Vibrational excitation, effect

Adler-Golden, S.M. Franck-Condon analysis of thermal and vibrational excitation effects on the ozone Hartley continuum. J. Quant. Spectrosc. Radiat. Transf. 30, 175-185 (1983) Adler-Golden, S.M., Schweitzer, E.L., Steinfeld, J.I. Ultraviolet continuum spectroscopy of vibrationally excited ozone. J. Chem. Phys. 76, 2201-2209 (1982)... 

G. C. Schatz, A quasiclassical trajectory study of reagent vibrational excitation effects in the OH 4- H2 H2O 4- H reaction,... 

An important area that has yet to be fully explored is the effect of the flexibility of water molecules. The intennolecular forces in water are large enough to cause significant distortions from the gas-phase monomer geometry. In addition, the flexibility is cmcial in any description of vibrational excitation in water. 

The semiclassical theory introduced above can be extended to low vibrationally excited states [32]. The multidimensionality effects are more crucial in this case. As was found before [62, 70], the energy splitting may oscillate or even decrease against vibrational excitation. This cannot be explained at all by the effective ID theory. 

Next we discuss the effect of deuteratlon on low frequency modes Involving the protons> Because of the anharmonlc variation of the energy as a function of tilt angle a (Fig. 4b), the hindered rotations of H2O and D2O turn out to be qualitatively different. The first vibrational excited state of H2O Is less localized than that of D2O, because of Its larger effective mass. The oscillation frequency of the mode decreases by a factor 1.19 and the matrix elements by a factor 1.51 upon deuteratlon. Therefore, the harmonic approximation, which yields an Isotopic factor 1.4 for both the frequency and the Intensity, Is quite Inappropriate for this mode. 

An extensive review of the literature reveals that the only studies of vibrational effects in insertion chemistry have focused on reactions of 0(1D)175-177 and C(1D)177,178 with H2. Since there is no potential energy barrier to insertion in these systems, reaction proceeds readily even for unexcited reactants.179 Since the efficiency of vibrational excitation was 20% in both studies, due to the large cross-sections for ground state reactions, only small changes were observed in the experimental signal. From an analysis of the product distributions, it was concluded that while H2(v = 0) primarily reacted via an insertion mechanism, direct abstraction seemed to become important for = 1). For 0(1D), this is similar to behavior at elevated collision energies.180... 

Third, there are clear differences in the images for dissociation at the same wavelength while probing different spin-orbit states. Two effects contribute to these differences. One is the slight difference in energy in the atomic states, most easily seen in the data at 234 nm where the 0(3P2) data clearly has the strong contribution from vibrationally-excited O2 while the other spin-orbit states do not. In this case the threshold for the dynamical process that forms the vibrationally-excited products has been crossed by the 158.265 cm-1 of the spin-orbit excitation. The second effect is that due to the nature of the J-level. It is known that there is a v—J correlation from the angular fits as well as from the fact that when the polarization of the... 

It is unclear exactly how the two potential surfaces, and hence the interaction regions between them, behave as the parent molecules bend. Our experimental results indicate that the more bent the ozone molecules are as they dissociate the more effectively is the available energy channelled into the OA T, ) fragment vibration. It is possible that as the parent molecules bend, the crossing seams move to a region on the repulsive state that more strongly favors the production of vibrationally excited 02(3 ) fragments. 

Observed angular distributions were quasi-specular and scattered rotational distributions were strongly dependent upon the incidence energy, both observations indicating the direct nature of the interaction. The most important observation of the work was the approximately Arrhenius surface temperature dependence of the vibrational excitation probability, exhibiting an effective activation energy close to the vibrational excitation energy of the scattered molecule (see Fig. 2). The authors also showed that the... 

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