Structure and dynamics of higher vibronic levels in the methyl radical Rydberg 3s state
- Univ. of California, Davis, CA (United States); and others
The structure and dynamics of vibronic levels in the methylradical Rydberg 3s state above the origin were examined by far-ultraviolet resonance Raman spectroscopy. Rotationally resolved Raman excitation profiles were obtained for the CD{sub 3} [0100] level of the Rydberg 3s state. The dissociation rates from the CD{sub 3} [0100] level were observed to be 2 times faster than those from the [0000] level. The Raman excitation profile analysis yields 47 271 cm{sup {minus}1} for the band origin of the [0100]-[0100] ground to Rydberg 3s absorption (X {sup 2}A{sub 2}{sup {double_prime}} {r_arrow} B {sup 2}A{sub 1} {sup {prime}}). The out-of-plane bend frequency, v{sub 2}{sup prime}, in the Rydberg 3s state is determined to be 1094 cm{sup {minus}1}. The structure and dynamics of the CH{sub 3} [1000]-[0000] vibronic transition were examined. Q branch excitation profiles of the v{sub 1} and 2v{sub 1} Raman features place the [1000]-[000] band origin at 206.85 nm. The Rydberg 3s state symmetric stretching frequency, v{sub 1}{sup prime}, is consequently estimated to be 2040 cm{sup {minus}1}. The dephasing nm. The Rydberg 3s state symmetric stretching frequency, v{sub 1}{sup prime}, is consequently estimated to be 2040 cm{sup {minus}1} The dephasing constant in the [1000] level is determined to be approximately 400 cm{sup {minus}1}, corresponding to a predissociation lifetime of 13 fs. 27 refs., 7 figs., 2 tabs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 237271
- Journal Information:
- Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 9 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
- Country of Publication:
- United States
- Language:
- English
Similar Records
Multiple-overtone resonance Raman scattering and fluorescence from I{sub 2} species adsorbed on silver surfaces
Measurement of vibrational frequencies of the H/sub 3/ molecule using two-step photoionization