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Multiple photoionisation in the rare gases from threshold to 280 eV

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 1979 J. Phys. B: At. Mol. Phys. 12 2465 (http://iopscience.iop.org/0022-3700/12/15/008) View the table of contents for this issue, or go to the journal homepage for more

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J. Phys. B: Atom. Molec. Phys., Vol. 12, No. 15, 1979. Printed in Great Britain

Multiple photoionisation in the rare gases from threshold to 280 eV

D M P Hollandt, K Codling?, J B West$ and G V Marrt
t J J Thomson Physical Laboratory, University of Reading, Reading RG6 2AF, England
$ Science Research Council, Daresbury Laboratory, Daresbury, Warrington WA4 4AD, England

Received 27 October 1978, in final form 5 February 1979

Abstract. A time-of-flight spectrometer has been coupled with a source of synchrotron radiation to measure the photoionisation cross sections for multiple ionisation of the rare gases He to Xe in the photon energy range 50-280eV. Comparison is made with theoretical calculations both in the case of double ionisation of He, Ne and Ar and in the case of single ionisation of Kr and Xe, where electron correlation effects are supposed to enhance the various cross sections. The importance of an accurate knowledge of monochromator scattered light in such experiments is emphasised.

1. Introduction

Measurements of partial cross sections for multiple ionisation caused by photon impact give valuable information on the dynamic effects of electron correlations. For example, the process of double-electron ejection from outer shells is particularly interesting in the low photon energy region, since double ionisation via the well understood shakeoff process is too small to account for the relatively large observed double ionisation yield (Carlson 1967). Calculations of absolute yields of multiple electron processes are difficult and therefore experiments such as those described below become a definitive test of atomic theory. In recent years several experimental investigations on multiple ionisation in the rare gases have been carried out using both photon impact and electron impact (pseudophoton) techniques. For example, Schmidt et a1 (1976b) performed a careful set of photoionisation experiments on He, Ne and Ar, repeating the earlier electron impact measurements of Van der Wiel and Wiebes (1971a, b) and causing Wight and Van der Wiel (1976) to re-evaluate the accuracy of their method. In these later electron-loss measurements, substantial agreement was finally achieved between photon and pseudo-photon experiments. Nevertheless, since the Schmidt et a1 experiments constitute the only work on multiple ionisation over an extended photon energy range, it was thought worthwhile to repeat these measurements with a straightforward tinie-of-flight mass spectrometer and to extend them to the inert gases Kr and Xe.

2. Experimental details
In the following sections the essential components of the experiment are described briefly, namely the light source capable of producing extreme ultraviolet (XLJV) radia0022-3700/79/152465 + 20$01.00

01979 The Institute of Physics

2465

2466

D M P Holland et a1
(TOF)

tion, the grazing incidence monochromator and the time-of-flight trometer. 2.1. Light source

mass spec-

The radiation was derived from the 5 GeV electron synchrotron NINA at Daresbury, which produced a continuum peaking in the x-ray region but extending through the ultraviolet, visible and infrared regions of the spectrum (Codling 1973).

2.2. Monochromator
The synchrotron radiation was dispersed vertically by a zero-deviation grazing incidence monochromator (West et al 1974). The hard x-rays from NINA were liable to cause severe damage to replica gratings and since the first optical component exposed to the radiation was the plane grating itself, an original phase grating purchased from the National Physical Laboratory was incorporated. Details of the theory and production of such gratings have been described by Franks et a1 (1975). The grating had 632 grooves per mm, a total ruled area of 20 mm X 17 mm and was gold coated. A groove depth of 100 8,was chosen to produce a high efficiency over the wavelength range of interest and, hopefully, a high second-order suppression. Owing to the pulsed nature of the TOF mass spectrometer (4 2.3) it was impossible to distinguish those ions produced by first-order radiation from those produced by second and higher orders and stray light. It was therefore extremely important to employ a monochromator possessing a good high-order suppression capability. A schematic diagram of the monochromator, which was designed specifically to have this capability, is shown by West et a (1974), where the phase grating is followed by a mirror which 1 focuses the diffracted radiation onto the exit slit. The table incorporated in that paper gives the wavelength ranges over which second order was found to be below 5 % of the total signal. In figure 1 the spectral output of the monochromator on the lowest wavelength range using a sodium salicylate and photomultiplier combination is shown. The scattered light contribution from the wing of zero-order is seen to be quite substantial. However, the relevant stray light for the present experiment is that which could produce ions (i.e. less than 1000 8,). This is shown as a broken line in the figure. The structure at 44 8, is associated with the carbon K-edge from the thin film of oil coating the mirror and grating. A large part of the data was taken in this range. The monochromator band pass was varied according to the available photon flux and the partial cross sections under investigation. The relevant band pass is given in tables 1-5.

2.3. Time-of-flight mass spectrometer

A number of variants of the TOF spectrometer were investigated before the final design shown in figure 2 was chosen. The focusing conditions and resolution of such a two-field spectrometer were examined originally by Wiley and McLaren (1955) and so the theory will not be elaborated here. It should be noted, however, that those workers used a pulsed electron gun, whereas in the context of this experiment, the synchrotron radiation was essentially a continuous source of xuv photons. This resulted in each ion peak having a low velocity tail. Although the resolution was thereby limited, it was quite adequate to resolve the peaks of all the ions detected in the present experiment.

Multiple photoionisation in rare gases

LOO

2467

IO,

Photon energy IV eI , 300

200

.. ..
.*

Figure 1. Output of the grazing incidence monochromator (see West er a1 1974). The broken line denotes the stray light of wavelengths less than about 1000 A.
PTFE

I G

Figure 2. Schematic diagram of the time-of-flight drift tube. I, pulse input; P, pulser plate; G, gas inlet; F, photon beam; T, drift tube; M, 80 CPI meshes; C, accelerating field; W, windowless electron multiplier; R, D, rotary and diffusion pumps.

The inert gas was introduced through a capillary, G, as shown in figure 2. The monochromatised photon beam entered at right angles to the gas beam. The pulser plate, P, pulsed the ions in the direction of the drift tube, T, with a voltage of typically 80 V. When the extraction pulse was not being applied, the plate was held at -2 V in order to sweep out any ions formed during the 'off' period. The drift tube was held at -60 V relative to the earthed cage. Highly transmitting meshes, M, covered both ends of the drift tube which was 50 cm long. The ions, with drift times in the range 10-30 k s , were detected by a windowless electron multiplier, W, with a first dynode collection area of 25 mm x 25 mm.
2.3.1. Ion collection efficiency. Under this heading two effects that cause discrimination

of ions of different charge states are c0nsidere.d. The first occurs because an ion may

2468

D M P Holland et a1

have a component of velocity perpendicular to the axis of the drift tube, the second because the collection efficiency of the electron multiplier itself may vary. In order to ensure that the experimentally determined ion ratios were meaningful, it was necessary to calculate what percentage of ions missed the detector due to their thermal motion. Such discrimination has been discussed by Van Brunt et a1 (1971) and Stockbauer (1973) and a similar analysis was performed here. It was assumed that the initial energy distribution of ions was Maxwellian and, furthermore, that their angular distribution was isotropic. The fact that the photon beam at the interaction region was 5 mm in height was taken into account. The result of the computer program showed, as expected, that the singly charged ions would be discriminated against relative to the multiply charged ions. (Owing to their longer drift time, they were more likely to miss the first dynode of the detector.) The appropriate correction (-7%) was made to the singly charged ion raw data but was almost insignificant for the multiply charged ions. The second discrimination concerns the detection efficiency of the first dynode of the multiplier. This problem has been studied by Van der Wiel et a1 (1969), amongst others. They suggested that if the first dynode were held at -4 kV, then ions of all charge states would possess a sufficiently high impact energy to be measured with 100% efficiency; naturally this assumes an appropriately set threshold level at the preamplifier. On the basis of further investigations, Wight and Van der Wiel (1976) suggested -8 kV. In the present experiment, tests showed that if the first dynode was held at -7 kV relative to the drift tube, no discrimination occurred. The anode was held at -4 kV in this mode of operation. With these voltages applied to the electron multiplier, the noise level was quite high and this combination could only be used in cases of good ion count rates. In situations where low cross section and photon flux combined, the first dynode was set at -3 kV and the anode was earthed. The ion collection efficiency correction required when working in this mode was determined from data taken in regions of high count rates and was of the order of 5%. As before, the singly charged ions experienced the greatest discrimination.

2.4. Data acquisition

The electronics system was designed and constructed by J & P Engineering (Reading). A pulse and delay unit provided a trigger pulse to activate a voltage pulse to the pulser plate, P, and at the same time started a clock controlling the input to a 256 channel buffer register. After a preset delay from the receipt of the start pulse, the shift register was advanced at a rate between 200 kHz and 10 MHz. After the 256th clock pulse, any counts in the buffer register were transferred to a store. Thus a spectrum of the number of ions versus drift time was gradually accumulated in the store which could be viewed by a CRO. The ion extraction pulse, of approximately 1 p,s duration, and whose height could be varied up to + l o 0 V, was applied at a rate of 2 kHz. The count rates even in the strongest peak were so low that the possibility of two ions of the same charge state arriving at the detector at the same time was extremely remote. The number of counts in the smallest ion peak was generally used as the criterion for the overall running time at a particular photon energy, which could be as long as 6 hours. The contents of the store were recorded on paper tape and an X Y recorder. A rate-meter monitoring the incident photon flux switched off the system if, due to synchrotron radiation fluctuations, the photon intensity fell below a pre-selected level.

Multiple photoionisation in rare gases

2.5. Treatment of data

2469

The results in the following section will be presented without reference to problems associated with their acquisition. Two problems should be highlighted. The first relates to possible pressure-dependent effects within the interaction volume, the second to stray light emitted from the xuv monochromator. When an ion is produced in the interaction region, it is conceivable that charge exchange may occur, of either the resonant or non-resonant type. Other processes, such as recombination, electron impact ionisation, etc, might be envisaged but all of these should be pressure dependent. Therefore, for each inert gas, and at various
Neon Dressure run at 170eV

600

I ~ l O - ~ T o r r I*

(a)

200

2'

2 4 0 - 5 ~ 0 ~ r I+:

600 -

coo ---I

Neon pressure dependence

I

035001

170 eV

2'

..
N

z .
m

m z

0.1 20001

2+

1000

.:
100
150

I 0

10

x'

r5

Pressure (Torr1

30 50

C h a n n e l number

Figure 3. ( a ) Time-of-flight spectrum of Ne at various f pressures for a photon energy o 170 eV. ( b )The pressure dependence of the Ne*'/Ne+ ratio at 170 eV.

2470

D M P Holland et a1

photon energies, the ion ratios were measured as a function of ambient pressure. The Torr. Measurements were made in the pressure range base pressure was 2 x 5 x 1OP6-1 x lop4Torr and the results extrapolated to zero pressure. For all gases apart from Ne, the pressure correction was no more than 3%. However for Ne the pressure correction proved to be significant, as can be seen from the raw data of figure 3(a). The two isotopes of Ne can clearly be resolved in these TOF spectra. In figure 3 ( b ) the pressure dependence of the Ne2+/Nef ratio is shown. A similar increase was observed by Schmidt et a1 (1976a). A second important correction involved the stray light from the monochromator. As mentioned in 2.2, the monochromator was designed to avoid problems of second order and this it did extremely well. However, the stray light remained and could not be eliminated without removing the first-order radiation itself. The stray light made its greatest percentage contribution at high photon energies (see figure 1) and, although small, was nevertheless extremely significant. The way that the problem was attacked was both empirical and iterative. Firstly, a ratio of stray-to-real light was chosen at a particular first-order wavelength. The stray light was assumed to have a contribution up to an energy of 280 eV and was divided into 20 eV intervals. First estimates of the partial ion cross sections were taken from the raw data and these cross sections were multiplied by the assumed spectrumof stray light. If too large a stray-light contribution were to be assumed in a particular energy range, then removing this contribution from the raw data counts could make the final result non-physical. For example, in Kr and Xe above 200 eV, if the contribution of low energy radiation (which produced single ions) was too large, its removal from the raw single ion counts could easily make the result negative. Indeed, it is precisely this problem, combined with the inherently low cross section for single ion production, that leads to such large error bars (-20%) in the Kr and Xe cross sections of figures 10(a)and 14(a). The best manufactured stray-light spectrum appeared to be one giving equal weighting to each 2 0 e V interval. This may not be too unreasonable since the synchrotron radiation output rises whilst reflectivities fall with increasing photon energy. The stray-to-real light ratio finally arrived at produced the broken straight line of figure 1.

3. Results and discussion

Key to experimental data. Symbol Meaning Present data Schmidt et al (1976b) Carlson (1967) Lightner et al (1971) Chang et al (1971) Samson and Haddad (1974a) Van der Wiel and Wight (1975) Cairns et al (1969) West et al (1976) Wight and Van der Wiel (1977) Wight and Van der Wiel (1976), figures 4-9 El-Sherbini and Van der Wiel (1972), figures 10-17

n
0

A
X

+
0

0 0

Multiple photoionisation in rare gases

2471

Before discussing the various partial cross sections for each inert gas, it seems sensible to give the table above a single key to the various figures; the key is consistent from figure to figure. A general comment should be made about the partial cross sections obtained by electron impact. The relative cross sections in the earlier data of Van der Wiel and co-workers have been normalised to the absolute photoionisation cross sections determined by Marr and West (1976) and West and Morton (1978), except where stated otherwise.

3.1. Helium
The double ionisation threshold of He occurs at 79.0 eV. Figure 4 shows a composite of all available data on the ratio of He2+/He+from just below threshold to 300 eV; the present data, which are listed in table 1, cover a more limited range from 80 to 200 eV. The large error bars at 180 and 200 eV are due to the large statistical error in the doubly

I f

.
I

+a OOL

_ _ _ _ _ - - - -3-- -

002.

oL3

./
80

1LO

200

. 260

Photon energy lev)

Figure 4. The ratio of partial cross sections He2+/He+. See key for explanation of data , Byron and Joachain (1967); ---, Brown (1970); points. Theoretical curves: -.-.-, Amusia etal (1975).

Table 1. The partial photoionisation cross sections for helium.

Photon energy (eV) 80 100 120 140 160 180 200 Band pass (eV)

u2+(Mb)

u"(Mb)
05729 0.067 0.433 *0*039 0.276*0*024 0.186 0.01 6 0.129*0.011 0~091*0~008 0.065 ztO.006

2 3 5 7 9 11 14

0.0094* 0.0022 0.0123 0.0020 0~0097~0~0011 0.0078* 0.0009 0.0055 *0.0007 0.0043 *0.0008 0.0030k 0.0008

charged ion count, associated with the small total photoionisation cross section (less than 0.1 Mb). The present data show agreement with the three values of Schmidt et a1 (1976b) at low energies. The electron impact results of Wight and Van der Wiel(l976) tend to lie higher on average. There is poor agreement with the earlier data of Carlson (1967), obtained using ion spectroscopy and a filtered x-ray bremsstrahlung source.

2472

D M P Holland et a1

The theoretical curves of Byron and Joachain (1967)-full curve-and Brown (1970)-broken curve-agree reasonably well with the Carlson data. Byron and Joachain obtained their ratios by calculating the double photoionisation cross section and then using the theoretical values of Salpeter and Zaidi (1962) and Stewart and Webb (1963) for the single ion cross section. Brown re-evaluated the double ion cross sections using accurate Hylleraas wavefunctions for the ground state and estimated the error to be less than 10%. The chain curve calculated by Amusia et a1 (1975) is valid at high photon energies only and predicts an asymptotic value of He2+/He+ of 0.023 compared with 0.017 by Byron and Joachain. All theoretical values appear low compared with experiment, although Brown suggests that the asymptotic value will not be reached until the photon energy exceeds 600 eV. 3.2. Neon Figures 5 and 6 show respectively, the ratio Ne2+/Net, and the individual double ionisation cross sections over a photon energy range from 60 to 280 eV. Table 2 lists the various cross sections, including the single ionisation cross section. Several previous investigators have studied multiple ionisation in Ne and their experimental data, together with the theoretical calculations of Chang and Poe (1975)-full curve-and Carter and Kelly (1977)-broken and chain curves-are plotted in figure 5. Chang et a1 (1971) performed an earlier calculation at 278 eV and this is shown as an open hexagon. It is apparent that the present results are significantly lower than all other experimental values. As mentioned earlier, the Ne ratio of double-to-single ionisation increased significantly with increasing pressure, showing a far greater pressure dependence than any of the other inert gases. The Ne data were taken at a background pressure of Torr, so extrapolating the experimental results to zero pressure reduced this 2X ratio; the detection efficiency correction also reduced the ratio. One factor that could conceivably have explained a lower value of the ratio would have been a significant

Figure 5. The ratio of partial cross sections NeZ+/Ne+.Theoretical curves: -, Chang and Poe (1975);---(dipole length) and-.-.- (dipole velocity), Carter and Kelly (1977).

Multiple photoionisation in rare gases

2 2 2 ~ ' 2s'2p5

2473

2~02~6

Photon energy lev)

Figure 6. The NeZf absolute partial cross section. Theoretical curves as in figure 5 .

Table 2. The partial photoionisation cross sections for neon. Photon energy Band pass (eV)
2 2 2 2 3 3 4 4 5 6 7 8 9 10 11 9 10 12 9 9 5 6 6 7 7

(ev)
70 75 80 85 90 95 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280

aZ'(Mb)
0.081 f0.008 0.098f00010 0.1 12 f0.012 0.126* 0.012 0.158 f0.016 0.170f0.017 0.177 f0.018 0.210 0.021 0,178 0.017 0.183f0.017 0.178 f0.017 0.149f 0.014 0.142*0.013 0.129 0.012 0.1 15 0.01 1 0.104f 0.010 0.076f0.010 0.079 f0.010 0.070* 0.009 0.060*0.008 0.046* 0.006 0.049*0.006 0.043 0.006 0.043 f0,005 0.027 0.004

cT'+(Mb)
5.99f0.52 5.59* 0.49 5.24 0.46 4.89 0.43 4.57 0.40 4.29 0.38 4.02 0.35 3.43f0.30 2.99 0.26 2.55 f0.22 2.17 f0.19 1.90k0.16 1.66*0.14 1.43h0.13 1.27 i 0.11 1.13*0.10 1.oo f0.12 0.87f0.11 0.77*0.10 0.69 0.09 0.63 0.08 0.56 0.07 0.50f0.06 0.45 f0.06 0543 0.05

* * *

*
*

* *

* *

* * *

variation in the stray-light contribution from one gas to another. However, the order in which the inert gases were studied was Ar, Ne, Xe, Kr and He, and the results for the remaining four gases, assuming the same stray light show overall agreement with other experimental results.

2474

D M P Holland et a1

The Ne double ionisation cross section is shown in figure 6. The experimental ratios have been converted into absolute cross sections by use of the total photoionisation data of Marr and West (1976). The theoretical curves are again by Chang and Poe (1975), and Carter and Kelly (1977). The position of the cross section maximum of Carter and Kelly seems to occur at too high a photon energy but the magnitude of the maximum shows fair agreement with the present experimental results. Chang et a1 (1971) predict a value for the double ionisation cross section of 0.050 i0.002 Mb at 278 eV which is not substantially higher than the general curve formed by the present data. The Carter and Kelly (1977) calculations allow the double ionisation to occur through two channels leaving the doubly charged ion with a configuration ls22s22p4or ls22s2p5. They suggest that the latter channel can provide a significant contribution to the double ionisation cross section. In the Chang and Poe (1975) calculation this 2s2p channel is neglected. The threshold for triply charged Ne occurs at 126.6 eV. Van der Wiel and Wiebes (1971b) suggest that triple ionisation accounts for at most 2% of the total ionisation in the L shell of neon at 250 eV. The fact that triply charged ions of Ne were not observed with the present apparatus implies a maximum contribution of less than 1%, in agreement with the earlier suggestion.

3.3. Argon
The present data for Ar agree well with all previous experimental results and the theoretical curves of Carter and Kelly (1976). The results are shown in figures 7-9 and in table 3. Figure 7 shows the ratio of Ar2+/Ar+over an energy range 40-280 eV. The threshold for double ionisation occurs at 43.4 eV. Apart from the results of Carlson (1967) which appear slightly low, especially at low photon energy, there seems to be a general agreement of a plateau value of 0.19 to 0.20 being reached after an energy of about 80 eV and extending to about 200 eV. The jump in the ratio above the L edge at 248 eV agrees reasonably well with the electron impact results of Van der Wiel and Wiebes (1971a), although general agreement with this previous work is poor. One feature that cannot be explained is the gradual rise of the ratio in the energy range 220-240 eV. (The change of scale at 220 eV

030jAr,*+ thresbold

,:

.
100

LO

160

- - , ,

220

..'

.J

280

Photon energy k V 1

Figure 7. The ratio of partial cross sections Ar2'/Ar'

Multiple photoionisation in rare gases

2475

Photon energy lev)

Figure 8. The Ar2+absolute partial cross section. Theoretical curves: L (dipole length) and V (dipole velocity) from Carter and Kelly (1976).

Photon energy lev)

Figure 9. The Ar3+ absolute partial cross section.

tends to hide the magnitude of the effect.) The single data point of 0,188 at 220 eV by Wight and Van der Wiel(l976) does not suggest a similar rise. An explanation cannot be sought in terms of an accidental increase of monochromator band pass, since the sharpness of the rise in ratio at the L edge (248 eV) is consistent with an expected band pass of approximately 5 eV, see also figures 8 and 9. In table 3 the Ar single ionisation cross sections obtained by using the total photoionisation data of Mixr and West (1976) are listed. Amusia et a1 (1977) have calculated the M-shell contribution to single ionisation in a random phase approximation with exchange (RPAE) approach. They also determined the contribution to single ionisation produced by the 2p6 subshell electrons when post collision interaction was taken into account. It is impossible to make any definite comparison between experiment and theory since the experimental bandwidth tended to smear out this highly localised effect. However, a rise in the single photoionisation cross section at 250 eV was definitely observed. Amusia et a1 (1974) had earlier predicted that the intershell correlation between the 2p6 subshell and M shell would be weak, so that the influence of

2476

D M P Holland et a1
Table 3. The partial photoionisation cross sections for argon.
Photon energy (ev) Band pass (eV)

u3'(Mb)

m2'(Mb)

u"(Mb)

55 60 65 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280

1 1 2 2 2 3 4 4
5

6 7 8 9 10 11 9 10 12 9 9 5 6 6 7 7

O~OlOfO~O08 0.017*0.011 0.008 0.009 0~007f0~010 0.010*0.009 : 0.014 i 0.012 0.006 f 0.01 1 0.018 f 0.012 0~013f0~010 0~010*0~011 0.015 fO.011 0.015 *0.012 0.378 0.054 0.398 f 0.057 0.506 f 0.069 0.529*0.072

0~136*0.012 0.194 i 0.017 0.201 *0.018 0.220 0.020 0.224 0.023 0.227 f 0.023 0.198 f 0.020 0.200 f0.020 0.184 0.018 0.161rt0.015 0.155f0.015 0~134f0.013 0.1 19* 0.01 1 0.119*0.011 0.103 i 0.010 05098i0.010 0.086 0.009 0.087 f 0,012 O.O98iO*O13 0.104 f 0.013 0.147f0.019 3.77f0.47 3.45 0.43 3.04 f0.38 2.69 f 0.34

* *

1.06*0.09 1~20*0~10 1.25 fO.11 . 1.26 i 0.1 1 1.24 f 0.11 1.17f 0.1 1 1.12*0.10 1.02f0.09 0.96 f 0.09 0.88 0.08 0.80*0,07 0.75 f 0.07 0.69zt0.06 0.63 0.06 0.59 f 0505 0.53 f 0.05 0.48 f 0.04 0.43 f 0.05 0.37+ 0.05 0,32*0.04 0.25 f 0.03 0.41 i 0 . 0 6 0,30*0.04 0.29 f 0.04 0.28 f 0.04

* *

the 2p6 subshell on single ion production should be insignificant. This correlation effect, though substantially smaller than that experienced between the 4d shell and outer 5s and 5p shells of Xe (see 3 . 3 , could be the cause of this step in the single ion cross section. A detailed MBPT calculation has been performed by Carter and Kelly (1976) to evaluate the double ionisation cross section for Ar. The calculations involve contributions to the double ionisation cross section arising from the pair excitation channels 3p2 and 3s3p, the latter accounting for over 20% of the total double ionisation cross section in the maximum. The MBPT approach has been extended by Carter and Kelly to include spin-orbit interaction. The triple ionisation cross section, figure 9, remains low until the L edge is reached when a steep rise is observed. Although the triple ionisation threshold occurs at 84.3 eV, no triply charged ions were observed until 130 eV. Between 130 and 240 eV the cross section remains at about the 0.01-0.02 Mb level.

3.4. Krypton
Previous experimental and theoretical data for the multiple ionisation of Kr in the energy range of the present experiment are scarce. The electron impact study of El-Sherbini and Van der Wiel (1972) is the only one to extend to high energy. The

Multiple photoionisation in rare gases

2477

partial cross sections of Kr ions ranging from singly to quadruply charged species are shown in figures 10-13. The experimental counts have been converted to absolute partial cross sections by using the total photoionisation data of Marr and West (1976), see table 4. The single ionisation cross section is shown in figure 10(a). From the double ionisation threshold at 38-6 eV and extending to 75 eV, the triple ionisation threshold, the experimental data of Samson and Haddad (1974) agree well with those of El-Sherbini and Van der Wiel(1972). At high photon energies the single ion count rate was extremely low, which accounts partially for the scatter in the values above 200 eV and the large associated error bars. It is debatable, therefore, whether the rise in cross sections at 210 eV is real. The single ion cross section in the vicinity of the 3d subshell threshold was subsequently re-examined by Van der Wiel and Wight (1975) and is shown in figure lO(6) together with the present experimzntal data and the theoretical curve of Amusia etal (1973,1974). A considerable discrepancy exists between the data
Ibl
12

T--

Lo
Photon energy IV eI

80 120 Photon energy IeVJ

Figure 10. ( a ) The Kr+ absolute partial cross section. (b) The Kr+ absolute partial cross section in the region of the 3d excitation. Theoretical curve from Amusia etal (1973,1974).

a
I6
%

1
6: .

O P

? ' e , .

LO

100

160 Photon energy IeVJ

220

28l

Figure 11. The KrZ+absolute partial cross section.

2478

D M P Holland et a1

'312

'5
3P5

'112

030

I
/;+;
160
,

O']

0
200 2LO Photon energy (eV)

280

Figure 13. The Kr4+ absolute partial cross section.

of Van der Wiel and Wight and the present results. The ion ratios from the present experiment and those from El-Sherbini and Van der Wiel(l972) were converted into cross sections using the photoionisation data of Marr and West (1976) but the later electron impact results were not. They were determined by normalising a relative spectrum with cross sections from Samson (1966) at 30 eV. The Van der Wiel and Wight data were published as differential oscillator strengths (df/dE) and these have been converted into cross sections using the formula v(Mb) = 109.8 df/dE(eV-'). However, the disagreement between the two sets of results appears larger than could be explained by the different normalisation procedures. The single experimental point at 90 eV is considerably lower than the data points of Van der Wiel and Wight in that

Multiple photoionisation in rare gases

Table 4. The partial photoionisation cross sections for krypton.
Photon energy (eV) 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 Band pass (eV)

2479

a4'(Mb)

a3'(Mb)

aZ'(Mb)

a'+(Mb)

2 3 4 4
5

6 7 8 9 10 11 9 10 12 9 9
5

6 6 7 7

0.05 f0.01 0*07*0.01 0.27 f0.03 0.49f 0.05 0.75 f0.07 1.08f0.10 1.38f0.12 1.58 0.14 O.O183tO*O02 1*72*0*15 1*88*0*16 0.025 f0.003 0.051 f 0.006 1.9Of 0.17 0.074f00.009 1 4 7 f0.16 0*091*0.013 1.84 f0.16 0.154f 0.021 1.79f0.17 0*214*0*030 1.75 *0.16 0.233*0*030 1.95 f 0.18 0.202f0.026 1.68 f 0.16 0.206 f0.025 1.75f0.16 0.253f0.030 1.57 f0.14 0.216f0.024 1.63f0.15 1.44f 0.14 0.221 f0.025

0.21 f0.02 0.39 f0.04 0.88 f0-08 1*10fO~10 1.67 f0.15 2.17 f0.19 2.61f0.23 2.91 f0.25 3.19f 0.28 3.24f0.28 3.24f0.28 3.20f 0.28 3.06*0*27 2.61 k0.24 2-65f0.24 2.55 f0.23 2.37 f0.22 2.30f0.21 2.24 f0.20 2.14 f0.19 1.88 f0.17

0.384f 0.05 1 0.131 f 0.028 0.255 f0.042 0.302 f0.048 0.218 f 0.040 0.202f0.038 0.168f0.036 0*193*0.043 0.099*0.035 0.097 f0.040 0.132 f0.054 0.168f0.073 0.248 f0.110 0.567f0.218 0.350f0.190 0.078 f0.154 0,367 f0.131 0.167 i 0.099 : 0.191 f0.098 0.095f0.104 0,357 f0.154

region. One reason may be that the energy bandwidth of the present experiment encompasses only the first of the 3d excitation resonances (3d94s24p6(2D5/~)5p) at 91.2 eV, whereas Van der Wiel and Wight scan them all. The Amusia et a1 (1973, 1974) calculations take into account intershell correlation between the 3d subshell and the N shell, which could increase the single ion production near the 3d threshold. Direct photoionisation of the d subshell makes a negligible contribution to the single ion yield due to the dominant role of Auger decay, which leads to a more highly charged ion. Nevertheless, Amusia et a1 have attributed the slight increase in single ion production as being due to virtual excitation of d electrons and subsequent transfer of excitation energy to the outermost shell. The Kr double ionisation cross section is shown in figure 11 and shows a steady rise after the 3d threshold followed by a gradual decrease. The double ion is, of course, produced by an initial hole in the 3d shell followed by an Auger rearrangement, in which a second electron is emitted. Good agreement is obtained with the data of El-Sherbini and Van der Wiel(l972). Although the present data points do not overlap with the threshold values of Samson and Haddad (1974), the two sets of data are consistent. The triple ionisation cross section, figure 12, has a similar shape to the doubly charged cross section. A continuous rise is observed through the 3d9, 3d94p5and 3d94s' thresholds since each process will contribute triply charged ions. An edge may be discernible following the 3p5 threshold but not as clearly as in the El-Sherbini and Van der Wiel data. Finally, the quadruply charged krypton cross section is shown in figure 13 and compared with the data of El-Sherbini and Van der Wiel(l972). No contribution was

2480

D M P Holland et a1

observed until a photon energy of 160 eV was reached, although the threshold occurs at 136 eV. 3.5. Xenon

In the energy range of the present experiment the Xe total photoionisation cross section is dominated by the 4d+ E f transition which reaches a maximum around 100 eV. It is not surprising, therefore, that peaks corresponding to this process are observed in both the double and triple ionisation cross sections. The cross sections for singly to quadruply charged ions are shown in figures 14-17 and are listed in table 5 . The ion ratios obtained in the present experiment and those of Samson and Haddad (1974) have been converted into ion partial cross sections by using the total photoionisation cross section data of West and Morton (1978). The same procedure has been applied to normalise the ion cross sections for charge states one to three from El-Sherbini and Van

Photon energy lev)

(b)

LO

80 120 Photon energy lev)

xAs
~

Figure 14. ( a )The Xe+ absolute partial cross section. ( b ) The Xe+ absolute partial cross section in the region of 1 0 the 4d excitation. Theoretical curve from Amusia et a/ (1973, 1974).

Multiple photoionisation in rare gases

248 1

o
LO

100

160 Photon energy leVl

220

281

Figure 15. The Xe2+ absolute partial cross section.

Photon energy lev1

Figure 16. The Xe3+ absolute partial cross section.

0 1 0 ' .
120

160 200 2LO Photon energy lev)

280

Figure 17. The Xe4+ absolute partial cross section.

2482

D M P Holland et a1
Table 5. The partial photoionisation cross sections for xenon.
Photon energy (eV) 65 70 75 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 Band pass (eV) 2 2 2 2 3 4 4 5 6 7 8 9 10 11 9 10 12 9 9

u4'(Mb)

a3'(Mb)

a2'(Mb)
1.31*0.12 2.90*0.26 4.76k0.42 8.60i0.75 16.27* 1.42 18.40 1.60 15*84*1.39 10.01rt0.87 5.24*0.46 2*49* 0.22 1.09iO*lO 0*51d=0.04 0.35 rt 0.03 0.36i0.03 0.41 k 0.04 0*57*0*05 0.62i0*05 0.74i0.07 0*83*0*07 0.69 rt 0.06 0.77 0.07 0.83 0.07 0.78*0.07 0.81i0.07

a'+(Mb)
1.280*0.115 0.948*00.084 0.843*0.079 0.868+0.082 1309*0.143 1.111 jzO.112 0.778*0.087 0.314*0.040 0.010*0*022 0,007 k 0.021 0.051*0.026 0.048*0.026 0,017 0.022 0.008*0-021 0.043 f0.026 0.036*0.029 0.009iO-022 0.049*0.032 0*010*0.033 0.063 i 0.027 0.008* 0.034 0.050* 0,036 0.061*0.025 0.017*0*034

5
6 6 7 7

0.021*0*003 0.025*0*003 0.135 *0.017 0.306*0.038 0.322*0.040 0.294i00036 0.271 0.034 0*196*0,025 0 . 1 1 0 i 0.019 0.152*0.026 0.154* 0,026 0.089*00.025 0.245*0.042 0.202 0,035 0.169*0.029 0.235 0.041 0,203 0.036

* *

0.43*0.04 1.59 0.15 2.51 0.22 5.81*0.52 7.49 0.67 6.23*0.56 4.26rt0.37 2.37*0.21 1.42rt0.12 0.83*0*07 0.50*0*04 0.34*0.03 0-25i 0.02 : 0526* 0.02 0.28 0.03 0.31 k0.03 0*34*0.03 0.35+0.03 0.34*0.03 0.41 0.04 0.39i0.04 0+39i 0.04 0.45 k0.04

*
*

* *

der Wiel (1972). However, this method could not be used for the quadruply charged ions since no values were given for the charge states one to three at high energies. Hence, the quadruply charged ion cross sections of El-Sherbini and Van der Wiel, and also the spectra presented in Van der Wiel and Wight (1975) and Wight and Van der Wiel(l977) have been converted from differential oscillator strengths to cross sections. The single ionisation cross section is shown in figure 14(a) from 30 to 280 eV. The present experimental data start at 65 eV and the agreement among the various data from 60 to 90 eV does not appear impressive. At high energies no other data exist with which to compare the present values. The scatter in the points, and the relatively large error bars are due mainly to the statistical uncertainty (the count rates above 150 eV were extremely low) and the scattered light problems discussed earlier. The single ionisation cross section in the vicinity of the 4d threshold has been studied experimentally by Van der Wiel and Wight (1975) and West er al (1976), and theoretically by Amusia et a1 (1973,1974). These results, together with the present experimental data, are plotted in figure 14(b). One notes that all the experimental results lie below the theoretical curve of Amusia et a1 (1973, 1974), so it would appear that the intershell interaction has been overestimated. As in the case of Kr, this interaction has been taken into account by considering the virtual excitation of the d electrons and subsequent transfer of excitation energy to the outer shell. This intershell interaction is more important in the case of Xe than it is in Kr, reflecting the relative strengths of the initial d-shell photoabsorption processes.

Multiple photoionisation in rare gases

2483

The Xe double ionisation cross section is shown in figure 15. Reasonable agreement is obtained near threshold with the previous experimental results of Samson and Haddad (1974), Cairns et a1 (1969), and Wight and Van der Wiel(1977), and over the entire energy range for the data of El-Sherbini and Van der Wiel (1972). As in Kr, a hole created in the 4d shell will lead to a doubly or triply charged ion. The peak centred around 100 eV shows the doubly charged contribution to this transition. The data of El-Sherbini and Van der Wiel do not extend above 200 eV. The Xe triply charged cross section, figure 16, has a very similar shape to the double ionisation cross section. It rises from the threshold at 65 eV to a maximum centred around 100 eV. Again a low plateau value is reached at high photon energy. Near threshold, reasonable agreement is obtained with the data of Cairns et a1 (1969) and Wight and Van der Wiel (1977). The magnitude of the peak obtained by El-Sherbini and Van der Wiel appears somewhat larger than that obtained in the present experiment. The Xe quadruply charged cross section is shown in figure 17. The only comparison which can be made is with the electron impact work of El-Sherbini and Van der Wiel (1972). For this ion cross section, the ion ratios of El-Sherbini and Van der Wiel were not normalised to the recent total cross section data of West and Morton (1978) but to the data of Samson (1966), see 0 3.4. The cross section following the 5p2 threshold at 112 eV is small but it rises after passing through the 4p5 threshold. At high energies the behaviour of the cross section is uncertain due to the scatter in the points.

Acknowledgments
The measurements were carried out at the NINA Synchrotron Radiation Facility with the aid of financial assistance from the Science Research Council, who also provided a Postgraduate Studentship for one of us (DMPH). Our particular thanks go to Bob Epstein and Caroline Logan of J & P Engineering (Reading) whose help with the data acquisition system was crucial. The expertise of J J Thomson Laboratory technicians R N Chamberlain, B E Bennett and G C Folkerd was invaluable.

References
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2484

D M P Holland

et a 1

Marr G V and West J B 1976 Atom. Data Nucl. Data Tables 18 497 Salpeter E E and Zaidi M H 1962 Phys. Rev. 125 248 Samson J A R 1966 Advances in Atomic and Molecular Physics vol2 (New York: Academic Press) Samson J A R and Haddad G N 1974 Phys. Rev. Lett. 33 875 Schmidt V, Sander N and Kuntzemiiller H 1976a Phys. Rev. A 13 1743 Schmidt V, Sandner N, Kuntzemuller H, Dhez P, Wuilleumier F and Kallne E 1976b Phys. Rev. A 13 1748 Stewart A L and Webb T G 1963 Proc. R. Soc. A 82 532 Stockbauer R J 1973 J. Chem. Phys. 58 3800 Van Brunt R J, Lightner G S and Whitehead W D 1971 Rev. Sci. Znstrum. 42 1052 Van der Wiel M J, El-Sherbini Th M and Vriens L 1969 Physica 42 411 Van der Wiel M J and Wiebes G 1971a Physica 53 225 -1971b Physica 54 411 Van der Wiel M J and Wight G R 1975 Phys. Lett. 54A 83 West J B, Codling K and Marr G V 1974 J. Phys. E: Sci. Znstrum.7 137 West J B and Morton J M 1978 Atom. Data Nucl. Data Tables to be published West J B, Woodruff P R, Codling K and Houlgate R G 1976 J. Phys. B: Atom. Molec. Phys. 9 407 Wight G R and Van der Wiel M J 1976 J. Phys. B: Atom. Molec. Phys. 9 1319 -1977 J. Phys. B: Atom. Molec. Phys. 10 601 Wiley W C and McClaren J H 1955 Rev. Sci. Znstrum.26 1150