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Vibrational motion, delocalization

There are three quite distinct perturbations that could have caused the vibrational motion to delocalize. The first is that the potential that governs the vibrational motion is not harmonic and it is not harmonic either in the simulations or, of course, in the real molecule. In our experience, under most circumstances this is the effect that comes in at the earliest times. We have seen this to be the case not only for a chemical reaction but also in simulations of femtosecond pump-probe experi-... [Pg.97]

The so-called Boson peak is visible as a hump in the reduced DOS, g(E)IE (Fig. 9.39b), and is a measure of structural disorder, i.e., any deviation from the symmetry of the perfectly ordered crystal will lead to an excess vibrational contribution with respect to Debye behavior. The reduced DOS appears to be temperature-independent at low temperatures, becomes less pronounced with increasing temperature, and disappears at the glass-liquid transition. Thus, the significant part of modes constituting the Boson peak is clearly nonlocalized on FC. Instead, they represent the delocalized collective motions of the glasses with a correlation length of more than 20 A. [Pg.528]

Beyond the Boson peak, the reduced DOS reveals for all studied glasses a temperature-independent precisely exponential behavior, g(E)/E exp( / o) with the decay energies Eo correlating with the energies E of the Boson peak. This finding additionally supports the view that the low-energy dynamics of the glasses are indeed delocalized collective motions because local and quasilocal vibrations would be described in terms of a power law or a log-normal behavior [102]. [Pg.528]

These TR results demonstrate that the localized model of Ru(bpy) + is valid on the timescales of electronic motions and molecular vibrations. It is virtually certain that delocalization (via, for example, intramolecular electron transfer or dynamic Jahn-Teller effects) occurs on some longer timescale. [Pg.480]

The coupling of the nuclear and electronic coordinates is probably not a major issue in the discussion of most outer-sphere electron-transfer reactions because (1) the nuclear motions, or molecular vibrations, at the donor and acceptor centers are independent of one another and (2) the D/A electronic coupling and the fraction of delocalized electron density are both small. One perspective on the classical, Marcus-Hush description of the electron-transfer reaction... [Pg.1187]

The particle beam LC/FT-IR spectrometry interface can also be used for peptide and protein HPLC experiments to provide another degree of structural characterization that is not possible with other detection techniques. Infrared absorption is sensitive to both specific amino acid functionalities and secondary structure. (5, 6) Secondary structure information is contained in the amide I, II, and III absorption bands which arise from delocalized vibrations of the peptide backbone. (7) The amide I band is recognized as the most structurally sensitive of the amide bands. The amide I band in proteins is intrinsically broad as it is composed of multiple underlying absorption bands due to the presence of multiple secondary structure elements. Infrared analysis provides secondary structure details for proteins, while for peptides, residual secondary structure details and amino acid functionalities can be observed. The particle beam (PB) LC/FT-IR spectrometry interface is a low temperature and pressure solvent elimination apparatus which serves to restrict the conformational motions of a protein while in flight. (8,12) The desolvated protein is deposited on an infrared transparent substrate and analyzed with the use of an FT-IR microscope. The PB LC/FT-IR spectrometric technique is an off-line method in that the spectral analysis is conducted after chromatographic analysis. It has been demonstrated that desolvated proteins retain the conformation that they possessed prior to introduction into the PB interface. (8) The ability of the particle beam to determine the conformational state of chromatographically analyzed proteins has recently been demonstrated. (9, 10) As with the ESI interface, the low flow rates required with the use of narrow- or microbore HPLC columns are compatible with the PB interface. [Pg.166]

A scheme as described here is indispensable for a quantum dynamical treatment of strongly delocalized systems, such as solid hydrogen (van Kranendonk, 1983) or the plastic phases of other molecular crystals. We have shown, however (Jansen et al., 1984), that it is also very suitable to treat the anharmonic librations in ordered phases. Moreover, the RPA method yields the exact result in the limit of a harmonic crystal Hamiltonian, which makes it appropriate to describe the weakly anharmonic translational vibrations, too. We have extended the theory (Briels et al., 1984) in order to include these translational motions, as well as the coupled rotational-translational lattice vibrations. In this section, we outline the general theory and present the relevant formulas for the coupled... [Pg.162]


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See also in sourсe #XX -- [ Pg.95 ]




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Delocalized motions

Vibrational motion

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