Double-resonance spectroscopy of autoionizing states of water
The goal of this research program is to develop a conceptual understanding
of the mechanisms for the conversion of energy and angular momentum among
the electronic, vibrational, rotational, and translational degrees of freedom
in the highly excited states of a prototypical triatomic molecule, water.
Such microscopic mechanisms serve as prototypes for the mechanisms responsible
for elementary chemical reactions. The goal of this program will be addressed
by studying the spectroscopy and dynamics of the Rydberg states of water
near their first ionization thresholds; these states are particularly interesting
because they can decay by either ionization or dissociation. The dependence
of these competing decay processes on the electronic, vibrational, and
rotational quantum numbers of both the decaying state and its fragments
is expected to provide substantial insight into the mechanisms of both
processes. The experiments will be performed by using a double resonance
scheme using VUV light to pump an intermediate Rydberg state; subsequent
absorption of light from a second laser will prepare highly excited Rydberg
states in a state-selective manner, and the different decay products will
be monitored by using a variety of detection techniques.
Early work on this project has yielded the first double resonance spectra
of vibrationally autoionizing states of water. Previous work utilized one-photon
excitation directly from the ground state; as a result, final states were
excited unselectively from several ground rotational states, and the observed
Rydberg autoionizing state transitions were weak, complicated, and rode
on a large background of direct photoionization. This made comparison to
theory somewhat speculative. Use of intermediate resonance with a relatively
low-lying Rydberg state offers a much cleaner experiment on several counts.
First, a single rotational state of the intermediate state can be populated,
resulting in drastic spectral simplification and a labeling of the possible
angular momenta of the final states. Second, since a Rydberg state has
nearly the same geometry as the molecular ion's ground state, one can excite
particular final vibrational states with a high degree of selectivity by
choosing the same vibrational state in the intermediate state (thank you,
Franck and Condon).
Figure 1 shows
the excitation scheme schematically. The intermediate state used for this
study is the C 1B1 state with one quantum of symmetric
stretch (100). The tunable VUV light near 120 nm which drives the first
step is produced using two-photon resonant difference frequency generation
in krypton gas. This process yields high conversion efficiency so that
a high enough intensity can be produced to excite a large fraction of the
ground state molecules to the C state. Strong excitation is required on
the first step due to the rapid predissociation of the C state, which results
in a large loss of the excited state population before it can be further
excited to the high Rydberg states of interest. A secon laser tunable between
550 nm and 470 nm promotes the excited molecules to the region between
the ionization limit and the threshold for production of ions in the (100)
vibrational state. In this region lies our quarry, Rydberg states with
one quantum of symmetric stretch which are degenerate with, and coupled
to, the continuum of the (000) vibrationally unexcited states. The vibrationally
excited states autoionize due to their coupling with the continuum, leading
to resonances in the photoionization probability versus wavelength.
Figure 2
shows a spectrum of autoionizing states in the region of principal quantum
number of n=6, excited from the 111 rotational state. The (100)
states stand out strongly above a small direct photoionization background,
and the signal-to-noise is pretty nifty compared to previous work. Detailed
analysis of such spectra are underway in collaboration with Mark Child
at Oxford. We now know that, surprisingly, the sharp transitions
in the spectrum are due to excitation of nf states, the first time such
states of water have been observed. The broader peaks are nd state
transitions.
Just to show that we can see them, figure
3 shows a spectrum of J=1 high-n vibrationally autoionizing Rydberg
states converging to several rotational levels of the ion core, excited
from the 000 rotational state. This is the first time these
states have been observed, and should provide a fascinating test of quantum
defect theory for this important triatomic molecule.
Last Updated: July 9 1997 Webmaster