Resonant Scattering Processes

Resonant Scattering Processes. One of the problems which has attracted great interest this year is again due to the development of finely tunable dye lasers as light sources, and poses the question of what will be the temporal characteristics of excitation by a pulse as it is tuned through an atomic or molecular resonance, 

The depolarization of light by atomic gases 462 and the use of Raman scattering to probe exciton-phonon coupling in molecular crystals 463 have been discussed. 

A new perturbation expansion has been derived and applied to the coupling between non-adiabatic Born-Oppenheimer states in polyatomic molecules, for which previous methods are often unreliable.466 Franck-Condon computations on excited states of simple ABa polyatomics, including S02, CS2, and many 

A method for determination of vibrational temperature of organic molecules in solution from bandwidth and Stokes-shift measurements has been presented,470 and several aspects of the structure of electronic spectra in polyatomic molecules have been discussed.471 

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Raman process the spin center transfer to another energy level via a virtual state involving two phonons and this is called non-resonance scattering process. 

Since the parallel components of the dynamic dipole are active in RAIRS, it is possible to use the azimuthal dependence to obtain the orientation of the adsorbate at the surface. A similar technique has been applied to adsorbates on metals in HREELS measurements made off specular in order to observe parallel modes through impact or resonant scattering processes. This was first demonstrated for the Rh(CO)2 molecule on anisotropic TiO2(110) surface [72]. The results of this study also allow a test of the three layer model theory (Fig.5,6) as applied to S-polarised radiation. Fig. 11 shows the FT-RAIRS spectrum for 1/3 monolayer of Rh(CO)2 on Ti02(l 10) measured with P and S polarised radiation. 

One of the most interesting features of the Raman spectmm is its dependence on tire incident light frequency, coj. When Wj is on resonance with the excited electronic state, the scattering process closely resembles a process of absorption followed by emission. However, as Uj is detuned from resonance there are no longer... 

Anomalous X-ray diffraction or resonant scattering refers to the modification of its intensity due to absorption processes involving interactions between the X-ray beam and the atoms in the sample. This interaction combines the chemical and short-range order sensitivity of absorption with the long-range order sensitivity of diffraction. This results in a chemical selectivity, i.e. it is possible to differentiate elements with close atomic numbers or even cations with the same number of electrons like Rb+ and Sr2+... 

In the vicinity of the atomic absorption edges, the participation of free and bound excited states in the scattering process can no longer be ignored. The first term in the interaction Hamiltonian of Eq. (1.11) leads, in second-order perturbation theory, to a resonance scattering contribution (in units of classical electron scattering) equal to (Gerward et al. 1979, Blume 1994)4... 

Equation (6) defines most of the intrinsic characteristics of the DEA process. For further information on the mechanism of transient anion formation and its effects in isolated electron-atom and electron-molecule systems, the reader is referred to the review articles by Schulz [17] and others [7,19,20]. Information on resonance scattering from single layer and submonolayer of molecules physisorbed or chemisorbed on conductive surfaces can be found in the review by Palmer et al. [21-23]. The present article provides information essentially on resonances in atoms and molecules condensed onto a dielectric surface or forming a dielectric thin film. 

By scattering within molecular solids and at their surfaces, LEE can excite with considerable cross sections not only phonon modes of the lattice [35,36,83,84,87,90,98,99], but also individual vibrational levels of the molecular constituents [36,90,98-119] of the solid. These modes can be excited either by nonresonant or by resonant scattering prevailing at specific energies, but as will be seen, resonances can enhance this energy-loss process by orders of magnitude. We provide in the next two subsections specific examples of vibrational excitation induced by LEE in molecular solid films. The HREEL spectra of solid N2 illustrate well the enhancement of vibrational excitation due to a shape resonance. The other example with solid O2 and 02-doped Ar further shows the effect of the density of states on vibrational excitation. 

Initial femtochemistry theoretical models were simply generalizations of those for the single-photon DIET processes, i.e., as dynamics induced by multiple electronic transitions (DIMET) [100]. The idea is simply that even if the excited state residence is too short to cause excitation to a ground state continuum after resonant scattering (tR < tc), it can still cause some vibrational excitation in the ground state. If resonant... 

As described in the main text of this section, the states of systems which undergo radiationless transitions are basically the same as the resonant scattering states described above. The terminology resonant scattering state is usually reserved for the case where a true continuum is involved. If the density of states in one of the zero-order subsystems is very large, but finite, the system is often said to be in a compound state. We show in the body of this section that the general theory of quantum mechanics leads to the conclusion that there is a set of features common to the compound states (or resonant scattering states) of a wide class of systems. In particular, the shapes of many resonances are very nearly the same, and the rates of decay of many different kinds of metastable states are of the same functional form. It is the ubiquity of these features in many atomic and molecular processes that we emphasize in this review. 

More recently, Mies and Kraus have presented a quantum mechanical theory of the unimolecular decay of activated molecules.13 Because of the similarity between this process and autoionization they used the Fano theory of resonant scattering.2 Their theory provides a detailed description of the relationships between level widths, matrix elements coupling discrete levels to the translational continuum, and the rate of fragmentation of the molecule. 

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