To my father, my first and foremost scientific and personal mentor. data from the McCoy group enabled the rotational analysis of Section 3.1, and geometries and MULTIMODE vibrational frequencies from the Bowman group enabled the discussion of Section 3.2.

The vibrational theory of olfaction assumes that electron transfer occurs across odorants at the active sites of odorant receptors (ORs), serving as a sensitive measure of odorant vibrational frequencies, ultimately leading to olfactory perception. A previous study reported that human subjects differentiated hydrogen/deuterium isotopomers (isomers with isotopic atoms) of the musk compound cyclo...

In order to rationalize subtle details in the liquid phase toluene Raman backscattering spectra, an analysis was performed based on a quantum-mechanical Hamiltonian operator comprising rotation of the methyl group and the angular dependence of vibrational frequencies and polarizability derivatives. The separation of the methyl torsion from the other vibrational motions appears to be necessary i...

Laser vibration sensing provides a sensitive non-contact means of measuring vibrations of objects. These measurements are used in industrial quality control and wear monitoring as well as the analysis of the vibrational characteristics of objects. In laser vibrometry, the surface motion is monitored by heterodyne laser Doppler velocimetry, and the received heterodyne signal is sampled to produc...

Vibrational probes can provide a direct readout of the local electrostatic field in complex molecular environments, such as protein binding sites and enzyme active sites. This information provides an experimental method to explore the underlying physical causes of important biomolecular processes such as binding and catalysis. However, specific chemical interactions such as hydrogen bonds can h...

For a variety of density functional theories, we examined the ground-state properties of the water monomer (geometry, vibrational frequencies, dipole moment, polarizability) and dimer (geometry, vibrational frequencies, bond energy, and barrier heights for the transition states for the interchange of hydrogen atoms within the dimer). Thus, we considered LDA (SVWN), seven pure GGA methods (BLYP,...

Femtosecond mid-IR transient absorption spectroscopy (TRIR) and time-dependent density functional theory (TD-DFT) calculations on Re(CO)(3)Cl(Me(2)BPTZ) [Me(2)BPTZ = 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine] are used to demonstrate that the lowest excited state of the complex is a triplet metal-to-ligand charge-transfer ((3)MLCT) state with a lifetime of 225 ps. The short excited-state li...

Raman and FTIR spectra of naphthalene and its cation have been systematically analyzed using ab-initio and density functional theory calculations. The optimized geometries, harmonic vibrational wave numbers and intensity of vibrational bands of naphthalene and its cation were calculated invoking different basis sets up to HF/6-311++G** and B3LYP/6311++G** level. Vibrational assignments have bee...

The relaxation mechanisms of local vibrational modes in solids are of central importance in understanding how such modes decay into phonons, the diffusion of impurities, and the loss of hydrogen passivation in technologically important materials. Interstitial oxygen in silicon is a model system for studying the relaxation of local vibrational modes into extended vibrational modes by measuring t...

We characterize the influence of graphene nanoribbon plasmon excitation on the vibrational spectra of surface-absorbed polymers. As the detuning between the graphene plasmon frequency and a vibrational frequency of the polymer decreases, the vibrational peak intensity first increases and is then transformed into a region of narrow optical transparency as the frequencies overlap. Examples of thi...