Electronic Spectroscopy and Dynamics of the CH/D-Ne Van der Waals Complexes

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Ohio State University

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Rotationally resolved spectra for the $A^{2}\Delta -X^{2} \Pi$ and $B^{2}\Sigma -X^{2} \Pi$ transitions of $CH/D-Ne^{1}$ have been recorded. Bands of both the A-X and B-X complexes were observed in association with the monomer 0-0 transition. In addition, complex bands associated with B-X monomer 1-0 transition were also recorded. Analyses of the ro-vibronic structures show that the complex is weakly bound in both the ground (X) and excited (A,B) electronic states. Preliminary results from the analysis of the highly congested A-X bands indicate that intermolecular bond length is unchanged upon excitation. A more detailed analysis is in progress and will be addressed. Analysis of the bands in the B-X system indicate that excitation to the B state reduces the binding energy and lengthens the intermolecular bond. The rotational levels of the X state were characterized by half-integer quantum numbers. This is in contrast to the situation for $CH(X)-Ar^{2}$ where the ground state exhibits integer rotational quantum numbers. The n=2 and n=1, k=0 bands in the B-X system showed homogeneous line broading as a result of rotational predissociation of the CH-Ne complex. B-X complex band assignments, rotational constants, and predissociation lifetimes will be discussed. Calculations are currently in progress on A-X system of CH/D-Ne in order to elucidate the origins of the rich rotational contours observed. Details and progress of the calculation will be reported on.


1) W. H. Basinger, U. Schnupf, and M. C. Heaven, {Electronic Spectroscopy and Dynamics Of the CHID-Ne Van der Waals Complex}. Submitted to: Faraday Discussion No. 97. Structure and Dynamics of Van der Waals Complexes. 2) G. W. Lemire, M. J. Mcquaid, A. J. Kotlar, and R. C. Sausa, J. Chem. Phys., 1993, 99, 91.
Author Institution: Department of Chemistry, Emory University