Elucidation of ultrafast photophysics with optical pulse shaping.

摘要

Optical pulse shaping is an incisive tool of laser spectroscopy that allows the experimentalist extensive flexibility to manipulate the electric field of an excitation laser pulse. In this thesis, four applications of optical pulse shaping are examined. In Chapter 2, a partially non-collinear implementation of two-dimensional electronic spectroscopy is demonstrated for the first time on rubidium vapor. The use of a pulse shaper in this context is advantageous as it significantly reduces the complexity of the experimental apparatus. Unfortunately, non-ideal pulse shaping due to pixelation effects in some pulse-shaping devices leads to spurious pulse generation when the spatial masks become highly modulated. To model the effects on recovered 2D spectra, the optical Bloch model is numerically propagated with an explicit inclusion of the electric field modified by pixelation effects. Finally, steps necessary to minimize distortions are outlined. Chapter 3 describes a series of experiments designed to study the mechanism of multiple exciton generation in semiconductor quantum dots through open and closed loop coherent control schemes. The data collected with open loop control methods indicate that the initially formed exciton relaxes on an ultrafast time scale (20 fs) revealing the reason for a lack of controllability in adaptive, closed-loop optimizations. Chapter 4 of this thesis examines the process of singlet fission in tetracene thin films employing coherent control and ultrafast pulse shaping. Singlet fission is a promising avenue to achieving highly efficient third generation photovoltaic devices, and in this work, closed-loop control suggests that low-frequency nuclear motions play a mechanistic role in tetracene singlet fission. Finally, Chapter 5 examines a specific class of pulse shaping, sinusoidal spectral phase modulation, which is widely employed in the coherent control community as a route toward an intuitive probe into molecular dynamics. This work seeks to build a bridge between the fields of nonlinear spectroscopy and coherent control by describing the light-matter interactions characteristic of this type of pulse shaping using the tools of time-dependent perturbation theory. This description allows experimentalists to predict and test theories of coherent control simply and with little ambiguity, furthering the usefulness of coherent control as a spectroscopic tool.