We have characterized the vibrational predissociation (VP) of the Ne(2)Br(2) van der Waals complex using time- and frequency-resolved pump-probe spectroscopy. After exciting Br(2) within the complex to a vibrational level 16<or=nu(')<or=23 in the B state, we follow the flow of halogen vibrational energy to the van der Waals modes in real time by recording the time-dependent behavior of Ne(2)Br(...

By using cavity ring-down spectroscopy technique, we have observed the channel leading to Br(2) molecular elimination following photodissociation of bromoform at 248 nm. A tunable laser beam, which is crossed perpendicular to the photolysis laser beam in a ring-down cell, is used to probe the Br(2) fragment in the B(3)Pi(ou)(+)-X(1)Sigma(g)(+) transition using the range 515-524 nm. The ring-dow...

a theoretical study of the kinetic and mechanism of 3-aug-cope rearrangement in gas phase was performed usingdet methods at b3lyp levels of theory with 6-3114ig(d,p) bass set at 298.i5k. equilibrium moleculargeometries and harmonic vibrational frequencies of the reactant, transition state did product were calculated. then,rate constant and activation thermodynamics parameters were calculated an...

Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate contr...

The PFI-ZEKE spectra of the first four vibrational levels of O;(a “n,) are reported. The rotationally resolved photoelectron spectra were assigned by diagonalizing the appropriate Hamiltonian in a Hund’s case a basis set. An extension of a previous model for rotational line strengths (the BOS model) to the intermediate coupling case was applied to the three vibrational bands with v+ = 1-3. As h...

Electronic structures of azaindole were studied using symmetry-adapted cluster configuration interaction theory utilizing Dunning's cc-pVTZ basis set augmented with appropriate Rydberg spd functions on carbon and nitrogen atoms. The results obtained in the present study show good agreement with the available experimental values. Importantly, and contrary to previous theoretical studies, the exc...

We use a combination of experimental THz time-domain spectroscopy and ab-initio density functional perturbative theory to accurately predict the terahertz vibrational spectrum of molecules in the crystalline phase. Our calculations show that distinct vibrational modes found in solid-state materials are best described as phonon modes with strong coupling to the intramolecular degrees of freedom....

The post-discharge kinetics is a very complex problem. Various radiative and non-radiative processes lead during the post-discharge period to the establishing of thermodynamic equilibrium. Generally, all these processes are vibrationally specific. A special interest deals with the processes of metastables. In presented numeric model of nitrogen plasma, the vibrational distribution function (VDF...

Changes in the electronic structure of pigments in protein environments and of polar molecules in solution inevitably induce a re-adaption of molecular nuclear structure. Both changes of electronic and vibrational energies can be probed with visible or infrared lasers, such as two-dimensional electronic spectroscopy or vibrational spectroscopy. The extent to which the two changes are correlated...