5 ×10−5

Above Barrier Resonances in HCl

D.J. Brown , A.J. Yencha , M.R.F. Siggel-King , Sunil Patel and G.C.M. King
1 2 3 3 1

1
Dept of Physics and Astronomy, Schuster Labs, University of Manchester, U.K. 2Dept of Chemistry, State University of New York at Albany, Albany, U.S.A.
1
3
CCLRC Daresbury Laboratories, Warrington UK

Introduction 40000
Red analyser
Results
35000 Blue analyser
Doubly ionised molecular states (dications) have The top spectrum in figure 5 shows a threshold

Intensity (arb Units)

30000
many current and possible future applications photoelectrons coincidence (TPEsCo) spectrum of
including lasing media for an XUV laser to energy 25000
HCl2+ . The photon energy interval is 20 meV and
storage for hydrogen fuel cells. Theoretically these 20000 each point has a cumulative dwell time of 20
systems are hard to calculate. This is because the 15000 minutes per point. There is clear evidence of three
properties of the dication are critically dependent on 10000
vibrational states numbered 0,1 and 2 in the
the height and width of the existence of a potential spectrum. The lower spectrum in figure 5 is the
5000
barrier[1] as shown in figure 1. Experimentalists can threshold photoelectron spectrum of HCl+ obtained
take motivation from the importance attached this 0
simultaneously.
1200 0 2+
HCl
class of molecule in ionospheric and interstellar 48 49 50 51 52 53
X ( Σ)
3 -

Coincidences (arb.units)
1000
Dication States
chemistry. Nominal Photon Energy 1
Figure 3: Main line and satellite states in a 800
The potential energy curve of hydrogen chloride threshold photoelectron spectrum of neon. 2
600
(HCl) is a combination of long range Coulomb 3 4

repulsion and molecular bonding forces. These two 400

effects combine to produce a local minimum that The Coincidence Technique 200
allows the formation of discrete vibrational states. Above Barrier Resonances? Baseline
With both electron analysers tuned to threshold and
The molecule can be excited from its ground state 0
both extraction fields operational it is possible to 1.3
into a doubly ionised quasi-bound X(3Σ-) state within HCl+

6
Counts/10
look for the two photoelectrons from a double- 1.2
the Franck-Condon overlap region (see figure 1).
ionisation event. In this mode it is important that 1.1
Figure 2: Schematic of coincidence both analysers are looking at the same part of the
Above Barrier Resonances spectrometer interaction region.
35.4 35.6 35.8 36.0 36.2
Photon Energy (eV)
36.4 36.6 36.8 37.0 37.2

It is well known that barrier penetration can occur
below a potential barrier via quantum tunnelling. It is
also possible that above the local maximum in the
barrier the outgoing wavepacket must also have a
finite probability of reflection. Thus allowing
vibrational resonances to exist above the coulomb
barrier.
Experiment
A schematic diagram of the apparatus is presented
in figure 2 which shows the coincidence electron
spectrometer. A beam of hydrogen chloride gas
emanates from a molybdenum capillary. The
effusing gas is illuminated with a beam of
synchrotron radiation from beamline MPW 6.1 at the
Daresbury SRS. The photon energy of this beam can
The time between the detection of one electron Figure 5: (top) A TPEsCO of the X(3Σ-) state of
(start) and the next electron (stop) is measured HCl++ , (bottom) TPE spectrum of HCl+.
using a Time to Amplitude Converter (TAC). Events
A scan over a narrower range with longer dwell
which contribute to random coincidence counts,
time of almost 43 minutes per point is presented
occur randomly in time and lead to a flat background
in figure 6. The top of the barrier has been
in the time spectrum as shown in figure 4. However,
calculated to occur at 36.1 eV [2]. The data
true coincidences due to correlated events form a
suggest that state 4 in the spectrum exists above
peak sitting on top of this flat background as can
counts over period spectrum was taken
4000 the barrier.
5500
clearly be seen. The true coincidence count rate is
1
about 3500
1 Hz and the true to random ratio is about
5000

Coincidences (arb. units)

3000
be set or ramped over a region of interest which for 10:1.
2500 4500
this excited state is from 35.4 to 37.2eV. The lenses 2
2000
and extraction elements of the two energy analysers Top of Barrier
4000
are tuned to efficiently collect and transmit only zero 1500

energy (threshold) photoelectrons from the 1000

3500 3
4
interaction region. This was done by observing the 500

the (1D)3s(2D) satellite state in neon which has a 0 3000

maximum cross-section at its threshold due to the -500

existence of a nearby resonance state [2]. A typical 0 2 4 6 8 10 2500

35.7 35.8 35.9 36.0 36.1 36.2
Time signal between start and stop signals ( µσ)
example of a threshold photoelectron spectrum Photon Energy (eV)
(TPES) in neon showing the satellite state and the Figure 4: A time coincidence spectrum
Figure 1: The potential energy curve of the X3Σ- Figure 6: A TPEsCO spectrum in the region of
mainline is shown in figure 3. obtained in HCl.
state of HCl++ [1]. the top of the barrier of HCl++ dication.

REFERENCES ACKNOWLEDGEMENTS
[1] F.R. Bennet et al : Molecular Physics (1999) 97, No.1/2 35-42. This work is being carried out with financial support from ESPRC.
[2] R I Hall et al : J Phys B (1991) 24, 4133-4146.