Radiofrequency/optical double resonance spactroscopy of $HO_{2}$.
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Date
1994
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
Using a Ti-sapphire laser and a radiofrequency wave guide in combination with a fast, mass-selected beam of $He_{2}$ in the meta-stable a ${^{3}}\Sigma_{u}{^{+}}$ state, we have measured the fine structure splittings in the a $(\nu=0, N=25, 27, 29$ and $\nu=2, N=7, 9, 11)$ levels to a precision better than 15 kHz. The experimental spin-spin and spin-rotation coupling parameters $\lambda$ and $\gamma$ (in MHz) are well represented as second order polynomial in the internuclear separation, R (in atomic units): \[ \lambda(R)=-1101.221+1349.2241(R-2)-427.22254(R-2)^{2} \] and \[ \gamma(R)=-2.39823+4.70583(R-2)-3.27895(r-2)^{2} \] Using these polynomial and the nuclear wavefunctions calculated from the a-state potential of Yarkony [1], we can reproduce the experimental values of $\lambda$ and $\gamma$ within 0.01 MHz. The laser excites molecules from the a-state to quasibound levels in the $c {^{3}}\Sigma_{u}{^{+}}$ state, which decay by tunneling through the potential barrier of the c-state. The experimental linewidths agree well with those calculated using the empirical c-state potential of Lorents et al. [2]
Description
[1] D. R. Yarkony, J. Chem. Phys. 90, 7164 (1989). [2] D. C. Lorents, S. R. Keiding, and N. Bjerre, J. Chem. Phys. 90, 3096 (1989).
Author Institution: Institute of Physics and Astronomy, Aarhus University
Author Institution: Institute of Physics and Astronomy, Aarhus University