TITLE

Autodetachment spectroscopy and dynamics of vibrationally excited dipole-bound states of H2CCC-

AUTHOR(S)
Yokoyama, K.; Leach, Gary W.; Kim, Joseph B.; Lineberger, W. C.; Boldyrev, A. I.; Gutowski, M.
PUB. DATE
December 1996
SOURCE
Journal of Chemical Physics;12/22/1996, Vol. 105 Issue 24, p10706
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
Direct observation of the rotational fine structure levels of a vibrationally excited negative ion dipole-bound state (DBS) is reported. Autodetachment resonances of H[SUB2]CCC[SUP-] were observed for the [SUP2]A[SUB1] - [SUP2]B[SUB1] transition in one quanta of ν[SUB6], ν[SUB4], and ν[SUB2] and two quanta of ν[SUB6] vibrational modes of the DBS. Rotational assignments for both the electronic ground state and the DBS were performed. Strong type (a) Coriolis coupling between ν[SUB6] and ν[SUB9] in both the electronic ground and excited states was observed, and coupling constants were determined. QCISD ab initio calculations were performed for the ground state, the negative ion, and the neutral state of H[SUB2]CCC. The calculations on the neutral agree well with measured vibrational frequencies of the dipole-bound state. The autodetachment resonances contain information about the detachment dynamics via the observed linewidths, showing, e.g., that motions along the dipole moment axis significantly enhance autodetachment, indicating that the DBS is unstable with respect to neutral core motion which modulates the magnitude value of the dipole moment.
ACCESSION #
9815291

 

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