| In this body of work, many tools to vibrational spectroscopy are presented. The techniques discussed include: transient absorption (pump-probe) spectroscopy, vibrational echo spectroscopy, and novel methods of internal Stark spectroscopy. Time dependent ultrafast infrared spectroscopy was utilized to investigate the inter- and intra-molecular interactions within various energetic materials while very novel Stark spectroscopy results of biologically relevant porphyrins are also demonstrated.; The first vibrational relaxation studies on many different energetic materials are presented, while a temperature dependent pump probe study was performed on a more exotic and recently de-classified material. Picosecond infrared pump-probe measurements of the vibrational relaxation of the asymmetric NO2 stretching mode that absorbs 6.26–6.40 μm (1597–1623 cm−1) of TNAZ, RDX, HMX, CL-20 (abbreviations defined later in the text), and nitromethane, are presented. In addition, a temperature dependent study was performed between 50 K and 298 K on TNAZ. All of the lifetimes fall in the range of 2 ps to 6 ps with the exception of nitromethane, which has a lifetime of 16 ps. The temperature dependence of TNAZ is flat and solvent independent, suggesting an intea-molecular relaxation pathway that does not involve low frequency modes. A clearer picture of molecular relaxation, the phonon bath, and the density of states within these systems is also presented.; Internal vibrational Stark studies of two Fe (II) Deuteroporphyrins support suggestions that fluctuating electric fields contribute to the dephasing of the CO within the protein pocket. Data is presented that clarifies the coulombic interactions between the equatorial porphyrin substituents, the distal ligand and the CO cause a distinct spectral shift. This data opens a new pathway toward understanding the ability of the bound CO to experience dynamics of the solvent while protected within the protein pocket. An involved treatise into crystal structure, ab-initio estimated charge distribution, chromatic bandshift, and the symbiosis between these leads to very accurate estimates of the Stark tuning rate. |
