Energy, electronic molecular dissociation

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

The dynamics of fast processes such as electron and energy transfers and vibrational and electronic deexcitations can be probed by using short-pulsed lasers. The experimental developments that have made possible the direct probing of molecular dissociation steps and other ultrafast processes in real time (in the femtosecond time range) have, in a few cases, been extended to the study of surface phenomena. For instance, two-photon photoemission has been used to study the dynamics of electrons at interfaces [ ]. Vibrational relaxation times have also been measured for a number of modes such as the 0-Fl stretching m silica and the C-0 stretching in carbon monoxide adsorbed on transition metals [ ]. Pump-probe laser experiments such as these are difficult, but the field is still in its infancy, and much is expected in this direction m the near fiitiire. 

Gorse C and Capitelli M 1996 Non-equilibrium vibrational, electronic and dissociation kinetics in molecular plasmas and their coupling with the electron energy distribution function NATO ASI Series C 482 437-49... 

Carbon deposition from CO on a cobalt catalyst at low pressures is known to be a structure-sensitive process. CO is adsorbed molecularly on the low index surfaces (Co (0001)), but its dissociation occurs on the Co (1012), Co (1120), and polycrystalline surfaces.5762 Deposition of carbon on Co (1012) and the probable formation of Co3C have been established by Auger emission spectroscopy (AES) and low-energy electron diffraction (LEED) techniques.66... 

At 2000 K there is sufficient energy to make the H2 molecules dissociate, breaking the chemical bond the core density is of order 1026 m-3 and the total diameter of the star is of order 200 AU or about the size of the entire solar system. The temperature rise increases the molecular dissociation, promoting electrons within the hydrogen atoms until ionisation occurs. Finally, at 106 K the bare protons are colliding with sufficient energy to induce nuclear fusion processes and the protostar develops a solar wind. The solar wind constitutes outbursts of material that shake off the dust jacket and the star begins to shine. 

The fact that surface structure, in particular steps and coordinatively unsaturated sites, has an influence on the state and reactivity of carbon monoxide is entirely in keeping with the empirical correlation (Fig. 6) between heat of adsorption, electron binding energies, and molecular state. Elegant studies by Mason, Somorjai, and their colleagues (32, 33) have established that with Pt(lll) surfaces, dissociation occurs at the step sites only, and once these are filled carbon monoxide is adsorbed molecularly (Fig. 7). The implications of the facile dissociation of carbon monoxide by such metals as iron, molybdenum, and tungsten for the conversion of carbon monoxide into hydrocarbons (the Fischer-Tropsch process) have been emphasized and discussed by a number of people (32,34). 

A measure of the ability of an atom within a molecule to attract bonding electrons toward itselP . For a bond between two atoms of different electronegativities, the electron molecular orbital cloud is not symmetric, and the atom with the higher electronegativity attracts the larger proportion of the cloud. The most popular quantitative description was presented by Pauling, who based his scale on bond dissociation energies (measured in kcal per mol). 

Electron-Induced Reactions—HREELS Measurements. Novel LEE-induced chemistry has also been observed in HREEL measurements of molecular solids and molecules physisorbed on the surface of RGS. For example, Lepage et ah, building on the initial observations of Jay-Gerin et al. [141], have employed HREELS to measure in situ, neutral dissociation products arising from the impact of low-energy electrons on thin multilayer films of methanol [37] and acetone [38]. The technique is similar to that developed earlier by Martel et al. [258] for chemisorbed systems, in that the same electron beam is used for both the production and the detection of the neutral fragments. However, in the work of Lepage... 

Most of the energy associated with an incident x-ray or y-ray is absorbed by ejected electrons. These secondary electrons are ejected with sufficient energy to cause further ionizations or excitations. The consequences of excitations may not represent permanent change, as the molecule may just return to the ground state by emission or may dissipate the excess energy by radiationless decay. In the gas phase, excitations often lead to molecular dissociations. In condensed matter, new relaxation pathways combined with the cage effect greatly curtail permanent dissociation. Specifically in DNA, it is known that the quantum yields for fluorescence are very small and relaxation is very fast [6]. For these reasons, the present emphasis will be on the effects of ionizations. 

An incorrect dissociation limit is a common failure of SCF MO wavefunctions (as we already noted for H2O). Thus for H2 the SCF MO wavefunction (n ) leads to a dissociation limit which is an equal mixture of atoms and ions because there is no correlation between the two electrons (there is an equal chance of finding the two electrons on the same atom and on different atoms). The addition of a configuration (cTj ), where is the lowest energy unfilled molecular orbital, removes this error, and in the dissociation limit the wavefunction has to be an equal mixture of and Thus a wavefunction that stops at this limit is called an optimum double configuration (ODC) function. 

Inelastic collisions between the high-energy electrons and neutral molecules result in, among other processes, electron-impact ionization and molecular dissociation. Electron-impact ionization helps to sustain the discharge, and molecular dissociation creates free radicals that contribute to the deposition processes. 

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