Recently, the predissociation lifetimes of the NeBr(2)(B) complex for different initial vibrational excitation (10<or=v(')<or=20) have been measured using time-resolved optical pump-probe spectroscopy [Taylor et al., J. Chem. Phys., 132, 104309 (2010)]. In the vibrational interval studied, the vibrational predissociation (VP) proceeds by the transfer of a single vibrational quantum and the life...

An overview of theories related to vibrational energy relaxation (VER) in proteins is presented. VER of a selected mode in cytochrome c is studied by using two theoretical approaches. One approach is the equilibrium simulation approach with quantum correction factors, and the other is the reduced model approach, which describes the protein as an ensemble of normal modes interacting through nonl...

Anharmonic vibrational calculations can already be computationally demanding for relatively small molecules. The main bottlenecks lie in the construction of the potential energy surface and in the size of the excitation space in the vibrational configuration interaction (VCI) calculations. To address these challenges, we use localized-mode coordinates to construct potential energy surfaces and ...

Vibrational energy transfer of the amide I mode of N-methylacetamide (NMA) is studied theoretically using the vibrational configuration interaction method. A quartic force field of NMA is constructed at the B3LYP/6-31G+(d) level of theory and its accuracy is checked by comparing the resulting anharmonic frequencies with available theoretical and experimental values. Quantum dynamics calculation...

We propose a design for an energy harvester which has the potential to harvest vibrational energy over a broad range of ambient frequencies. The device uses two flexible ceramic piezoelectric elements arranged in a buckled configuration in the absence of vibrations. Experimental data show that this design allows enhanced harvesting of energy relative to a comparable cantilever design, both for ...

Energy migrations at metal nanomaterial surfaces are fundamentally important to heterogeneous reactions. Here we report two distinctive energy migration pathways of monolayer adsorbate molecules on differently sized metal nanoparticle surfaces investigated with ultrafast vibrational spectroscopy. On a 5 nm platinum particle, within a few picoseconds the vibrational energy of a carbon monoxide a...

Results of a fully three-dimensional classical trajectory calculation of vibrational energy transfer are presented for the collision of HF(v = I) with HF(v = I) and its deuterium analog. A cross-correlation method, together with quasiclassical trajectories, is introduced to relate the changes in vibrational states of the two molecules to probabilities and rate constants. Multiple collisions are...

A general formulation of nonperturbative quantum dynamics of solutes in a condensed phase is proposed to calculate linear and nonlinear vibrational line shapes. In the weak solute-solvent interaction limit, the temporal absorption profile can be approximately factorized into the population relaxation profile from the off-diagonal coupling and the pure-dephasing profile from the diagonal couplin...

Picosecond time-resolved IR-UV pump-probe spectroscopy has been carried out to elucidate vibrational energy relaxation (VER) of the NH stretching vibrations of 2-aminopyridine monomer (2AP) and dimer [(2AP)(2)] in supersonic beams. In bare 2AP, intramolecular vibrational energy redistribution (IVR) of the NH vibrations is described by the two-bath mode model, in which the initial vibrational en...

Picosecond time-resolved IR-UV pump-probe spectroscopy has been carried out in order to elucidate vibrational energy relaxation (VER) of the NH stretching vibrations of 2-aminopyridine monomer (2AP) and dimer ((2AP)2) in supersonic beams. In bare 2AP, intramolecular vibrational energy redistribution (IVR) of the NH vibrations is described by the two bath mode model, where the initial vibrationa...