In a previous paper (J. Chem. Phys. 131, 044511 (2009)), it has been shown that on ultrashort length and time scales, the speed of vibrational energy transport along a molecular chain is limited by intrasite vibrational relaxation rather than the actual inter site propagation. However, since intrasite vibrational relaxation is length independent, the inter site propagation rate is expected to b...

High rotational levels of the 001 (Σ(u)) state of BeD(2) are perturbed by the nearby 03(3)0 (Φ(u)) state. Deperturbation analysis results in an experimental value for the vibrational energy of the 030 level.

The mode-specific vibrational energy relaxation of the amide I' and amide II' modes in NMA-d(1)/(D(2)O)(n) (n = 0-3) clusters were studied using the time-dependent perturbation theory at the B3LYP/aug-cc-pvdz level. The amide modes were identified for each cluster based on the potential energy distribution of each mode. The vibrational population relaxation time constants were derived for the a...

We observe electron emission when vibrationally excited NO molecules with vibrational state v, in the range of 9 < or = v < or =18, are scattered from a Cs-dosed Au surface. The quantum efficiency increases strongly with v, increasing up to 10(-2) electrons per NO (v) collision, a value several orders of magnitude larger than that observed in experiments with similar molecules in the ground vib...

The influence of solute-solvent interactions on the vibrational energy relaxation dynamics of perylene and substituted perylenes in the first singlet excited-state upon excitation with moderate (<0.4 eV) excess energy has been investigated by monitoring the early narrowing of their fluorescence spectrum. This narrowing was found to occur on timescales ranging from a few hundreds of femtoseconds...

Four different types of macroscopic models developed for the vibration-chemistry coupling in nonequilibrium flows for re-entry applications are presented. First, using an approach based on nonequilibrium thermodynamics, global rate coefficients of dissociation of N2 and O2 under parent molecular or atomic impact and backward molecular recombination are determined. Then a Two-Level Distribution ...

Fluorescence and phosphorescence are photon emission processes that occur during molecular relaxation from electronic excited states. These photonic processes involve transitions between electronic and vibrational states of polyatomic fluorescent molecules (fluorophores). The Jablonski diagram (Figure 1) offers a convenient representation of the excited state structure and the relevant transiti...

We investigate the effects of local vibrational excitations in the nonsymmetrized current noise S(ω) of a nanojunction. For this purpose, we analyze a simple model the Holstein model in which the junction is described by a single electronic level that is coupled to two metallic leads and to a single vibrational mode. Using the Keldysh Green’s function technique, we calculate the nonsymmetrized ...

The methods producing cold molecules from cold atoms tend to leave molecular ensembles with substantial residual internal energy. For instance, cesium molecules initially formed via photoassociation of cold cesium atoms are in several vibrational levels nu of the electronic ground state. We applied a broadband femtosecond laser that redistributes the vibrational population in the ground state v...