Z. Phys. D.

- Atoms, Molecules and Clusters 5, 241-252 (1987) Atoms,Molecules

and Clusters
for PhysikD

© Springer-Verlag 1987

Quantum Theory of Post-Collision Interaction

in Inner-Shell Photoionization
J. Tulkki
Laboratory of Physics, Helsinki University of Technology, Espoo, Finland

G.B. Armen, T. ~berg,* and B. Crasemann

Department of Physics and Chemical Physics Institute, University of Oregon,
Eugene, Or USA

M.H. Chcn
Lawrence Livermore National Laboratory, Livermore, California USA

Received June, 1986;

final version November 6, 1986

We have performed fully quantum-mechanical and relativistic calculations of the post-

collision-interaction effect in x-ray-induced argon K-L2La(1D) Auger and xenon
L2-L3N4(J=3 ) Coster-Kronig-electron emission. The Dirac-Fock computations
include a complete integration over intermediate one-hole continuum states in the lowest-
order expression of the resonant double-photoionization cross section. The results are
in excellent agreement with synchrotron-radiation measurements of the post-collision-
interaction shifts. We have also made nonrelativistic Hartree-Fock test calculations of
the argon K-L2L3(~D) and xenon L3-M4Ms(1G4) Auger-electron line shapes. The
quantum-mechanical results are compared with rigorous semiclassical calculations which
have been made without using the stationary-phase approximation. The results of this
computational analysis are interpreted in terms of an analytical line-shape formula based
on asymptotic Coulomb wave functions. As a consequence the most salient features
of the post-collision interaction in inner-shell photoionization are explained.

PACS: 32.80.Pb; 32.80.-t; 32.80.Hd

1. Introduction
When two or more electrons are ejected as a result
of a collision, they exchange energy and angular mo-
mentum. In this work we consider the post-collision
interaction (PCI) between two electrons in the residu-
al Coulombic field of an ion. The doubly-ionized ion
is assumed to be produced in a near-threshold inner-
shell photoionization process, leading to the ejection
of a slow photoelectron and a fast Auger or Coster-
Kronig electron.
The theory of the PCI effect in photoionization
* Permanent address: Laboratory of Physics, Helsinki University
of Technology, SF-02150 Espoo, Finland
has been pursued along four lines, namely, using the
semiclassical approximation [1-4], diagrammatic
many-body theory [5, 6], resonant-scattering theory
I-7-9], and the complex-coordinate approach [10]. In
this paper we use the resonant-scattering theory for
the description of the PCI effect. Previously, we have
discussed the connection between this and the dia-
grammatic many-body approach [8]. Here we shall
indicate the connection with the semiclassical meth-
ods [1-4].
A few quantum-mechanical calculations of the
PCI effect in inner-shell photoionization exist [9, 11
14]. They are all based on the concept of "shake-
down" transitions [15], inherent in all theories. How-
ever, they differ in the choice of the one-electron basis
242
functions and in the treatment of the photon-electron
and electron-electron interaction matrix elements.
The quantum approach has been applied to Auger
transitions in argon and xenon, representing the de-
cay of both long-lived [-11, 13] and short-lived [3,
12, 14, 15] inner-shell hole states. Agreement between
measurements of the PCI shift [9, 16, 17] and quantal
calculations [9, 13] is generally good. However, inclu-
sion of the PCI effect in the K photoabsorption cross
section of argon at the same level of sophistication
[12] made the agreement between theory and mea-
surement [18] worse. Hence one should not draw
too far-reaching conclusions regarding the validity of
the lowest-order quantal approaches [5-14] merely
by comparing calculated and measured PCI shifts.
Studies of Auger-electron line shapes including com-
parisons between quantal and semiclassical ap-
proaches are needed as well.
The PCI effect in inner-shell photoionization rep-
resents one aspect of the complex dynamics of elec-
tron excitations, which inevitably accompanies the es-
cape of a photoelectron from an inner shell of a many-
electron atom. A consistent description of the influ-
ence of this phenomenon on total and differential in-
ner-shell photoionization cross sections requires rela-
tivistic quantum theory. Hence we have used a recent-
ly constructed Dirac-Fock (DF) continuum program
[12, 14] in conjunction with a multiconfiguration DF
package [193 for the calculation of line shapes in Ar
K - L 2 La(aD) Auger and Xe L 2 - L 3 N4(J= 3) Cos-
ter-Kronig-electron emission. These two transitions,
for which measurements as a function of photon ener-
gy exist [20], differ largely in the kinetic energy of
the emitted electrons and in the initial-state lifetime.
We have also performed a comparison between
nonrelativistic quantal and semiclassical line shapes
as a function of the initial-state lifetime and the pho-
ton energy. This simulation has been carried out for
the Xe L~-M4Ms(1G4) Auger-electron transition
employing the quantum-mechanical calculation pro-
cedure reported earlier [9]. The approach has been
checked against Dirac-Fock PCI calculations of the
Ar K-L2Ls(1D) transition for which relativistic ef-
fects are not important. The semiclassical calculations
are based on the work of Niehaus and Zwakhals [3]
but without the use of the stationary-phase approxi-
mation for the evaluation of the line shape.
In Sect. 2 we outline the resonant-scattering-
theory (RST) approach to photon-induced inner-
shell-vacancy decay [7, 8]. Previously we have consid-
ered the evolution of inelastic x-ray scattering (IXS)
into fluorescence [21-23]. With regard to the PCI
effect, the analog is to consider the evolution of dou-
ble-electron photoionization (DEPI) into Auger-elec-
tron emission at the threshold for inner-shell ioniza-
J. Tulkki et al.: Quantum Theory of Post-Collision Interaction
tion. We derive the lowest-order formula [8, 9] of
the Auger-electron line shape which accounts for the
"shake-down" mechanism. An example is given in
Appendix A. However, we exclude the contribution
from resonant spectator lines [9] which determines
the Auger emission below and at the threshold. Effec-
tively it limits our theory to excess photon energies
Eexc> 2F~, where F~is the full width at half-maximum
(FWHM) of the initial inner-shell hole state [9].
Details concerning the numerical procedure and
wave functions for the DF method are given in Sect.
3. After convoluting the calculated Auger line shapes
with the final-state density function and with the spec-
tral window function, we compare our results with
measured PCI shifts. The final-state density function
accounts for the lifetime of the doubly ionized final
state in the Auger emission. The results of our com-
parison between the quantal and semiclassical results
are described in Sect. 4.
In Sect. 5 our numerical results concerning the
Auger-electron line shapes are interpreted in terms
of an analytical line-shape formula. This interpreta-
tion is based on the use of asymptotic Coulombic
wave functions in the lowest-order PCI formula. The
derivation of the analytical formula is described in
Appendix B. Our result shows that at large excess
energies the PCI effect is soMy determined by the
Coulombic field outside the atom. It clarifies the cor-
respondence between the quantal and semiclassical
approaches to PCI. We also discuss the present limita-
tions of the quantum theory of the PCI effect and
indicate how they can be removed.
2. Theory
The fundamental idea behind the scattering-theory
treatment of PCI is to generalize the conventional
multi-channel scattering theory to allow for the two
electrons in the outgoing channel [7]. The key ele-
ment is the transition matrix element TBA(gI,~;2)
which describes the Auger process as a one-step pro-
cess in which two electrons are emitted in channel
B as a consequence of the photon-electron interac-
tion. Channel A thus corresponds to photons with
energy he) impinging on an atom in its ground state.
In atomic units the probability of emission of elec-
trons with kinetic energies el and e2 is
d2w = 2 ~ ~ITBA(el, ~2)[2 3(O3--lff" --~1--~2) d~l de2,
KA BA
(1)
where the summations are carried out over all mag-
netic quantum numbers. The summation over B fur-
J. Tulkki et al.: Quantum Theory of Post-Collision Interaction 243

thermore accounts for all final channels which are Table 1. Comparison between the resonance behavior of IXS and
allowed by the selection rules, and the summation DEPI. The classification of the states refers to the stationary states
involved in the transition-matrix amplitude of (2)
over A and the degeneracy ~A, for any averaging over
initial polarization directions. The energy If~. is the Property IXS" DEPI
energy required for ionization of the two electrons.
Initial state One-photon states One-photon states
plus atomic ground plus atomic ground
2.1. Transition Matrix Element state state
Intermediate No-photon and two- No-photon states plus
The transition matrix element between two specific states photon states plus atomic one-hole
atomic one-hole states
channels A and B is states
Final state One-photon states No-photon states
Tm~(el, e2) = (Z~ (~1, e2) ]Vt ZA(co)) plus atomic one-hole plus atomic two-hole
(Z/7 (~1,82)]H--El X,o(z)5 (X,,(T)I V] ZA((O)5 dz scattering states scattering states
+ y, 7J Resonances X-ray fluorescence
v 0 ~:, +8~ +Ii~, - < ( ~ ) Auger or Coster-
(2) at Eexc> 0 Kronig-electron
emission
where H = H e + V is the sum of the many-electron Resonances Resonance lines Spectator lines
Hamiltonian H e and the photon-electron interaction at E ~ ~<0
operator V, and where E is the total final-state energy Post-collision Weak Strong
[7, 8, 21]. In this form, (2) also accounts for inelastic interaction
x-ray scattering (IXS), provided the stationary final-
The resonance behavior is due to the no-photon intermediate
state scattering wave function ZB and the intermedi- states
ate state Z~(z) are interpreted accordingly [21].
In the case of double-electron photoionization
( D E P I ) , ) ~ should be evaluated using ingoing-wave
boundary conditions [24, 25] for both electrons [26]. have a significant influence on DEPI cross sections
The intermediate states Z~(z) represent the single-elec- close to the double-ionization threshold. The many:
tron ionization continua including excitations. Thus, body perturbation-theory calculation of Poe and
the integration over z includes a summation over neg- Chang [28] provides an example of the influence of
ative z values. Depending on c9, the summation over the forbidden L 1 - - L 2, 3 Coster-Kronig transition on
v in (2) can often be limited to the degenerate states the neon 2p DEPI cross section.
associated with a specific inner-shell threshold i. The The doubly ionized or excited states may not only
complex energy g~(z) is then given approximately by interact with ZA(0~),representing the ground state plus
photon field, via the manifold of singly ionized and
Ei(z)~Ii +'c--a il~i, (3) excited states. The first amplitude in (2) describes the
direct interaction which nevertheless vanishes in the
where Ii is the single-electron ionization energy and frozen-core approximation. In this approximation the
F~- 1, the lifetime of the residual singly ionized inner- wave functions of the ionized electrons are determined
shell hole state [21]. In (3) it has been assumed that in the field of an ion core which is constructed from
F~is independent of z. This is not always a good ap- ground-state spin orbitals.
proximation, especially when super-Coster-Kronig It is clear from (2) that the resonance behaviors
transitions are involved [27]. of IXS and DEPI are similar. Independently of details
If the photon excess energy Eex c = (2)-- I i is greater of the many-electron interaction matrix involved in
than zero, the second amplitude in (2) exhibits reso- (2), the Lorentzian shapes of either x-ray or Auger-
nance behavior, since according to (2) and (3) the de- electron emission lines evolve as a result of a few
nominator is equal to Eexc-z + 1 iF/. The denomina- general conditions. The distortion of these line shapes
tor also becomes large for negative z values such that is mainly a consequence of the coupling, mediated
Eeoc = - fz]. This region is associated with spectator by the singly-excited intermediate states. At large ex-
lines, as discussed in [9]. In the limit of large values cess energies, this coupling becomes unimportant, and
of E .... the resonance behavior of (2) accounts for consequently the photon-induced x-ray or Auger-
the emission of Auger electrons with characteristic electron emission can be treated as a two-step process.
energies ~A= I i - - I H, in association with the ejection In Table 1, a comparison is made with reference to
of photoelectrons of energy 8= o)-I~. According to (2) between the resonance behaviors of IXS and
(2), virtual Auger transitions for which 8A< 0 may also DEPI. It is assumed that only one inner-shell-hole
244
threshold contributes to the sum over v in (2). Accord-
ing to Table 1, the PCI effect is classified as weak
for IXS and strong for DEPI. This difference stems
from the fact that in IXS the intermediate and final
atomic states are both one-hole states, whereas there
is a change from one- to two-hole states in DEPI.
The change of the wave functions of the excited or
ionized electrons is therefore smaller in IXS than in
DEPI for the final-state interaction H - E in (2).
2.2. The Lowest-Order P C I Formula
The calculation of the probability given by (1) as a
function of 81, and e2 is not tractable, even for the
simplest Auger transitions, unless the amplitude given
by (2) is considerably simplified. We shall (i) limit
ourselves to isolated inner-shell ionization thresholds
and neglect any interference effects between the direct
and resonant amplitudes in (2). The error from this
approximation is of the order of Ffli [8]. Further-
more, we shall (ii) neglect the final-state inter-channel
interaction between the double-electron channels B.
Finally, we shall (iii) express the many-electron wave
functions in (2) as superpositions of Slater determi-
nants that have the appropriate symmetry and parity.
The one-electron basis functions are either Dirac-
Fock four-spinors or Hartree-Fock spin orbitals.
In order to understand the significance of the sec-
ond and third approximations, let us assume for the
moment that a common one-electron basis is used to
construct the initial, intermediate, and final many-
electron states in (2). Since V is a one-electron opera-
tor, the intermediate states Z,(z) correspond to singly-
excited configurations [niliji] zlj [29], where [z) is
either a discrete or a continuum state. The final states
correspond to double-hole configurations "~¢I,(el, ca)
=[n¢ llj I, nf, lf, jf,] e I l l j l , e 2 12j2 and 7ff,(82, 81).
The operator H - E reduces to the many-electron Ha-
miltonian He, containing one- and two-electron oper-
ators. It follows from the properties of matrix ele-
ments between Slater determinants that g~(el, 82)
= ( ) ~ (~1, ea)l H - E I z i ( z ) ) vanishes unless the states
[81) or [82) coincide with Iv). Let us suppose that
the former case corresponds to 7ii,(el, e2), and the
latter, to 7ii,(82, 81). We have W B ( e l , 8 2 ) = 6 ( e l - z )
WB(e2) or W~(ei, e2)=6(e2--z) W~(eO, where WB is the
amplitude for any of the multiplets that can be con-
structed for [n~ tiji] ~ [n y tl j I , n I, If, j l,] Auger tran-
sitions. For 7ii,(ea, 82), the amplitude (2) reduces to
WB(82) VA(81)
TBa(e a, 82) ~- 82 _ e A -I- i F i / 2 ' (4)
where 8a = I f - - I H, is the nominal Auger-electron en-
ergy, and VA (83 is the photon-electron interaction ma-
trix element between the ground state and one of the
J. Tulkki et al.: Quantum Theory of Post-CollisionInteraction
one-hole states, associated with [niliji]el lj. For
7~i,(82, 80, el and g2 change place in (4). The substitu-
tion of both amplitudes in the probability expression
(1) and the integration over e2 result in the conven-
tional two-step formula for Auger decay following
photoionization. At 81=Ee=c occurs the Lorentzian
Auger-electron peak, respectively.
The derivation of (4) shows that the significant
contribution to the corresponding resonant ampli-
tude in (2) comes from regions around el~Eexe and
8z ~SA. For E~xc >0, the energy el is therefore usually
much smaller than 82. With regard to the interchannel
interaction in Z~ (el, 82), it follows that it is a good
approximation to treat the interaction between the
Auger-decay channels [30] separately from the pho-
toelectron channels. The major consequence is a re-
distribution of the intensity among the possible mul-
tiplets of the Auger [nl lijJ ~ [n¢ lsj s, n s,/s'Js'] tran-
sitions. The interchannel interaction may consequent-
ly not influence very much the exchange of energy
and angular momentum between the photoelectron
and the Auger electron. This fact justifies the second
approximation, in which the two continuum electrons
are now represented asymptotically by the asymmet-
ric product of Coulombic waves of given angular mo-
menta I.
The third approximation involves separate self-
consistent solutions for the initial, intermediate, and
final configurations. The intermediate-state contin-
uum wave functions ]z) are evaluated in the field of
the singly ionized atom, corresponding to [ni lij~]. In
contrast, the final-state continuum wave functions
[81) and 182) are evaluated in the field of the doubly
ionized atom, corresponding to [ns lsj s, n s, Is.is, ].
Hence we have 14~(el, e2)~ (E 1 ['17) l~{ZB(82) or
(ca Iv)WB(80, where the overlap elements (8, ]~c) (v
= 1, 2) describe shake-down transitions from singly-
to doubly-ionized one-electron continuum states. The
proportionality of the electron-electron interaction el-
ement I/VB(el, ez) to either (81[~) or (ezl~) is only
valid to lowest order in nondiagonal overlap elements
as illustrated by the example in Appendix A. In the
following we shall assume that this "shake-down" ap-
proximation is valid.
We shall restrict ourselves to closed-shell atoms,
for which the initial state is a 1So state. In the nonrela-
tivistic limit the intermediate states are therefore
[niIi]rllP, and the final states, [n s t s , n s,ls,]
1'3L 181821 a 1p. Upon neglecting the direct amplitude
and after executing appropriate summations in (1),
we have
d2o- 2nc~
delde2- 3 c°~[Ft~(el)l@2IIv')12
llA
+FlA(e2) l(el II Z,)12] ~(C0--el --82 --lJ'r') (5)
J. T u l k k i et al. : Q u a n t u m T h e o r y of P o s t - C o l l i s i o n I n t e r a c t i o n 245

for the partial doubly differential cross section, corre- of [9], except that there we also considered the specta-
sponding to the Auger multiplet In il~]zLi tor transitions. The cross sections given by (5) and
[n s ls ' ns ' is,] 1, 3 LS e IA 2Li with decay rate /~A (e), for (8) do not account for the final double-hole-state life-
which an explicit expression can be found in [241 . time Fil}. This deficiency is removed by replacing
In (5), l = li_+ 1 (/;>0), and lA satisfies the triangular the Dirac delta function in (5) with the normalized
rule LT+ Ia > Li> tL s-- 1A[. The function tr') is given final-state density function
by
~ S S ' (81' 82) = (~ff,/2 7~) [ ( E ' - - ~l -- 82) 2 -~- ~f~,/4] - 1, (9)
7 It) ([ni tJ "el 1p It D (~) t[1S) dr
oj E ~ - t + iU2 ' (6) which results in an obvious modification of (8).

where the integration includes the summation over

discrete t'c) states and where the reduced electric di-
pole matrix element may be evaluated rigorously 3. Dirac-Fock Calculations and Results
within the self-consistent-field scheme. In the frozen-
core approximation it is given by The relativistic generalization of the cross section giv-
en by (8) is
([ni li] rl 1Pll D (1) II~S)
da
= ( __ 1 ) / m ~ -- 1 ~ D 1( r 1, n i li), (7) de-3co~ ~ [~AJA(e) l((E'--e)lj[r')J2
l j, lAJA
where l~,~ = max (l~, l) and where D ~ is the dipole radi- +I~IAJA(E'--~'=) [(e/jl r')12], (10)
al matrix element.
where

lz) ([ni liji] zlj, J = 1 I]~[:t.(A(~)(f~) + GA°)(f,,))-GA°(f~)]ll J = 0 ) d z

I~) = o~ (11)
E~¢ -- r + iFii/2

involves the relativistic E 1 multipole matrix element

In noncoincidence experiments with a single de- in an arbitrary gauge [12]. In our calculations we
tector for observing electrons, one measures the cross have chosen the Coulomb (velocity) gauge, corre-
section sponding to G = 0. The results are however not sensi-
da 2roe tive to the choice of gauge [12, 14].
d e - 3 ~o ~ [FiA(e)l((E'-e)llr')] 2 The initial-, intermediate-, and final-state wave
I, 1A functions were constructed from one-electron Dirac-
+r~A(E,_~) (~,l[~,)f2], (81 Fock (DF) four-spinors. The bound-state spinors
were obtained using the multiconfiguration DF pack-
where E' = o0- Is f, = E~xo+ eA" In the region of the age of Grant et al. [31] and the continuum spinors
Auger peak, e ~ eA, the first terms in the square brack- from a recently constructed DF continuum program
ets of (8) dominate, provided E~x~~>0. For low e values [12, 14]. In this approach, the continuum wave func-
the second terms dominate. They describe the photo- tions are calculated by keeping the bound orbitals
peak at the position ~ ~ E ~ which varies as a function fixed for each ionic configuration. In the present case,
of o). Both peaks have distorted non-Lorentzian the intermediate- and final-state ionic configurations
shapes, such that the Auger peak has a maximum correspond to Z~ = 1 and Z f = 2, respectively. The La-
at e=eA +A and the photopeak at e . = E ~ - - A where grangian-multiplier technique is used to ensure ortho-
A is a positive PCI shift. According to (8), the shape gonality between the continuum and bound-state or-
of the Auger peak is the mirror image of the shape bitats. The large component P,~(r) and the small com-
of the photopeak. Simple arguments [6] based on ponent Q~(r) of the continuum four spinor are thus
asymptotic Coulomb wave functions and the station- obtained by iteratively solving the two coupled first-
ary-phase approximation show that the distortion of order equations
the Auger peak is such that the high-energy slope
is enhanced and the low-energy slope is reduced with dPdr t-~ P ~ - [ 2 c + ~ (Yr(r)+8)] Q~=~(r),
respect to the Lorentzian line shape. This universal
behavior of the "shake-down" transitions is examined (12)
in Sect. 5 and Appendix B.
The use of the approximation (7) in (8) yields (3)
dQdr ~ Q" + Ic \(-Y!~)-+e)
r
246 J. Tulkkiet al.: Quantum Theory of Post-CollisionInteraction

50 ! I I ! I " I I ~......... I 1 I I 1 30

25 Eexc = 17 eV . . ~ i ~ ~ e - 43 eV t5

0 0

-25 -15
r reol I~t ~[I reol porl
~-50 .............. I I I I I I I ', I I ............ I I -30

15
25

0 0

-25 -15
[
o00no,,po,, tl, oo0ioo,,0o,,
-r~n ................;.... I I I ,,! ;kr~ i | ...... I i t 1 -30
0 25 50 75 100 125 0 .... __ 40 60 80 0 50 I00 150 ZOO
Distance (e.u.)
Fig. 1. Real and imaginary parts of the relativistic intermediate-state PCI function, (11), as functions of radial distance, for the xenon
Lz- L3N4(J= 3) Coster-Kronigtransition

where t¢=l for j=t-½ and - ( l + 1) for j=l+½. The
nuclear and direct electron-electron interaction po-
tentials are included in Y, whereas the inhomogeneous
terms ~(r) and t/(/) contain the nonlocal exchange po-
tential and the Lagrange multipliers [14, 24]. The
normalization condition
oo
S (P~P~'~+Q~ Q~'~)dr=f(e-e')
0
is fulfilled by fitting the numerical solution to a linear
combination of the regular and irregular solutions
of the Coulombic Dirac equation outside the ion [32].
The Coulombie solutions were calculated exactly by
use of a special numerical approach, which permits
an accurate evaluation of the pertinent Whittaker
functions at distances of a few atomic units. The most
time-consuming part of the calculation is the con-
struction of the function (11). Typically, the integra-
tion over z requires the evaluation of 3000 continuum
wave functions in steps of 0.1 eV.
The PCI effect of two transitions was considered,
namely the argon K-LzLa(1D) Auger and xenon
L2-L3N4(J=3) Coster-Kronig transitions. In the
former case, we have eA=2661 eV and Fi=F(K)
=0.66 eV [33], and in the latter case, ea=228 eV and
F~=F(L2)=3.05 eV t34]. The integration over • in-
cluded the summation over 4p to 7p Rydberg states
in the Ar case and over the 5d state in the Xe case.
Two inconsequential approximations were made in
order to save computer time:
(a) in the cross section (10), the second "photo-
electron" term in the square bracket was neglected
since we have Eex~~ ea in our calculations, and
(b) in the Ar case, the integration over ~ was lim-
ited to the j = 3/2 (l= 1) states, and in the Xe case,
to the I---2 (j = 3/2) states.
Figure 1 shows the real and imaginary parts of
L~'>, given by (11), as functions of the radial distance
(13)
r, for the Lz-L3N4(J=3) transition. As discussed
in detail in Sect. 4, the function I~') undergoes
damped oscillations at large r in accordance with Fig.
1. The corresponding Coster-Kronig line profile, i.e.
the cross section given by (10), is shown as a function
of e - eA in Fig. 2 for Eox~= 7 eV and 43 eV, respective-
ly. The large PCI shift, A, and asymmetry are conse-
quences of the short lifetime of the intermediate 2p_~
hole.
In Fig. 3, the calculated PCI shifts are compared
with measurements [20]. The dashed line represents
the shifts, resulting from the evaluation of the cross
section given by (10). The dash-dotted line shows the
result of incorporating the final-state density function
of (9) in the cross section. In the Ar case, we have
Fyy,~2F(La)=0.31 eV, and in the Xe case,
Fyy.~ F(L3)= 2.82 eV [34]. Finally, the modified cross
section was convoluted with the spectrometer window
function, which is a 2.3-eV wide Gaussian. This func-
tion was determined by fitting it to several Auger
lines of known width, measured at large excess ener-
gies. The result is indicated by the solid curve in Fig.
3. Agreement with the measured shifts is very good
J. Tulkki et al.: Quantum Theory of Post-Collision Interaction 247

I J 1 1 .... "r- -- i
4. Auxiliary Calculations

1068 Eexc=7eV Before taking the good agreement between measured

and calculated shifts as final evidence for the validity
of the lowest-order PCI theory, one should consider
a number of points.
4 First, as mentioned in Sect. 1, the calculation of
2 k aN4(O:3) the total cross section

~o o ---T 1 f 1 1 1 i i'da
a(o~)= ~ o -~ede (14)
"~8_~=4610 Eexc=4 3 ~
for the near-threshold Ar K photoionization [121 did
not lead to complete agreement with the experiment
of [181. In (14), da/de is given by (10). In fact, the
omission of the PCI effect leads to a somewhat better
2 ~ Lz-L~N4(d=5) agreement with the experiment [12]. It should be
stressed that the reduced E1 dipole matrix element
0 I I_ I.............J .......... L I
in (11) has been calculated previously and in this work
-3 -2 -I 0 l 2 3 4
by including all monopole matrix elements between
Retotive Coster-Kronig energy (eV) the intermediate- and final-state spinors.
Fig. 2. The PCl-distortedshape of the xenonL2--L3 N4(J=3) Cos- Secondly, we have found numerically that it is
ter-Kronig-electronline. The cross section of (10) is indicated in an excellent approximation to evaluate the integral
arbitrary units, as a functionof the relativeCoster-Kronigenergy
~--ea (~A=228eV) @lz') in (8) by taking the overlap
2 1 oo.,
| I I I ......
(eI~')WKB=Tifk~ 0S e'~¢'-kkaRdr (15)
Ar K-LzL3

between the WKB wave functions, corresponding to

i 2
½k~=E~x~+i(FJ2)--Vi(R), and -~ki=Eex,-g+e, A
0 i I I .... ;-÷= -VI(R), respectively. Here, the potentials are given

,T- 3
_*+ Xe L2-L~N4
by
V~(R)= - R - 1+ (.~_)li(l~+ 1)R -2,
(/3 (16)
Vf(R)= --2R -1 + (-~-)ly(lf+ 1) R -2

This is the approach of Niehaus and Zwakhals [31,

0 1 l i
0 I0 20 30
Eex c (eV)
Fig. 3. The PCI energy shift A as a function of the photon excess
energy E .... for the argon K--L2L3(1D) and xenon L2 L3N4
(or = 3) transitions. Black dots with error bars represent the experi-
mental results from [20]. The broken curves indicate the shifts calcu-
lated before convoluting the line shapes with the final-state density
functions (9) and the spectrometer window function. The chain
curves show the influence of the final-state density, and the solid
curves the shifts after inclusion of both convolutions
above E~**~-2Fi, which excludes the spectator-elec-
tron line region. Previously, similar calculations based
on a Hartree-Fock approach were found to agree with
measurements of the shift of the Xe L 3 - M4 Ms (1G4)
Auger line as a function of photon energy [9].
except that we have not invoked the stationary-phase
approximation in our calculation of the overlap ele-
I ment (elY). The close agreement between the quan-
40 50 tum-mechanically and semiclassically calculated
Auger-line profiles is illustrated in Fig. 4, where the
line shape of the Xe L 3 - M 4 M s ( t G , , ) transition is
studied as a function of EeoC and ~ ( = F(La)~ 3 eV
in reality). In the WKB calculations we have l,= tI
= 2. In the quantal calculations, an approximate Har-
tree-Fock (HF) approach was used [35], It is rather
surprising that there is no difference between the
quantal and WKB line shapes, even for very larger
F~, since theoretical considerations [6] indicate that
the semiclassical approach is strictly valid only in the
limit F~~ 0.
Thirdly, Russek and Mehlhorn [41, following a
suggestion of Ogurtsov [361, have recently presented
a novel semiclassical PCI model. This approach ac-
248 J. Tulkki et al.: Quantum Theory of Post-CollisionInteraction

' I ~ ' I , I I I I I I
' I ' ' ' I ' ' ' ' I
I0
Eexc = I0 eV t
Eexc = 20 eV
8

F' = 5.64 eV / ~ r = 5.64 ev

6

= 2
2
?= o I I I I I I I I I I I I I I
~, I0
>, Eexc = IOeV ~ I E = 20 eV
exc Fig. 4. Comparison between
Hartree-Fock line shapes (dots) and
P = 14.1eV semiclassical WKB line shapes (solid
6 curves) for the xenon
/ La -- M 4 M5(l G4) Auger transition,
with fictitious large widths F ( L 3 ) .
The cross sections, normalized at
the maximum, are indicated as
functions of the relative Auger
energy e-- eA
0 I0 20 0 I0 20
Relative Auger energy (eV)

counts for the time it takes for the Auger electron this relation is still compatible with r > ], especially
to pass the slow photoelectron, and predicts that the if F < 1. Hence one may argue that it is a good ap-
PCI shift should vanish at E~xc > CA" This prediction proximation to consider the motion of the "slow"
does not follow from the model of Niehaus and Zwak- electron semiclassically I16] or, as we shall do in the
hals [3] which, on the other hand, agrees with our following, to use asymptotic wave functions.
findings. The lowest-order PCI theory may thus lead The line-shape calculations reported in Sect. 3 and
to an overestimate of the PCI shift at large E .... even 4 indicate that it does not matter very much which
though there is no indication of such overestimate type of one-electron continuum wave functions is used
in the Xe L 2 - L 3 N 4 ( J = 3 ) case, where the last mea- in the evaluation of (el lz'). The PCI line shape there-
sured point is at E ~ 0 . 2 e A [-Fig. 3]. Preliminary fore seems to be independent of the atomic structure,
D F calculations show, however, for the Xe Ns in accordance with the qualitative arguments given
- 0 2 3 O23(~S) transition that the lowest-order shift above. As we shall see, the only parameters of signifi-
does not vanish at Eexc > CA. cance are the excess energy E, intermediate-state life-
In Sect. 5 we show why the Auger line shape and time F -1, and the change Q = Q f - Q i of the ionic
the PCI shift are insensitive to the structure of the charge in the Auger-electron emission.
residual ion and to the exchange interaction between We shall simplify our problem by setting Q = QI
the escaping electrons and the ion. Our considerations and Qi = 0. The asymptotic wave functions are given
also clarify the correspondence between the quantum by (B 1) and (B2) of Appendix B, where the details
and semiclassical approaches and indicate in which of the calculation are discussed. The energy depen-
direction the lowest-order PCI theory should be im- dence of the reduced dipole matrix element (7) has
proved. not been taken into account. As a consequence, a
closed formula for [z') is obtained. According to (B 5),
this is
5. Interpretation of PCI Line Shape
]z'} = -- n r - 1 ]//2/n fl e i~r+°(a) + O (r- 5/2), (17)
In the cross section of (8), the overlap element (ell Y)
is restricted to small k = [ / ~ < 1. In the final state where we have f12 = 2 E + i F . The leading term in (17)
the "slow" electron is therefore mainly localized in is a damped spherical W K B wave which according
regions outside the ion, corresponding to r > k - 1 > 1. to (B 6) is approximately
Since we have z ~ e, this is also true for the electron
in the intermediate states, except that its motion is [z') ~ -- n r - 1 ~ e - (r/2 kE)~(COSk~ r + i sin kE r),
damped by F, i.e., it is confined to r < F-~. However, (18)
J. Tulkki et al. : Quantum Theory of Post-Collision Interaction 249

i I F I ' I I l I I I I I I

I0
,~",~"'~ Ar K - L2Ls
8

6
-- • ee°°° --
4 • eeo -
,. 2 - eooo -
- .~/ Eexc-- 17 eV - Fig. 5. Comparison between Dirac-
ooooe o° Fock line shapes (dots) and
0 ~ 1 F I I I I Coulomb line shape (solid curve) for
I0 the argon K - L 2 Ls(1D) and xenon
~ Ar K- k2L3
L2--L3 N4(J=3) transitions. The
-

E 8 Coulomb line shapes were evaluated

from the amplitude (B7), with Ao(k)
and AL(k ) given by (B 10~(B 12).
The heights of both sets of curves
4 were set equal, since the analytical
formula for the Coulomb line shape
2 does not provide absolute cross
sections, in contrast to the DF
0 t I I L I I I calculations
-I 0 I 2 -2 0 2 4
Relative Auger/Coster- Kronig energy (eV)

where kE = ~ . The damping and the 90° phase shift cases, although the analytical formula tends to overes-
between the real and imaginary parts are nicely illus- timate the PCI shift and the distortion at low excess
trated in Fig. 1 which shows the result of a rigorous energies. Figure 5 shows the result of our analysis
calculation of ]Y). The result (17) is obtained without for a low-E and a high-E case. Altogether, our consid-
the restriction that F is small. The result is in accor- erations indicate that the deformation of the Lorentz-
dance with Fig. 4 which shows good agreement be- ian line shape is not only insensitive to the structure
tween quantum-mechanical and WKB line shapes of the residual ion and to the exchange effects, but
even for E ~ F, regardless of the magnitude of F. also to the angular momentum and to the non-Cou-
In the evaluation of the amplitude {~l[~') with lombic part of the potential energy of the escaping
the asymptotic wave function (B 1) it is not possible electrons. This does not exclude the possibility that
to neglect the integral term in (B 5), even though it the absolute value of the photoionization cross section
rapidly vanishes in the limit of large r. The inclusion may depend on finer details in the PCI effect [12].
of this quantum-mechanical term ensures that the line Our results emphasize the universality in the way
shape has the Lorentzian property (Bg) in the limit shake-down transitions influence the shapes of the
Q--+ 0 and E ~ oo. In contrast, the WBK amplitude photoelectron and Auger-electron lines. Whenever
(15) suffers from the defect that its absolute square there is a time delay between the emission of the two
is not strictly a Lorentzian for Vi(R)-- Vs(R). The cal- electrons, the slower electron suddenly experiences a
culation of {81l'c'), which is rather lengthy, was per- loss of kinetic energy due to the escape of the delayed
formed for l = 0 and 5 s = 6 = 0 . The result is given one. Hence the PCI effect can be looked upon as
in the form (B 7) which separates the non-Lorentzian a consequence of the sudden increase of the attractive
amplitude Ao(k) from the Lorentzian amplitude Coulomb field of the ion. As pointed out by Russek
AL(k). It follows from the corresponding expressions, and Mehlhorn [4], this change is not completed until
(B 10) and (B 11), that the asymmetry of the line shape the Auger electron has passed the photoelectron. This
is determined by dependence of {e Iv') on the ratio fact tends to diminish the PCI shift at large E and
Q/k, where k = ]/2e. Hence the limit e~ E ~ oo coin- compels it to vanish when the Auger electron does
cides with the Q ~ 0 limit (B 8). Test calculations for not have sufficient kinetic energy to overtake the pho-
F ~ 1 eV and 3 eV showed, however, that this limit toelectron. According to our considerations, the dis-
is reached very slowly (E~ 106F). appearance of the shift is not included in the lowest-
A comparison between the analytical line-shape order PCI theory since it is assumed that Q is indepen-
formula and the DF results has been carried out for dent of E. A better approximation would be to as-
both the Ar K--L2La(1D) and Xe L2--LsN4(J=3) sume that Q is a function of the excess energy,
transitions. Very good agreement is found in both Q=Q(E), such that Q=Q(gA)~O. This is probably
250 J. Tulkki et al.: Quantum Theory of Post-Collision Interaction

the simplest way to account for the non-passing effect After integration over the angular variables we find
quantum mechanically. A more fundamental but
d2a
elaborate way would be to include the interaction --=4rc2~co
between the final [n I ly, nI, Is,] ~"3 Ls e~ Ie 2 IA ~P d q de 2
states. The disappearance of the PCI shift and the +1
associated modification of the line shape [41 may be- Z [l(lS2glSe2pxp'MLIZeff]ls22s21S)] 2
come acute when E approaches eA of an inner-shell ML = -- 1

low-energy Coster-Kronig transition, in spite of the q_ ] ( l s 2 F,2 Sg 1 p 1p, ML [Zeff] 1S 2 2s 2 1S)12]

short intermediate-state lifetime involved.
In conclusion, we have treated the PCI effect as • 6(E~xc+ea--~l --e2), (A1)
a property of the resonance behavior of the double where we have E~x¢=co--I1, and eA=Ii~--I2~ 2. The
photoionization process. It has been demonstrated quantity
that the non-Lorentzian shape of the resonant pho-
toelectron and Auger-electron peaks is almost entirely
determined by the asymptotic behavior of the wave
functions of the ejected electrons in the ionic field
Neff= k(
v=l\
Zv-~- 2 I dT
ML=--I 0

and by the lifetime of the inner-shell hole state. This
fact explains the success of semi-classical models for
both long- and short-lived inner-shell hole states. Our
quantum-mechanical considerations also indicate
how the lowest order theory of the resonant double
photoionization process should be modified to incor-
porate the screening of the photoelectron by the de-
layed Auger electron in the final state.
This research has been supported in part by the Finnish Academy
of Sciences, by the National Science Foundation under Grant No.
PHY-8516788, by the U.S. Air Force Office of Scientific Research
under Contract No. F49620-85-C-0040, and by the U.S. Department
of Energy under Contract No. W-7405-ENG-48.
AppendixA. Double 2s 2 Photoionization Cross Section
for the ls z 2S2(1S) State
It is instructive to evaluate the cross section for the
photoionization process
hco + l s 2 2s2(1S) --4 1sZgl se 2 p(1p)
including ls2sZzp(1p) resonant states, with the use
of one-electron wave functions. Fundamentally we
start from antisymmetric ]ls z k~ k~2) final states, in
which the Ik +) (v = 1, 2), with appropriate "ingoing-
wave" boundary conditions, represent the outgoing
electrons in the directions ~1 and ~2, respectively. The
calculation involves the summation over the plus and
minus spin states, expansion of the plane waves into
spherical waves, and the expression of products of
spherical harmonics as superpositions of eigenstates
of the total angular momentum operators L2 and L~.
(He__E)[ls2sZzp ip, ML ) (ls2s2zp 1p, Mcl z~]
E~o - z + i q j 2 ) (A2)
is an effective dipole operator, corresponding to lin-
early polarized light. This result is consistent with
the general expressions (1) and (2). In the present case,
the orbital angular momenta are restricted to ll =0,
l 2 = l. If la and 12 were equal, there would be only
one final many-electron state for each (el, 52) and ML
in (A 1). If separate self-consistent solutions are used
for the initial, intermediate, and final states, the cross
section (A i) reduces to a superposition of radial
monopole and dipole matrix elements. The resulting
expression is quite complicated. It is an excellent ap-
proximation, however, to set ( l s l 2 s ) = <2s[ l s ) = 0
and (ls] l s ) = (2s 12s) = 1, and to neglect amplitudes
which are proportional to products of nondiagonal
monopole matrix elements. If this is done, the cross
section (A 1) reduces to
d2a 8~zzct
co[1T(~I, e2)l2 +IT(e> el)] 2]
dex d e 2 - 3
.6(Eexc+eA--el--e2), (A3)
where
r(el, e2)=D0(ea s, 2 s ) / ) l ( e 2 p, 2s)
- R ° ( e l s, ls; 2s, 2s)
Do(g 2 p, z p ) D 1 (zp, l s ) dv
T
(A4)
oJ E~xo--z+iFlj2
Here, D O is the monopole and D 1, the dipole radial
matrix element, respectively. The modified matrix ele-
ment/)1 (e2 p, 2s) is

/)1 (e2 P, 2s)= D1 (e2 P, 2s)

~[R°(e2 p, Is; zp, 2s)-½ Rl(ls, ~2 P; zP, 2s)] Ol(zp, l s ) d r
o1 E~x~--'c + i ~ j 2 (A5)
J. Tulkki et al.: Quantum Theory of Post-CollisionInteraction 251

In (A4) and (A5), R k denotes the Slater integral such
that F(81)=2~lR°(e~ s, is; 2s, 2s)[ 2 is the Auger rate
for the [-ls] ~ [2s 2] ea s(2S) transition. If one neglects
the direct D E P I amplitude represented by the D o/5~
term in (A4), then (A4) thus follows also from apply-
ing (5)-(7) to the present case. The ratio of the modi-
fied direct and resonant amplitudes is of the order
of R°(gA s, lS; 2S, 2S)Do(gAS1, 2S), which is a very
small dimensionless number.
Appendix B. PCI Effect with Asymptotic Continuum
Wave Functions
pressed in terms of the error function, shows that
the second term in (B 5) goes to zero with increasing
r as r-5/2. F o r large r and for E>2F, which is the
region of interest in this work, we therefore have
lT')g--rcr-ll/2/~e-"(cosqr+isinqr), (B6)
where q and 7 are defined in (B4).
The calculation of the integral ( e l ] z ) was per-
formed for / = 0 and for 6j~=(5=0. Identical results
were obtained by first integrating over r or first over
y. The result is of the form
<el ~'> = - [A0 (k) + AL(k)] , (B7)

We examine the structure of the overlap element where

(e/l'c') and the function It'), which appear in the
lim A o (k) = 0,
cross section given by (5). We consider the process Q-+O
o J + X - - , X + + e - + e -, where we assume that the (BS)
"slow" electron sees the arbitrary charge Q. This is lim AL(k) = 2(k 2 - fi2)- 1.
the only atomic parameter involved besides the excess Q~0
energy E and the intermediate-state lifetime F - t. The
This result is consistent with
wave function [~I) is given by
lim I(e t z') 12= [(½ k 2 - E) 2 q- t"2/4] - 1, (B 9)
f Q zc O+0
Ig l) = r 1(2/re k)~ sin [k r + ~- log 2 k r - I
which shows that the PCI effect vanishes in the Q ~ 0
+ arg F (l + 1 -- iQ/k) + 5f (k)] (B 1) limit. The amplitudes Ao(k) and AL(k ) are

and A ~k~ - i + i e =Q/Zg~t~k~-~

o,. ]-- 2 w ]
]~) = r - ~(2/~zk') ~ sin [k'r + (5(k')J, (B 2)
• {c+ E(k+~) - ~ + - ( k - f i ) - ~ q
so that z = ( 1 / 2 ) k '2. The k dependence of the reduced -c_ [(k + ~) -~- - ( k - / ~ ) - ~ - ] }
dipole matrix element (7) is neglected. Hence we con-
sider the function AL (k) = ( ~ / 2 f i ) e-~ o_/zkEC + (J1 --da)+ C_ (J3 - J4)],
(B 10)
? d~ where
Iv'> = j (B3)
o (E+iV/2)--r
C + = F (1 + i Q/k) (2 k) ± ~o/k exp [ ± i arg F (1 - i Q/k)J,
and define f i = q + i 7 such that 8 2 = 2 E + i l , i.e.,
c~+ = 1 + iQ/k, (B i1)
q = [(E 2 + F2/4F + E3~,
(B4) and
y = E(E2 + C 2/ 4 ) =~- E] ~.
j _~/4 F(½+iQ/k) F ( - ~ - , - i Q / k ; ½ ; +fl/k)
U p o n transforming (B3) into a contour integral and
using the theorem of residues, we find 1, z = c F ( 1 ) F ( I +iQ/k) (k ~fl) ~÷
(B12)
J , ~-- ir~/4 F(½--iQ/k)
J'C') = - - ; g r - 1 ] / 2 / ~ - / ~ e ifl'+a(fl)
3'4--~ r (1)/~(1 -iQ/k)
e i6(iy) e - yr y½ dy
(B5) F(--½, +iQ/k; ~; +fl/k)
0

We have used the property c 5 ( i y ) = - 6 ( - i y ) . Since In (B 12) the upper signs refer to J1 and J3, and lower
6(k') vanishes for small values of k', we neglect the ones to J2 and ,/4, and F is the hypergeometric func-
phase shift term in the integral, which can then be tion. It is understood that this function should be
evaluated rigorously. The result, which can be ex- evaluated by analytic continuation for [fl/k[ > 1.
252
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J. Tulkki et al.: Quantum Theory of Post-Collision Interaction
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J. Tulkki
Laboratory of Physics
Helsinki University of Technology
S-02150 Espoo
Finland
G.B. Armen
T./~berg
B. Crasemann
Department of Physics and
Chemical Physics Institute
University of Oregon
Eugene, Oregon 97403
USA
Mau H. Chen
Lawrence Livermore National Laboratory
Livermore, CA 94550
USA