Photodissociation Spectroscopy and Dynamics of Free Radicals, Clusters, and Ions


Book Description

The photodissociation spectroscopy and dynamics of free radicals and ions is studied to characterize the dissociative electronic states in these species. To accomplish this, a special method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with the technique of fast beam photofragment translational spectroscopy. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states. Branching ratios to various product channels, the translational energy distributions of the fragments, and bond dissociation energies are then determined at selected photon energies. The detailed picture of photodissociation dynamics is provided with the aid of ab initio calculations and a statistical model to interpret the observed data. Important reaction intermediates in combustion reactions have been studied: CCO, C2H5O, and linear C{sub n} (n = 4--6).










Photodissociation Dynamics and Spectroscopy of Free Radical Combustion Intermediates


Book Description

The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(E{sub T}), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculations are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.







The Energetics and Dynamics of Free Radicals, Ions, and Clusters


Book Description

Structure and energetics of free radicals, ions, and clusters are being investigated by photoelectron photoion coincidence and analyzed using ab initio molecular orbital and statistical theory (RRKM). Molecules or free radicals are prepared in a molecular beam. Translational temperature is found from measured time of flight peakwidth; the vibrational temperature, from shift in dissociation onset. Free radicals are produced by pyrolysis in the nozzle; their subsequent cooling is demonstrated. Ion dissociation rates in the range from 10[sup 4] to 10[sup 7] s[sup [minus]1] are measured from the asymmetric TOF distribution; this method was used to measure the dissociation rates of cold and warm butene ions. 2 figs.










Studies of Transition States, Clusters, and Radicals by Negative Ion Photodetachment and Photodissociation


Book Description

Our AFOSR-supported research during the last three years focused on several experimental programs at the interface of ion spectroscopy and molecular reaction dynamics. We have developed a new method for high resolution photodetachment spectroscopy of negative ions based on photoelectron imaging (SEVI, or Slow photoElectron Velocity-map Imaging) and applied it to simple test systems as well as a pre-reactive van der Waals complex. We have measured photoelectron spectra of solvated transition state precursor anions, and used the vibrational structure in these spectra to infer to effect of various solvents on the strong hydrogen bond in the anion core. This work led to a series of experiments in which we measured the infrared spectra of several strongly hydrogen-bonded anions and the protonated water dimer H5O2+. These experiments were performed on the Free Electron Laser for Infrared experiments (FELIX) which produces high power, tunable infrared pulses over a broad spectral range, enabling the first measurements of the low (