Excited ions rotational excitation

Since the rotational constant of HeNe" " is largest among rare gas heterodimer ions, rotational fine structures in the electronic transition of FteNe" can be easily separated. Therefore, reliable data for the rotational distribution of HeNe" (B 1/2) can be obtained. When emission spectra obtained from the He afterglow reactions of Ne are measured at various He and Ne pressures, the HeNe (B 1/2-X 1/2) emission system is observed, as shown in Figure 10. Possible excitation processes of HeNe (B 1/2) are as follows ... 

Duncan M A, Bierbaum V M, Ellison G B and Leone S R 1983 Laser-induced fluorescence studies of ion collisional excitation in a drift field rotational excitation of N in He J. Chem. Phys. 79 5448-56... 

In (a), an ion and a gas atom approach each other with a total kinetic energy of KE, + KEj. After collision (b), the atom and ion follow new trajectories. If the sum of KE, + KEj is equal to KE3 + KE4, the collision is elastic. In an inelastic collision (b), the sums of kinetic energies are not equal, and the difference appears as an excess of internal energy in the ion and gas molecule. If the collision gas is atomic, there can be no rotational and no vibrational energy in the atom, but there is a possibility of electronic excitation. Since most collision gases are helium or argon, almost all of the excess of internal energy appears in the ion. 

For molecules and ions having more than one atom, the extra energy can make the component bonds rotate and vibrate faster (rovibrational energy). Isolated atoms, having no bonds, cannot be excited in this way. 

As excited atoms, molecules, or ions come to equilibrium with their surroundings at normal temperatures and pressures, the extra energy is dissipated to the surroundings. This dissipation causes the particles to slow as translational energy is lost, to rotate and vibrate more slowly as rovibrational energy is lost, and to emit light or x-rays as electronic energy is lost. 

The phase space theory in its present form suffers from the usual computational difficulties and from the fact it has thus far been developed only for treating three-body processes and a limited number of output channels. Further, to treat dissociation as occurring only through excitation of rotational levels beyond a critical value for bound vibrational states is rather artificial. Nevertheless, it is a useful framework for discussing ion-molecule reaction rates and a powerful incentive for further work. 

There exist a series of beautiful spectroscopy experiments that have been carried out over a number of years in the Lineberger (1), Brauman (2), and Beauchamp (3) laboratories in which electronically stable negative molecular ions prepared in excited vibrational-rotational states are observed to eject their extra electron. For the anions considered in those experiments, it is unlikely that the anion and neutral-molecule potential energy surfaces undergo crossings at geometries accessed by their vibrational motions in these experiments, so it is believed that the mechanism of electron ejection must involve vibration-rotation... 

Section III.C). Using a rotational temperature to characterize an ion source can be misleading, as the reactions used to form the ions of interest can be quite exothermic, producing vibrationally and even electronically excited ions. These degrees of freedom are more difficult to cool than rotations. Transitions from vibrationally excited molecules provide very useful information, if they can be identified and analyzed. Hot FeO (produced using 3% N2O in helium) has a... 

Obviously, a great deal more information could be obtained if the isomeric ions could be probed spectroscopically. Vibrational states of the various isomers are not generally well known, but some structural information is available. Thus, the rotational structure of vibrational transitions may provide a better signature for particular isomers. Certainly, insufficient data are available about the potential surfaces of electronically excited states for electronic excitation to be used as a probe, e.g., as in the very sensitive laser induced fluorescence. At present, there are sensitivity limitations in the infrared region of the spectrum, but this may well be an avenue for the future. The study of isomeric systems and their potential surfaces has just begun ... 

Photoelectron spectroscopy (PES, a non-mass spectral technique) [87] has proven to be very useful in providing information not only about ionization potentials, but also about the electronic and vibrational structure of atoms and molecules. Energy resolutions reported from PES are in the order of 10-15 meV. The resolution of PES still prevents the observation of rotational transitions, [79] and to overcome these limitations, PES has been further improved. In brief, the principle of zero kinetic energy photoelectron spectroscopy (ZEKE-PES or just ZEKE, also a nonmass spectral technique) [89-91] is based on distinguishing excited ions from ground state ions. 

A low AH for a cooperative cluster rotation allows excitation of a cluster of atoms from normal to saddle-point positions. Such an excitation may, in turn, lower the energy of the saddle-point sites relative to the normal sites, thus effectively introducing a AHg(T) that collapses in a smooth transition. At temperatures T> T, the mobile ions become disordered over the normal and saddle-point sites. Such a situation appears to be illustrated by stoichiometric LijN and PbFj (Goodenough, 1984). 

In support of this model, it is noted that LnFj - which has F ions on both octahedral and tetrahedral sites of a face-centred-cubic Ln -ion array - becomes a fast F -ion conductor below its melting point without any change in the cation array (O Keeffe and Hyde, 1975). This observation shows that some low-energy excitation other than the displacement of F ions into octahedral sites is operative, as is postulated with the cluster-rotation model for PbF2. 

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