Ultracoherent Transient Spectroscopy

Abstract

A major and ongoing focus of our research effort has been the development of laser pulse sequences analogous to those used in nuclear magnetic resonance, to study relaxation phenomena in condensed phases. Sequences of multiple rectangular 90° and 180° pulses with various phases have been used extensively in high resolution and solid state NMR for nearly three decades, and have been shown to enhance forbidden transitions, selectively refocus some intermolecular interactions, or even increase physiological image contrast for tumor identification. By contrast, the conventional approach to optical coherent transient spectroscopy (splitting a single high power pulse into several parts) generates pulse sequences with well defined delays, but generally totally unknown phases; in addition, the pulse shape is not easily controlled. This approach has proven extremely useful in the past, particularly if noncollinear pulses are used to exploit propagation effects, but growing recognition of the fundamental complexity of condensed phase relaxation processes (and the defects of a two-level approximation) reveals a fundamental need for a more powerful approach.