time-domain method. It is shown that, when the usual unequal oscillator strengths are considered, self-induced transparency cannot be recovered and higher spectral components can be produced even for small-area pulses. (c) 2005 Pleiades Publishing, Inc.

Optimization of high-order harmonic by genetic algorithm for the chirp and phase of few-cycle pulses

The brightness of a particular harmonic order is optimized for the chirp and initial phase of the laser pulse by genetic algorithm. The influences of the chirp and initial phase of the excitation pulse on the harmonic spectra are discussed in terms of the semi-classical model including the propagation effects. The results indicate that the harmonic intensity and cutoff have strong dependence on the chirp of the laser pulse, but slightly on its initial phase. The high-order harmonics can be enhanced by the optimal laser pulse and its cutoff can be tuned by optimization of the chirp and initial phase of the laser pulse.

Accurate determination of the absolute phase and temporal-pulse phase of few-cycle laser pulses

A Fourier analysis method is used to accurately determine not only the absolute phase but also the temporal-pulse phase of an isolated few-cycle (chirped) laser pulse. This method is independent of the pulse shape and can fully characterize the light wave even though only a few samples per optical cycle are available. It paves the way for investigating the absolute phase-dependent extreme nonlinear optics, and the evolutions of the absolute phase and the temporal-pulse phase of few-cycle laser pulses.

A scaling law of photoionization in few-cycle regime

In this paper, a scaling law of photoionization of atoms irradiated by intense, few- cycle laser pulses is established. The scaling law sets a relation to the phase- dependent ionization with the kinetic energy of photoelectrons, the duration and peak intensity of short pulses, and the ionization potential of the target atoms. We find that it will be advantageous to manifest the phase- dependent photoionization by choosing the target atoms with larger ionization potential, using laser with smaller carrier- frequency, and increasing the pulse intensity. (c) 2007 Optical Society of America.

Iridium and rhodium analogues of the Shilov cycle catalyst; and the investigation and applications of the Reduction-Coupled Oxo Activation (ROA) mechanistic motif towards alkane upgrading

This dissertation will cover several disparate topics, with the overarching theme centering on the investigation of organometallic C-H activation and hydrocarbon transformation and upgrading. Chapters 2 and 3 discuss iridium and rhodium analogues of the Shilov cycle catalyst for methane to methanol oxidation, and Chapter 4 on the recently discovered ROA mechanistic motif in catalysts for various alkane partial oxidation reactions. In addition, Chapter 5 discusses the mechanism of nickel pyridine bisoxazoline Negishi catalysts for asymmetric and stereoconvergent C-C coupling, and the appendices discuss smaller projects on rhodium H/D exchange catalysts and DFT method benchmarking.

Polarization evolution of a few-cycle ultrashort laser pulse propagating in a degenerate three-level medium

The propagation of an arbitrary polarized few-cycle ultrashort laser pulse in a degenerate three-level medium is investigated by using an iterative predictor-corrector finite-difference time-domain method. It is found that the polarization evolution of the ultrashort laser pulse is dependent not only on the initial atomic coherence of the medium but also on the polarization condition of the incident laser pulse. When the initial effective area is equal to 2 pi, complete linear-to-circular and circular-to-linear polarization conversion of few-cycle ultrashort laser pulses can be achieved due to the quantum interference effects between the two different transition paths.

Quantum path control in few-optical-cycle regime

We theoretically show that selection of a single quantum path in high-order harmonics generation can be realized in a few-optical-cycle regime with two-color schemes. We also demonstrate, in theory as well, the generation of spectrally smooth and ultrabroad extreme ultraviolet supercontinuum in argon gas which can produce single similar to 79 as pulses with currently available ultrafast laser sources. Our finding can be beneficial for generating isolated sub-100 as extreme ultraviolet pulses.

Carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium

We theoretically investigate carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium. Our results show that a soliton pulse can be generated during the two-photon resonant propagation of few-cycle pulse in the polar molecule medium. Moreover, the main features of the soliton pulse, such as pulse duration and intensity, depend crucially on the carrier-envelope phase of the incident pulse, which could be utilized to determine the carrier-envelope phase of a few-cycle ultrashort laser pulse from a mode-locked oscillator.