Date of Award
Doctor of Philosophy (PhD)
John B. Hopkins
This dissertation describes the development and application of pump-probe Raman spectroscopy using 8 ps laser pulses as a technique for the study of relaxation phenomena in the condensed phase. I show three examples of systems studied by this technique. First, the dissipation of the heat deposited in the cage of solvent molecules surrounding a photodissociated diatomic solute is directly measured in the solvent Raman spectrum. Second, we provide a full characterization of the excited $A\sp\prime$ state of iodine which is formed in solution following photodissociation. This work discusses the solvent dependence of the iodine atom recombination process and points toward (iodine atom-solvent molecule) complexes as an intermediate species leading to recombination on the $A\sp\prime$ state. We measure and rationalize the rates for both vibrational relaxation within and electronic relaxation out of the $A\sp\prime$ state. Turning to a laser system, we measure the chromophore-to-protein vibrational relaxation time in deoxyhemoglobin. We learn that mechanical energy finds its way out of the heme and into the protein matrix with 2 to 5 ps exponential time constant. Both the study of iodine and deoxyhemoglobin emphasize that measuring the dynamics of the Stokes and anti-Stokes transient Raman signals provides a direct and powerful method to study vibrational population relaxation. Raman spectra are directly sensitive to vibrational level spacings and populations. As a result, Raman bands dynamics can be affected by electronic, vibrational, and conformational processes. Most previous Raman picosecond experiments have lacked the sensitivity necessary to probe the weak, transient anti-Stokes spectrum, which provides invaluable information on vibrational population dynamics. We also use a subtraction procedure to isolate the transient features in the spectrum, making our spectra taken at kiloHertz repetition rates very sensitive to small changes in the spectrum. This enables us to compare directly the time dependence of changes in the Stokes spectrum with the time dependence of changes in the anti-Stokes spectrum.
Lingle, Robert Jr, "Picosecond Pump-Probe Raman Spectroscopy of Excited States and Relaxation Phenomena in the Condensed Phase." (1991). LSU Historical Dissertations and Theses. 5256.