Control of Chemical Dynamics Using Arbitrary Shaped Optical Pulses and Laser-Enhanced NMR Spectroscopy.

A key feature of this thesis is the application of novel laser techniques to various fields of spectroscopy. The overall effort has been towards achieving either chemical control or enhanced spectroscopic resolution. The issue of chemical control forms the major bulk. Over the past decade, theoretical and technological developments have made it possible for a modern day chemist to be a more active participant in nature's chemical processes. Consequently, although the idea of manipulating chemical reactions has been a long term dream, it is only now that realization of such dreams has become realistic. One of the major contributions that is leading towards this realization is the development of pulse shaping techniques. Here, we concentrate on the important developments in this area that has come by recently, particularly emphasizing new results from our laboratory. We discuss in detail the current state-of-the-art, and present some experimental and theoretical demonstrations of chemical control by using arbitrarily shaped pulses. The major strength of our approach to pulse shaping has been in considering "robustness in the laboratory" as a primary constraint. Most of the shapes, addressed here, work under adiabatic conditions where the exact shape of the pulse is not critical as long as the basic criteria dictated by the adiabatic theorem are satisfied. A novel approach of "molecular pulse shaping"--using the molecule itself to generate its own pulse shape--is presented as an example of the ultimate form of robustness. Finally, we get into the issue of resolution enhancement by coupling laser radiation into a Nuclear Magnetic Resonance (NMR) spectrometer. Spectroscopic resolution enhancement is an everlasting effort in the field of NMR--even more for biological NMR. We present some of the recent experimental findings in our laboratory that show selective dispersion in the NMR spectrum when it is acquired under a non-resonant laser irradiation of the sample. Albeit promising, the observed effects are weak and the theoretical understanding of these experiments is not profound enough for implementing any immediate applications.