Reactive collision dynamics by far wing laser scattering: Mg+H2

We have measured the far wing absorption profiles of the MgH2 collision system leading to both the nonreactive formation of Mg* and into two distinct final rotational states of the reaction product MgH (v″=0, J″=6, 23). We have observed qualitatively expected behavior including a pronounced red wing...

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Veröffentlicht in:The Journal of chemical physics 1986-11, Vol.85 (10), p.5493-5504
Hauptverfasser: KLEIBER, P. D, LYYRA, A. M, SANDO, K. M, ZAFIROPULOS, V, STWALLEY, W. C
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Sprache:eng
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Zusammenfassung:We have measured the far wing absorption profiles of the MgH2 collision system leading to both the nonreactive formation of Mg* and into two distinct final rotational states of the reaction product MgH (v″=0, J″=6, 23). We have observed qualitatively expected behavior including a pronounced red wing in the reactive absorption profile indicating strong reaction probability on the excited attractive potential surfaces. We have also observed novel aspects of the excited state dynamics including reactive vs nonreactive channel competition effects and a strong far blue wing reactive absorption suggesting significant reaction probability even for trajectories on the repulsive surfaces. We have developed a simple theoretical model to semiquantitatively explain our experimental results. This model uses standard quasistatic theory to estimate the absorption probability as a function of detuning between levels of MgH2 and with assumed nonreactive vs reactive branching ratios, accounts for the subsequent evolution on the excited potential surfaces. This theory correctly predicts the overall shapes of the profiles and in general gives reasonable predictions for the relative magnitudes of the wing intensities.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.451560