THE HIGH ENERGY EXCITED SHAKE-UP
ELECTRON SPECTRA OF KRYPTON
B. Eriksson, S. Svensson, N. Mårtensson, U. Gelius
To cite this version:
B. Eriksson, S. Svensson, N. Mårtensson, U. Gelius. THE HIGH ENERGY EXCITED SHAKEUP ELECTRON SPECTRA OF KRYPTON. Journal de Physique Colloques, 1987, 48 (C9),
pp.C9-531-C9-534. <10.1051/jphyscol:1987987>. <jpa-00227408>
HAL Id: jpa-00227408
https://hal.archives-ouvertes.fr/jpa-00227408
Submitted on 1 Jan 1987
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JOURNAL DE PHYSIQUE
Colloque C9, supplbment au n012, Tome 48, dbcembre 1987
THE HIGH ENERGY EXCITED SHAKE-UP ELECTRON SPECTRA OF KRYPTON
B. ERIKSSON, S. SVENSSON, N. MARTENSSON and U. GELIUS
Department of Physics, Uppsala University, PO Box 530,
S-751 21 Uppsala, Sweden
The Kr3p and Kr3d core level shake-up spectra have bcen studied using monochromatized X-ray
photoelectron spectroscopy (XPS).The spcctra show interesting differences which can be explained
by intermediatecoupling calculations. In the KT3p shake-up spectrum the spin-orbit splitting of the
3p core level dominates. However a rich Iinc structure ,due to correlation effects can also be discerned. The Kr3d shake-up spectrum is very con~plcxdue to intermediate coupling.
.
Core electron shake-up spectra froni closedshell atoms have been studied for almost two
decades. These spectra have been found to be
valuable for tests of various theoretical
methods and models. So far it has been
sufficient for the assignment of the spectra to
include only the effect of the term splitting of
the various shake-up configuration series.
Relativistic effects have been taken into account in a limited way by considering the
spin-or-bit splitting of the core level and
superimposing this splitting on all the valence
excited states.
In this work the core-electron shake-up
spectra associated with the Kr3p and Kr3d
subshells have been studied using monochromatized high energy excited(l487eV
photon energy) XPS. The enhanced resolution obtained in a monochromatized photoelectron spectrum reveals a more complex
structure than has been previoudy reported
11.21. The earlier results could be
satisfactorily described by simply calculating
the average energy for the different final state
configur~tions.1~contrast
to this the assignment of the high resolution spectra has to be
A
Kr 3d shake-up
A
.-cIn
C
Fig.1 The Kr3d
shake-up spectrum.
he structures 1-12
can be assigned to
!he 3d94p5npand
13-14 to the 3d94s5s
configurations.
a
e-
1
d
0
.In
C
Q)
C
C
11
I
46.0
I
36.0
13
I
26.0
16.0
Binding energy (eV) (rel. 3d5,J
Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:1987987
JOURNAL DE PHYSIQUE
C9-532
The Kr3d shake-up spectrum is shown in
Fig. 1. A large number of structures can be
seen, which are numbered in order of
increasing binding energy. In order to make a
preliminary assignment of the satellite
spectrum we have calculated shake-up
energies using the relativistic MCSCF
program by Grant et a1.131. Calculations were
made for the 3d94p5np and the 3d94snsconfigurations, with n=5, 6 and 7. The
calculated shake-up energies are given in
table 1.The effect of correlation was included
in an approximate way by simply shifting the
calculated energies so that the energy of the
Kr4p312 and Kr 4s core holes takes the
experimental values. This shift is
approximately 1 eV for the Kr4p312 core
hole. For the Kr4s core hole this shift is
approximately 3eV.
made using intermediate coupling. The spinorbit splitting is much larger for the Kr3p
than in the case of the Kr3d level. As a
consequence the shake-up specna show an
interesting difference. The main features of
the Kr 3p shake-up spectrum can be
described by spin-orbit doublets of roughly
the same relative intensity ratio and spin
orbit splitting as the main line. In the case of
the Kr 3d spectrum the term splitting is of the
same magnitude as the spin-orbit splitting
and an assignment has to be made by taking
intermediate coupling into account.
The spectra were recorded using our
electrostatic ESCA instrument which is
provided with an AIKa crystal monochromator. The pressure in the sample
compartment was held at such a low pressure
that the inelastic scattering contribution to the
spectra could be neglected.
.
r
..
Kr 3p shake-up
. .
.
,.
5
.
.
< '.
.
.,...'
,-•
:.<:
...:..:
a
.
.
.
~"~:.~;;;;.:~,.:;p.-
c6p-
JF-
-
'
.:.
A-.
.
...\..-..'. .
.-...*'.(3p1 ,*) 5P
+ corr. sat.
%%.
t
.
:
'
\
-:
.
(3P&P
.'-
+ con. sat. ,
:
c6p-
:.,;:.
.
+7P-
Binding energy (eV) @el. 3p3,*)
Fig.2 The Kr3p shake-up spectrum. The main structures are
interpreted as originating from the 3p54p55p wrfiguration.
The fine structures arc also due to electron correlation.
.p4
C9-533
Calculated Sd^pSSp-energies
(rel.3d 5/2 )(eV)
Calculated 3d'4s5s energies
(rel. 3d 5/2 )(eV)
(lD 2 )5p 1 / 2 2 D 3 / 2
(3D 3 )5s 2 D 5 / 2
(3D2)5s 2 D 3 / 2
2
(lD 2 )5p3/2 D 5 / 2
1
2
( D2)5pi/2 D5/2
( 1 D 2 )5 P 3 / 2 2 D 3 / 2
(3D 3 )5p 1 / 2 2 D 5 / 2
(3D3)5p3/2 2 D3/2
(3D3)5p3/2 2 D5/2
( 3 F 4 )5p3/2 2 D 5 /2
( 3 Di)5pi/2 2 D 3 / 2
( 3 D 2 )5pi/2 2 D 3 /2
(3Dl)5p3/22D3/2
(3D 2 )5pi/2 2 D5/2
(3D2)5P3/2
2
D5/2
(3D2)5p3/2 2 D 3 / 2
(3F 3 )5p3/ 2
(3DI)5P3/2
3
2D
2
3/2
D5/2
2
( F 3 )5p3/2 D5/2
(3F 3 )5pi/2 2 D 5 / 2
(3F 2 )5pi/2 2 D 3 /2
(3p 1 )5p3/2 2 D 3 / 2
( 3 Pl)5pi/2 2 D3/2
( 3 F 2 )5p 3 / 2 2 D 5 / 2
( 3 F 2 )5p 3 / 2 2 D 3 /2
( 3 F2)5pi/2 2 D 5 / 2
( 3 Pl)SP3/2 2 D5/2
(3P0)5P3/2 2 D3/2
( 3 P2)5pi/2 2 D5/2
(1F3)5P3/2 2 D5/2
(3p 2 )5pi/2 2 D 3 / 2
(3p 2 )5p 3 / 2 2 D 3 / 2
( 1 F3)5pi/ 2 2 Ds/2
(3P2)5p3/2 2 D5/2
('F3)5P3/2 2 &3/2
('Pl)5P3/2 2 D3/2
(1P\)5P3P.2D5/2
(lPl)5P1/22D3/2
17.13
17.26
17.43
17.43
17.53
17.59
17.75
8.11
18.30
18.36
18.50
18.53
18.56
18.66
18.71
18.72
18.80
18.97
19.00
19.08
19.14
19.21
19.26
19.29
19.37
19.56
19.72
19.80
19.81
19.83
19.95
19.98
20.28
20.73
20.81
20.93
(3D2)5S2D5/2
(3DI)5S2D3/2
(lD2)5s2D5/2
(1D2)5S2D3/2
35.15
35.35
35.80
36.40
36.69
37.19
Calculated 3ps4p5Sp-energies
(rel.3p3/2)(eV)
OP^VW^W.
O-vtfvm^w
(xP\)5pm2pm
0P\)5P3/22P\P.
( 3 D 3 )5p3/2 2 P3/2
( 3 D 2 )5pi/ 2 2 P3/2
( 3 D 2 )5p3/2 2 Pl/2
( 3 D2)5p3/2 2 P3/2
( 3 Di)5pi/2 2 Pi/2
( 3 Di)5pi/2 2 P3/2
( 3 P2)5p3/2 2 Pl/2
( 3 Di)5p 3 /2 2 P3/2
( 3 Dl)5p3/2 2 p l/2
( 3 P2)5p3/2 2 P3/2
(3p 2 )5pi/2 2 P3/2
( 3 P0)5pi/2 2 Pl/2
( 3 P0)5p3/2 2 P3/2
( 3 Sl)5pi/2 2 Pl/2
( 3 Sl)5p3/2 2 P3/2
(3Si)5pi/2 2 P3/2
( 3 Pl)5pi/2 2 P3/2
( 3 Sl)5p3/2 2 Pl/2
( 3 Pl)5p3/2 2 P3/2
( 3 Pl)5p3/2 2 Pl/2
( 1 D 2 )5p3/2 2 p 3/2
( 3 Pl)5pi/2 2 Pl/2
(1r>2)5pi/2 2 P3/2
( 1 D2)5p3/2 2 Pl/2
( 1 S 0 )5P3/2,1/2 2 P
17.48
17.52
17.67
17.91
18.36
18.79
18.94
19.07
19.39
19.45
19.60
19.61
19.69
19.82
20.08
20.45
20.56
26.24
26.41
26.63
26.77
26.85
26.90
26.94
26.98
26.99
27.13
27.73
29.04
Table 1. Calculation of energies of shake-up states in an intermediate
coupling scheme.
C9-534
JOURNAL DE PHYSIQUE
Structures number 1-12 can possibly be
assigned to the 3d94p5np-configurations.
The two structures 13 and 14 are more
straightforward to interprete. We conclude
that they originate from the 3d94s5s configuration, because of both position and
shape.We assign the 3d94s(3D3)5s 2 ~ 5 1 2
and the 3d94s(3D2)5s 2D3/2 to structure 13.
The rest of the 3d94s5s-configuration can
possibly explain structure 14.
The Kr3p shake-up spectrum, shown in
Fig.2, differs substantially from the Kr3d
spectrum. One reason for this is that the
Kr3p core hole state itself is influenced by
strong interactions of super Coster-Kronig
type involving the 3&nl and 3& &I- configurations 141. This interaction gives rise to
a complicatedline shape with a number of
satellite lines and to a substantial correlation
energy shift of the main lines. However, if
these correlation effects are neglected, the
intermediate coupling calculations give a
result which is rather close to a spin-orbit
doublet picture. The Kr3p shake-up spectrum
thus consists mainly of two peaks. These
two peaks seem to originate from the
Kr3p312 and the Kr3pl/2 core holes,respectively. In this respect they resemble the
Hg4f(6s-ns) /5/ and the Xe3d(5p-np) 161
shake-up spectra. Thus to a first approximation we have neglected the correlation
satellites and calculated the 3p54p5np-configurations, which are given in Table 1.As
above, we roughly approximate the
correlation effects by just shifting the
calculated energies so that the experimental
and theoretical values of the Kr3p3/2 core
hole coincide.This shift of -2.6eV makes it
possible to assign the two main shake-up
structures, which both contain correlation
satellites. As can be seen from table 1, the
calculated energies fall into two groups, one
coming from the Kr3/2 and the other from
the Kr3pl/2 core hole. See Figure 2. In conclusion intermediate coupling plays an important role to describe the complex Kr3d
shake-up spectrum whereas for the Kr3p
spectrum the spin-orbit coupling dominates.
The fine structure in this latter spectrum most
probably originates from correlation effects.
The final assignment of these spectra has to
await more eliborate relativist& calculation
including the electron correlation effects and
should i l s o include calculations of the
intensities of the states involved.
Acknowledgement
The authors want to thank J.O.Forsell and
H.Ryd&er for their skillfull assistance. This
work has been supported by the Swedish
Natural Research Council.
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