Picosecond real‐time studies of mode‐specific vibrational predissociation

Vibrational predissociation in the HCl dimer.

We present results of a combined theoretical and experimental study on the vibrational predissociation of the HCl dimer. On the theoretical side, photodissociation linewidths and product-state distributions for monomer stretch excited states with total angular momentum J=0 were computed, using the Fermi golden rule approximation. The resonances investigated include excitation of the hydrogen bo...

Ab initio vibrational predissociation dynamics of He-I2(B) complex.

Three-dimensional quantum mechanical calculations on the vibrational predissociation dynamics of HeI2 B state complex are performed using a potential energy surface accurately fitted to unrestricted open-shell coupled cluster ab initio data, further enabling extrapolation for large I2 bond lengths. A Lanczos iterative method with an optimized complex absorbing potential is used to determine ene...

Vibrational predissociation spectroscopy of Ar-tagged, trisubstituted silyl cations

Vibrational predissociation spectra of the (CH3)2RSi Arn, (R = H and CH3, n = 1 and 2) ions are compared with harmonic calculations to structurally characterize these putative reactive intermediates. Although the vibrational photofragmentation behavior indicates that the Ar–Si bond is quite strong relative to that found in closed shell ions, formation of the Ar adducts is calculated to cause on...

NeCl2 and ArCl2: transition from direct vibrational predissociation to intramolecular vibrational relaxation and electronic nonadiabatic effects.

Pump-probe results are reported for NeCl(2) excited to the Cl(2) B state, undergoing vibrational predissociation, and then probed via E <-- B transitions. Intensities, lifetimes and product vibrational branching ratios are reported for 16 < or = v' < or = 19 Cl(2) stretching quanta. The intensity of the signal rapidly decreases above v' = 17. Detailed wave packet calculations of the vibrational...

A hybrid classical/quantum approach to cluster fragmentation dynamics: Application to the vibrational predissociation of He2Cl2