ARTICLE IN PRESS

Radiation Physics and Chemistry 70 (2004) 417–433

Structure and photoionization of confined atoms

V.K. Dolmatova,*, A.S. Baltenkovb, J.-P. Conneradec, S.T. Mansond
a
Department of Physics and Earth Science, University of North Alabama, Florence, AL 35632, USA
b
Arifov Institute of Electronics, Akademgorodok, Tashkent 700125, Uzbekistan
c
The Blackett Laboratory, Imperial College, London SW7 2BW, UK
d
Department of Physics and Astronomy, Georgia State University, Atlanta, GA 30303, USA

Abstract

Phenomenological approaches on the basis of simple model potentials for the description of various situations where
the atom is spacially confined, such, e.g., as atoms inside a C60 -like environment or in impenetrable cavities of small
radii are reviewed along with the trends in modifications in structure and photoionization of such confined atoms.
r 2003 Elsevier Ltd. All rights reserved.

PACS: 31.10.+z; 32.80.Fb

Keywords: Compressed atoms; Endohedral atoms; Shell filling; Photoionization

1. Introduction atoms (Lawrence et al., 1981), the reversible storage of

This paper reviews research activities that branch out
from traditional atomic physics in a very significant
respect: the objects of study are no longer free atoms but
confined atoms, i.e., atoms which are trapped inside
hollow spatial cages whose sizes are commensurable
with the sizes of atoms. Obviously, a confined atom
behaves differently from the free atom. Therefore, the
various properties of confined atoms, such as the
modification of their atomic orbitals, energy levels, the
filling of electronic shells, polarizability, photoioniza-
tion/photoabsorption, hyperfine structure, etc., can
provide insight into understanding of the phenomenol-
ogy of the confined atoms. Examples of situations and
phenomena of direct relevance to confined atoms are
helium droplets (Zicovich-Wilson et al., 1994), nano-size
bubbles formed in liquid helium (Goodfriend, 1990),
atoms A encapsulated in hollow cages of carbon based
nano-materials, such as endohedral fullerenes A@C60
(Shinohara, 2000; Moriarty, 2001; Forro! and Mih!aly,
2001), the chemical reactivity and chemical valence of
*Corresponding author. Tel.: +1-256-765-4320; fax: +1-
256-765-4795.
E-mail address: vkdolmatov@una.edu (V.K. Dolmatov).
ions in certain solids (Connerade, 1997; Connerade and
Semaoune, 2000a), the appearance of helium bubbles
under high pressure in the walls of nuclear reactors
(Walsh et al., 2000), and ESR, NMR and magnetic
moments of compressed atoms (Buchachenko, 2001),
etc. Confined atoms are also very close in principle
to the concepts underpinning confinement within
‘‘quantum dots’’ (Johnson, 1995; Sako and Diercksen,
2003a, b). Thus, the concept of a confined atom
provides insight into various problems of interdisciplin-
ary significance.
The present paper reviews many of results on confined
atoms obtained after 1996 on the basis of simple
phenomenological models where the confinement is
imitated by placing an atom inside a model potential
!
(results prior to 1996 were well reviewed by Jaskolski,
1996). Two different types of confinements are con-
sidered, as specified below.
In Section 2, we consider results of latest studies on
multielectron atoms confined inside an impenetrable
spherical cage of adjustable radius. There is, of course,
no actual ionization continuum in a hard-wall cavity.
Therefore, this model is appropriate when simulating
effects of high pressure on bound energies and
wavefunctions of atoms. Correspondingly, herein, we

0969-806X/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.radphyschem.2003.12.024
 ARTICLE IN PRESS
418 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
review modifications in energies and rearrangements in
the filling of shells, as well as the disappearance of
known and the appearance of new regularities in the
periodic table of atoms under strong pressure. Although
our primarily interest is towards confined multielectron
atoms, discussion of hydrogenic atoms and molecules as
well as two-electron atoms is provided as well.
Section 3 is devoted to atoms confined inside the
empty cage of a penetrable soccer-ball-like environment.
This model is appropriate when studying endohedral
fullerenes A@C60 ; where A is an atom—the ‘‘endohe-
dral’’ atom—encapsulated in the empty cage of the C60
molecule (Shinohara, 2000; Moriarty, 2001; Forro! and
Mih!aly, 2001). Here, we review modifications in
structure and photoionization of such endohedral
atoms. This topic is particularly relevant, because with
photoionization experiments on A@C60 by laser and
synchrotron radiation under way, it becomes a matter of
practical importance to be capable of distinguishing
which part of the spectrum of the endohedral fullerene is
due to photoionization of its confining shell and which,
to photoionization of the encapsulated atom alone.
Following notations adapted in herein referenced
papers, (see, e.g., Connerade et al., 2000a), we use the
notation ‘‘@A’’ for a confined atom A, reserving ‘‘A’’
for a free atom. Atomic units (a.u.) are used throughout
the paper.
2. Compressed multielectron atoms
2.1. Preliminaries
The concept of a confined atom was, of course,
introduced many years ago. It has attracted much
attention of investigators since 1937, when Michels et al.
(1937) proposed to simulate the effect of pressure on an
atom by placing it inside an impenetrable spherical cage.
This work was followed by the work of Sommerfeld and
Welker (1938) with calculations of the ground-state
hydrogen atom confined inside an impenetrable sphe-
rical potential
( a.u. In a subsequent work, Sen et al. (2002b) demon-
0 for 0ororc ;
Vc ðrÞ ¼ ð1Þ
N otherwise;
where they uncovered the existence of the critical radius
r0 ¼ 1:835 a.u. below which the 1s electron of hydrogen
is no longer bound by the proton but by the cage itself.
This simple model of an atom inside potential (1) has
found numerous applications to date.
Recently, a great deal of new work on confined atoms,
including, hydrogen and hydrogen-like ions, has been
reported. The problem is probed not only with the use of
potential (1), but also by means of the imposition of
constraint conditions on the wavefunctions on borders
of a non-specified impenetrable potential (Pupyshev,
2000), by modelling the spatial confinement by the
!
impenetrable power potential (see, e.g., Bielinska-W a- z’
et al., 2001a),
1
Vn ðrÞ ¼ onþ1 rni ; ð2Þ
2
the Woods–Saxon potential VWS ðrÞ (Costa et al., 1999),
2l
VWS ðrÞ ¼ ; ð3Þ
1 þ exp½ðR  kÞZ
as well as the shell-potential Vshell represented by the
concentric inner and outer spherical potential walls of
radii ra and rb ; respectively (Sen et al., 2002a)
(
N for ra ororb ;
Vshell ðrÞ ¼ ð4Þ
0 otherwise:
Despite the fact that the first consideration of the critical
radius r0 below which the ground-state H atom gets
ionized under pressure was introduced by Sommerfeld
and Welker (1938), it was not until recently that the
systematic studies of the critical radius r0 for the excited
states of the hydrogen atom, centrally confined by
potential (1), along with related accurate non-relativistic
wavefunctions and binding energies, have been investi-
gated (Varshni, 1997, 1998; Laughlin et al., 2002). Sen
et al. (2002a) studied static dipole polarizability of the
hydrogen atom placed in an impenetrable spherical shell
potential (4) and ended up with a remarkable result.
They demonstrated the dramatic increase, by several
orders of magnitude, in the static polarizability of the
shell-confined hydrogen which overshoots by far the
maximum possible increase in the static polarizability of
H confined inside the spherical box potential (1). Based
on these results, these authors predicted values for the
inner ra and outer rb radii for the shell-confined
hydrogen atom at which the metallic behaviour of H
may be attained. Interestingly, the difference between ra
and rb ; for which metallic behaviour may occur, can be
several times larger than the size of the atom. For
instance, the corresponding radii ra and rb ; pair as
follows: ðra ; rb Þ ¼ ð2:54; 5:0Þ; ð3:01; 8:0Þ; and ð3:29; 10:0Þ
strated that the polarizability of the exotic hydrogenic
ions with fractional nuclear charges Z ¼ 1=2; 2=3; 4=3;
and 5=3 exhibit strong dependence on both the radius of
an impenetrable spherical confinement and the nuclear
charge. Banerjee et al. (2002) investigated the mean
energy, static polarizability, and hyperpolarizability of
the spherically confined hydrogen atom and demon-
strated the extreme sensitivity of these characteristics to
the radius of the confinement. To list but one of them, it
is the change in a sign of the hyperpolarizability when it
becomes negative under confinement. Saha et al. (2002a)
investigated, using time-dependent variation perturba-
tion calculations, the transition energies, oscillator
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
strengths and transition probabilities for dipole allowed
states in the hydrogen atom compressed in a weakly
coupled plasma, where, again, the compression was
modeled by embedding the atom at the center of an
impenetrable spherical box (1). In a later work, Saha
and Mukherjee (2002) extended the study to the
positronium atom in a weakly coupled plasma. Huang
et al. (1999) studied relativistic effects on the confined
hydrogenic atom and provided criteria for importance
of relativistic effects in compressed hydrogen and
hydrogenlike ions.
The above work on hydrogen is related to the atom
centrally confined in a spherical impenetrable box. The
generalization of the study to the off-center confined
hydrogen in an impenetrable spherical box was per-
formed in recent papers by Changa et al. (2000), where
they developed a perturbation theory for the off-centre
confined atom, and by Ting-yun et al. (2000) with the
use of a variational calculation using B-splines.
The compressed hydrogen molecular ion was investi-
gated, using the configuration interaction method, by
!
Bielinska-W a- z’ et al. (2001b), where they studied the
structure and vibronic spectra of the hydrogen mole-
cular ion placed in a spherically symmetric harmonic
oscillator potential. Alternatively, Mateos-Cort!es et al.
(2002) investigated electronic and vibrational properties
of the hydrogen molecular ion inside penetrable prolate
spheroidal box.
A number of studies have been performed on the scale
of confined two-electron atoms which are the simplest
representatives including electron correlation effects in
confined atoms. Correspondingly, Bielinska-W! a- z’ et al.
(2001a) investigated energy spectra of two-electron atoms
confined in a spherically symmetric potential of mixed
Coulomb and harmonic form using a combination of a
Hartree–Fock approximation along with the configura-
tion interaction method. Rivelino and Vianna (2001)
presented a new configuration interaction model to treat
confined multielectron systems and calculated the total
energy for the He ground state, assuming, again, that the
atom is enclosed in an impenetrable spherical box (1).
Saha et al. (2002b) investigated the behaviour of ground-
state energies of confined two-electron isoelectronic series
from He to Arþ16 by embedding the ion in a charge
neutral environment, like that of plasma, and approx-
imating the confinement potential as a screened Coulomb
potential between charges within the Debye model.
Energy levels were shown to turn into unstable as the
screening was increasing. Within ultimately the same
model, Mukherjee et al. (2002) investigated the influence
of the Debye screening on the energy spectra of the
ground state and of the first three 1 S excited states of
helium-like ions with 2pZp10 embedded into a plasma-
like environment; dependencies of the energies of two-
electron atoms on both the nuclear charge and the Debye
parameter were demonstrated.
419
A series of recent work has been devoted to multi-
electron atoms centrally confined by an impenetrable
spherical potential (1). Connerade (1997) employed this
model to establish new principles underlying soft
chemistry at the atomic level. Connerade and Dolmatov
(1998) calculated, within the framework of non-relati-
vistic Hartree–Fock (HF) equations, generalized by
adding the Vc ðrÞ potential (1) to the HF potential,
modifications in both the ground state 4s and 3d5 and
excited state 3d% (due to the 3p-3d% excitation)
orbitals in the confined Crð3p6 3d5 4s1 Þ atom. For the
Cr% ð3p5 3d5 3d% 4s1 Þ excited configuration, the binding
energy of the spectator 4s and 3d valence electrons was
found to decrease with the decrease in the confinement
radius rc ; whereas the energy of the 3d% excited electron
at first increased and then decreased, the phenomenon
earlier referred to (Connerade, 1997) as ‘‘atomic swing’’.
Also, Connerade and Dolmatov (1998) witnessed
induced orbital collapse of the 3d% orbital when, due
to increasing pressure on the atom (i.e., due to
decreasing rc ) the 3d% orbital suddenly collapsed into
the inner region of the atom, even though the radius rc
of the spherical box was much greater (rc X11 a.u.) than
the size of the atom. Of especial importance was that
changes in the wavefunction of a multielectron atom due
to increasing external pressure were similar to those
induced by an increase in the effective nuclear charge of
the free atom, with the implication that in compressed
multielectron atoms the filling of shells should be more
hydrogenlike with increasing pressure. With the impetus
of this finding, Connerade et al. (2000a) detailed, within
the term averaged HF approximation, the energy
spectra of ground-state, and some ionized and excited
configurations of multielectron atoms and ions of the 3d
and 4d periods of the periodical table: Sc, Ca, K, Cr,
Mn, Ni, Sr, Pd, Ga, Ge, In and Sn. The valence d
orbitals were found to be highly compressible, i.e., they
undergo considerable contraction with increasing pres-
sure (decreasing rc ) which results from the induced
orbital collapse and underpins shell filling of a number
of compressed atoms. In the same work, new regularities
were found to appear while the former (e.g., the effect
known as s–d competition) disappear in the overall
organization of the periodic table for confined atoms.
Also, demonstrated was the effect of ‘‘autoionization’’
of atoms by pressure, similar to that discussed by
Sommerfeld and Welker (1938) and by Varshni (1998)
for ionization of hydrogen by pressure, although, of
course, for a multielectron atom, there is a richer variety
of phenomena, owing to the presence of more than one
ionization threshold. Finally, Connerade and Semaoune
(2000a) extended non-relativistic calculations of multi-
electron atoms confined in an impenetrable spherical
box model to relativistic Dirac–Fock calculations, to
detail pressure induced modifications in heavier atoms of
d-series where they found dramatic importance of
 ARTICLE IN PRESS
420 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
relativistic effects, in some cases. The application of this
relativistic model to atomic caesium showed that the
remarkable compressibility of caesium originates from a
purely atomic mechanism, namely the pressure induced
orbital collapse of the 5d orbital of Cs. Based on this,
they concluded that, generally, the pressure induced
orbital collapse can also drive a reversible insertion of
atoms into solids, and this idea was supported by the
discussion of a possible application to lithium-ion
batteries.
Some of these results on multielectron atoms, such as
modifications in wavefunctions, energies and the filling
of shells in multielectron confined atoms are detailed
below.
2.2. A multielectron atom in an impenetrable spherical
box
Details of wavefunctions of valence and/or excited-
state electrons in atoms as well as the filling of electronic
shells is fundamental to chemistry, because the order of
filling determines the electronic properties of free atoms;
a simple example is valence. Consistent study of the
modifications of outer wavefunctions in multielectron
atoms and the ability of these atoms to rearrange their
structure upon being compressed was recently detailed by
Connerade et al. (2000a) and Connerade and Semaoune
(2000a). In this subsection, we give examples that atoms
exhibiting orbital collapse, i.e., essentially all the transi-
tion atoms with regard to d- and f-orbital collapse are
extremely sensitive to an increase in the pressure on the
atom. The phenomenon of orbital collapse is due to
competition between the inner short range well, which
develops in transition and rare-earth elements, and the
outer, long range part of the effective radial potential for
d and f states (see, e.g., Connerade, 1998 and references
therein). When a transition element or rare-earth is
placed inside an external impenetrable cavity, the long-
range outer well is replaced by a finite well which is less
binding, and so the competition between the inner and
outer wells can be altered in favor of the former. As a
result, orbital collapse into the inner well can be induced
by gradually reducing the radius rc of the cavity.
2.2.1. Electronic wavefunctions
Fig. 1 exemplifies modifications in the excited 3d%
orbital of the confined excited @Cr% ð3p5 3d5 4s 3d% Þ;
7
P atom (Connerade and Dolmatov, 1998). The
calculations were performed using the ‘‘spin-polarized’’
Hartree–Fock (SPHF) (Slater, 1974) approximation for
the confined @Cr% atom modified by adding the
spherical box potential (1) to the equations and solving
them with the Dirichlet boundary conditions Pnl ð0Þ ¼
Pnl ðrc Þ ¼ 0; where Pnl is the radial function for an
atomic orbital of given principal n and orbital l quantum
numbers.
0.8 Cr
rc = 5 a.u.
10
3d* radial orbital (a.u.)
0.6 11
X 14
0.4 Y
15
0.2 20
30
0.0
0 4 8 12 16 20 24
R (a.u.)
Fig. 1. Excited 3d% (due to the 3p-3d% transition) radial
wavefunction of @Cr% ð3p5 3d5 4s3d% Þ; 7 P calculated for
different values of the confinement radius rc ; as marked in the
figure. Note, that there exists two classes of solutions to the
SPHF equations, characterized by two different zones X and Y
through which, to a good approximation, all curves of a given
family pass.
It is clearly seen that the 3d% orbital undergoes
considerable contraction. This is due to the induced
orbital collapse, with decreasing rc which occurs
between rc ¼ 14 and rc ¼ 11 a.u. which is noticeably
greater than the size of the excited atom. Note, induced
orbital collapse was also illustrated for the excited 3d%
orbital of the confined excited @Caþ% ð3p6 3d% Þ atom
in the work of (Connerade et al., 2000a) where
calculations were performed using the Hartree–Fock
configuration average code (Fisher Froese, 1977).
Fig. 2 shows 3d% wavefunction for different Z for
@Cr% ð3p5 3d5 4s3d% Þ (Connerade and Dolmatov,
1998). An important observation is that the modification
in 3d% orbitals can equally well be modified by altering
the nuclear charge Z of the atom. Indeed, Looking at
these figures, one can see that much of the character of
the functions in Fig. 1 is preserved in Fig. 2; even the
inner zone X occurs at approximately the same radius in
both figures. Such similarity in the dependence of a
wavefunction on either rc or Z was observed (Connerade
et al., 2000a) for the 3d% excited orbital of
@Caþ% ð3p6 3d% Þ as well.
The similarity in dependencies of the wavefunctions
on either rc or Z implies that, in compressed multi-
electron atoms, the filling of shells should be more
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433 421

consequence of these opposing motions, the total energy

Z=25.0 Cr
0.8 of the configuration remains remarkably steady in the
24.4 same range. Notice also the faster change of binding
3d* radial orbital (a.u.)

24.05 energy in the range 11oR0 o14; which happens to be

0.6 precisely the range in which induced orbital collapse
occurs.
X
0.4 24.045
2.2.3. The filling of shells
The filling of electronic shells is a fundamental
Y property of atoms, because the order of filling deter-
0.2
mines their electronic properties. It is exemplified below
24 that atoms exhibiting orbital collapse, i.e., essentially all
0.0 the transition atoms with regard to d-orbital collapse,
are especially sensitive to the increase in pressure on the
0 4 8 12 16 20 24 atom (Connerade et al., 2000a). The implication is that
R (a.u.) all the usual chemical properties of transition metals (in
particular, their valence) are modified under pressure. In
Fig. 2. 3d% excited (due to the 3p-3d% transition) orbital of Fig. 4, the cases (Connerade et al., 2000a) of compressed
@Cr% ð3p5 3d5 4s3d% Þ; 7 P calculated for different values of Z;
K, Ca, Sc, Cr, Mn and Ni which lie at the beginning of
as marked.
the 3d raw of the periodic table are shown.
It is seen that, with decreasing cavity radius rc ; i.e.,
0 with increasing pressure on the atom, configurations
3d * involving a 3d electron drop below corresponding
configurations in which a 3d electron is replaced by 4s.
-8 This behaviour is due to induced orbital collapse for
Energy (eV)

4s orbitals with lX2; owing to the replacement of the long-

-16
-24 -3
E0x10
0 5 10 15
rc (a.u.)
Fig. 3. Binding energies for 3d and 4s orbitals, as well as for the
excited 3d% orbital (due to the 3p-3d% transition) and the
total energy E0 of @Cr% ð3p5 3d5 4s3d% Þ; 7 P as a function of the
radius rc of an impenetrable spherical potential (1).
hydrogen-like with increasing pressure and may thus
differ from their free counterparts.
2.2.2. ‘‘Atomic swing’’ effect
In Fig. 3, we show the SPHF calculated results
(Connerade and Dolmatov, 1998) for the binding
energies of the ground-state 3d and 4s and excited
3d% electrons and the total energy for the excited
@Cr% ð3p5 3d5 4s3d% Þ; 7 P atom.
The significant point is that the binding energy of the
spectator 4s and 3d valence electrons is decreasing, while
the binding energy of the excited 3d% electron at first
increases and then decreases as the cavity radius is
reduced—the effect previously predicted by Connerade
(1997), referred to as ‘‘atomic swing’’ effect. As a
range outer potential well by a less binding finite well.
As a result, the outer 3d electrons find it easier to
penetrate the core than the 4s electrons, because the 3d-
5 orbitals exhibit orbital collapse whereas the 4s-orbitals
3d
do not.
Furthermore, as seen from Fig. 4, for rc t4 a.u., in all
20 25 30 atoms considered the 3d shell fills earlier than for free
atoms. It is only beyond Ni that the 4s-subshell begins to
fill under pressure. The ordering of filling of shells in
compressed atoms is thus closer to the one which would
occur if the levels followed the strict hydrogenic ordering
implied by the aufbau principle. Hence, orbital collapse
also has the consequence that well-known 3d–4s
competition disappears under compression, so that all
elements down the row now exhibit a similar tendency.
Let us compare atoms along successive rows of the
periodic table. For free atoms, successive rows of the
transition sequences do not fill in the same order. In
the regions of d-filling, two elements taken from
the corresponding position in two successive rows have
either the same ground configuration, or the number of
d and s electrons is different. Each one of these two
situations was considered by Connerade et al. (2000a) by
picking up atoms from each end of the long periods. In
Fig. 5, shown are results (Connerade et al., 2000a) for
the atom at the beginning of the 4d row, the Sr atom.
Fig. 5 should be compared with results for @Ca
which is the atom at the beginning of the 3d row (Fig. 4).
For rc t4 a.u., @Sr has the lowest configuration 4d2 ;
similar to the @Ca’s 3d2 configuration in the same range
 ARTICLE IN PRESS
422 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433

of rc ’s in Fig. 4. Generally, the behaviour of the

Sc
-675
configuration energies for @Sr parallels the behaviour
-759
-597 of the outermost configurations of @Ca, crossing over
2 3
4s 3d from an s2 to a d2 ground state for rc between 4 and 5
a.u.
2
-760 3d 4s A case where the ground configurations in the 3d and
-676 4d rows are not the same, can be exemplified (Con-
4 6 8
-598 2 nerade et al., 2000a) by choosing Ni and Pd from the
3d
Ca end of a row. The Pd atom is the only free atom of the
Total energy (a.u.)

periodic table whose the outermost subshell is a d10

K 4 6 8 subshell, which is closed. In contrast, the lowest
3d 4s configuration of free Ni is different: 3d8 4s2 : Conse-
-599
quently, when Pd is placed inside a cavity no change of
ordering in @Pd is induced by compression, since the
-1042 -1148 5 2 Mn ground state is already 4d10 : For @Ni, however, as
5 3d 4s
3d 4s follows from Fig. 4, 3d10 becomes the lowest configura-
-1149 7 tion under pressure. Hence, differences between succes-
Cr 3d
sive rows tend to disappear as the pressure is increased.
2 4 6 8 As follows from the above discussion, the influence of
3d
6 the external cavity tends to restore the same order of
-1043
filling for both the 3d and the 4d rows, and this order is
the one predicted by the aufbau principle, with the d
-1505 Ni subshell filling first.
8 2 9
3d 4s & 3d 4s
-1506 2.2.4. Relativistic effects
10 In principle, these rules for filling should extend also
3d to heavier systems. However, for heavy elements, a full
2 3 4 5 6 7 8 9 treatment of relativistic effects would really be neces-
rc (a.u.) sary. The problem of confined atoms with inclusion of
relativistic effects was modelled by Connerade and
Fig. 4. Total energies of some lowest configurations of atoms Semaoune (2000a). The applicability of the model was
as a function of the radius rc of a spherical impenetrable tested by comparing the calculated and experimental
potential (1). Considered are elements from different parts of data (Takemura et al., 1981) for atomic size of the Cs
the 3d transition row: close to the start of the row (K, Ca and atom versus pressure. It was shown that the theoretical
Sc), near the middle of the row (Cr and Mn) and towards the model (1) reveals a discontinuity in the volume decrease
end of the row (Ni). All the curves exhibit crossings. This is
of metallic caesium. The magnitude of the discontinuity,
because the 3d orbitals are more compressible than 4s. ( within the non-relativistic model, and 0:38 A (
0:306 A
within the relativistic model, was in good agreement
with the experimental value, 0:3 A; ( of Takemura et al.
Relativistic effects, however, pose a subtle question
concerning boundaty conditions for confined atoms and
-3128 are outside the scope of this paper.
Sr
Total energy (a.u.)

2 2.2.5. ‘‘Autoionization’’ by pressure

-3129 5s
When a many-electron atom is compressed, its ground
state rises in absolute energy, as was demonstrated
2
-3130 4d above. The same is true for an ion but, because the
4d 5s radius of an ion is smaller than that of an atom, the rise
is much smaller. Consequently, there is always a crossing
-3131 point: for cavities smaller than a critical size, the ground
state of the atom lies higher in energy than the ground
2 4 6 8 state of the ion. This was shown in the work of
Connerade et al. (2000a) by the rise in the total energy
radius, rc (a.u.)
of neutral @Ca, singly ionized @Caþ ð4s1 Þ and singly
Fig. 5. Total energies of 5s2 ; 4d5s and 4d2 of Sr, as a function ionized-excited @Caþ% ð3d% Þ: Obviously, the ground
of the radius rc of a spherical impenetrable potential (1). state of the atom is no longer stable when it lies higher in
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
energy than the state of the ion. When this occurs,
ground states transform, so to speak, into autoionizing
states in the compressed atom.
2.2.6. Induced mixed valence
The outstanding features in Figs. 4 and 5 are the
crossing points between various configurations. At such
crossing points, an atom can exist in a superposition of
different kinds of quantum states on a sufficiently short
timescale. By analogy with the solid (Sommerfeld and
Welker, 1938), this situation resembles mixed valence:
the atom has a choice as to how many electrons remain
attached, and how many go into the conduction band,
and both possibilities coexist on the same site.
2.2.7. ESR, NMR and magnetic moments of compressed
atoms
Other very important aspects of compressed atoms of
direct relevance to the discussion in this and the next
section of the paper, are general trends in the behavior
of magnetic parameters displayed by compressed atoms.
For these, we refer the reader to an excellent recent
review paper by Buchachenko (2001). The paper collects
available experimental and theoretical data on the ESR
and NMR spectra, as well as the magnetic moments of
compressed atoms and detailes trends in these phenom-
ena with special emphasis on the electron–nuclear
(hyperfine) coupling as a parameter characterizing the
modification of atomic orbitals and the redistribution of
spin density in atoms under compression.
2.3. Conclusion
Generally, in the periodic table of confined atoms,
there appears a tendency of shell filling to follow the
rules of the Bohr–Stoner aufbau principle beyond the
point where it breaks down for free atoms, and for the
long sequences of the periodic table to replicate from
one row to the next. The illustrated concepts of the pure
aufbau ordering in the filling of shells for compressed
atoms, of modifying orbital collapse, of the interplay
between this aufbau ordering in the filling of shells and
modified orbital collapse as well as the disappearance of
known and emergence of new regularities in properties
of confined atoms are of importance for foundations of
a consistent theory of confined transition, rare-earth and
actinide atoms. The calculations reviewed in this section
give only a first insight into the rather complex problem
of confined quantum systems. Effects which remain to
be better understood to complete the theory to its logical
end are the LS dependence of orbital collapse for some
critical cases, the influence of multiplet structure on level
crossings, as well as the manner in which relativistic
effects should be built into the theory (Connerade and
Semaoune, 2000a), so that heavier species can be
included. Once all this is achieved, the whole periodic
423
table will be established within a single consistent theory
for confined atoms. The theory will definitely be useful
for the chemistry of elements in the solid and in various
compressed phases, once, in particular, properties such
as valence can differ from those of the corresponding
free atoms.
3. Endohedral atoms
3.1. Preliminaries
Endohedral atoms A@C60 (see, e.g., review papers by
Shinohara (2000), Moriarty (2001) and Forro! and
Mih!aly (2001)), where A is an atom confined inside a
hollow cage of the carbon fullerene C60 ; have attracted
much attention of investigaters in recent years not
merely as new, facinating subjects for studies, but
because of an industrial interest in these objects as well.
With photoionisation (photoabsorption) experiments on
C60 in the extreme ultraviolet (Kou et al., 2003), as well
as on endohedral fullerenes A@Cn in the ultraviolet
photon energy region (Shinohara, 2000) underway, it
becomes a matter of practical importance to be capable
of distinguishing which part of the spectrum of the
endohedral fullerene is due to photoionization of
the cage and which is from the photoionization of the
endohedral atom itself. This brings up the necessity of
studying the structure and photoionization of the
endohedrally confined atom A itself. This is, to the best
of our knowledge, an experimentally unexplored area to
date. Due to the utter complexity of the problem from a
theoretical side, simplifications, even considerable sim-
plifications allowing us to uncover rich variety of effects
which can occur in A@C60 systems rather than to make
detailed precise predictions for a particular spectrum,
are more than justified as a step in understanding which
aspects of the spectra are most interesting. At the same
time, the differences in predictions between various
models could be a step in identifying useful measure-
ments which could be performed.
In this section, two simple approaches, based on the
modelling of the C60 cage by either a spherical, short-
range potential shell of inner radius R and thickness D
(
U0 for RoroR þ D;
Vshell ðrÞ ¼ ð5Þ
0 otherwise;
or by the d-potential
(
U0 dðrÞ for r ¼ R;
Vd ðrÞ ¼ ð6Þ
0 otherwise;
where R is the radius of C60 ; are reviewed.
The simulation of the C60 -like shell by potential (5)
was, perhaps, first suggested by Pushka and Niemenen
 ARTICLE IN PRESS
424 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433

(1993) in their study of photoabsorption of the atom A
from the A@C60 formation in the framework of the
time-dependent density-functional theory combined
with a jellium model for the confining shell. They
revealed the appearance of oscillation structure,
though weak enough, in photoemissions of thus
confined atoms Xe and Ba from Xe@C60 and Ba@C60 ;
correspondingly. The potential (5) was later on em-
ployed by Xu et al. (1996) to interpret physics hidden
behind observed oscillations in the photoionization
cross section of the C60 cage itself. To date, the model
potential (5) has found useful applications in a number
of investigations of structure and photoionization of
thus simulated endohedral atoms A@C60 (Connerade
et al., 1999a, b, 2000b, c, 2001; Connerade and
Semauone, 2000b; Dolmatov et al., 2002) where a
number of important findings were revealed. To list a
few of them, the prediction of unusual level crossings
and degeneracies resulting in avoided energy level
crossings, exemplified by the H@C60 formation (Con-
nerade et al., 1999a), the appearance of confinement
resonances in photoionization cross sections of A@C60
atoms (Connerade et al., 1999b, 2000b, c), effects of
selective compression of the atomic orbital by an
attractive shell (Connerade et al., 1999b; Connerade
and Semauone, 2000b), the significant redistribution of
oscillation strengths and ‘‘reversed’’ action of electron
correlation in @A atoms compared to free atoms
(Connerade et al., 1999b), etc. When potential (5) is
used to simulate the C60 cage, it is natural to use
experimental values for rc and D: Specifically,
(
rc E3:04 AE5:75 (
a.u., and DE1 AE1:89 a.u. (Xu
et al., 1996). The potential depth, U0 ; can be obtained
from experimental data on the negative C60 ion (Wang
3.2. Evolution of the energy spectrum
We start our discussion by considering the evolution
of the discrete energy spectrum Enl of centrally confined
endohedral hydrogen, H@C60 ; obtained (Connerade
et al., 1999a) on the basis of modelling the C60 cage by
potential (5) and solving, numerically, related radial
.
Schrodinger equation. In the cited work, R and D
matched the experimental valued specified in Section
3.1. However, since the potential depth U0 of the
fullerene cage could be altered in a variety of ways, such
as changing the number of C atoms it contains, etc., the
study included a broad range of these values, in order to
explore the physics more generally. The calculated 1s to
4f energy levels of @H are shown in Fig. 6.
Looking at ns levels, the lowest state, the 1s, for small
values of U0 it remains at 13:6 eV; the 1s binding
energy of free H. This is because the extent of the 1s
radial wave function in H is such that it is essentially
zero at the inner radius of the confining potential well,
5.8 a.u., so that for small U0 it does not ‘‘feel’’ the effects
of the outer confining well . The 2s state, on the other
hand, has a significant portion of its amplitude in the
region of the confining well and, thus, very quickly gets
bound primarily in this outer well, so that its energy is
lowered as the outer well deepens. Eventually,
with further deepening of the outer well, the 2s state
bound in this well has energy comparable with the 1s
state in the inner well. At this point of degeneracy, or
0 4s, 4p
E nl (eV)

et al., 1993), who determined the electron affinity of -5 3p 4d

2:65 eV for C60 : A straightforward fit to this energy for 4f
an electron placed inside the empty spherical attractive
-10 2p 3d
shell defined above yielded (Connerade et al., 1999a) 3s
U0 ¼ 8:22 eV: 1s 2s
The d-potential approximation was employed by -15
Amusia et al. (1998) for the description of the electron 0 1 3
2
scattering from C60 and later on by Baltenkov (1999) (a)
and Amusia et al. (2000) for the investigation of
different aspects of angle-integrated and angle-resolved 0
photoionization cross sections of @A atoms. A unique
result of this approximation is that the photoionization -5 -0.8
4s 4p
cross section of the endohedrally confined atom, 4d
s@A ðoÞ; was found to be a modulated photoionization -10 -1.2 4p 4s
cross section of the free atom, sA ðoÞ; with a modulation
factor SðoÞ which is a strongly oscillating function 0 2 4 6
-15
of the photon frequency o : s@A ðoÞ ¼ SðoÞsA ðoÞ: This
4 5 6 7
allows one easily to conclude that the photoionization
(b) U0 (a.u.)
cross section of an endohedrally confined atom is
oscillating resonance functions of o resulting in the Fig. 6. Binding energies of 1s to 4f states of H placed in the
appearance of resonances in photoionization cross geometrical centre of potential (5) with rc ¼ 5:8 a.u., D ¼ 1:9
sections of A@C60 : a.u. as a function of U0 :
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
Probability, W2s
0.6
0.4
0.2
0.0
0 1 2 3
U0 (a.u.)
Fig. 7. Probability, W2s ; that a 2s electron is located within the
attractive spherical shell with R ¼ 5:8 a.u., D ¼ 1:9 a.u., as a
function of U0 :
near-degeneracy, a strong interaction between the
two states leads to the avoided crossing clearly seen at
U0 ¼ 0:7 a.u. At still greater outer well depth the
situation reverts to one state bound in the inner well and
one in the outer well. Since the lowest energy level is
defined to be 1s, the level now bound in the outer well is
the 1s, whereas the level in the inner well at 13:6 eV is
the 2s. Thus, one observes a phenomenon in which the
2s, formerly bound in the outer well ‘‘collapses’’ into the
inner well, while the 1s, formerly in the inner well,
simultaneously ‘‘collapses’’ into the outer well. The
behaviour further repeats for 3s and 4s, etc. As an
illustration, the probability that the 2s electron is in the
outer well, i.e., at a value of radius r between 5.8 and 7.7
a.u., is shown in Fig. 7. The probability increases as U0
increases from zero, reaches a maximum, then decreases
at the avoided crossing, to roughly zero, when the 2s
wavefunction ‘‘becomes’’ the free H 1s orbital. Then it
increases again at the next avoided crossing, above
which it is bound in the outer well and the probability is
large.
Unusual for hydrogen is the level ordering with
increasing outer well depth. Above U0 ¼ 1 a.u., the level
ordering is seen to be 1s, 2p, 3d and 4f. This is followed
by the group 2s, 3p and 4d above U0 ¼ 2:25 a.u., and 3s
and 4p above U0 ¼ 6:75 a.u. The lower levels are thus no
longer grouped by principal quantum number n; but by
a number of nodes Nnl ¼ n  l  1; ordered within each
group by increasing l: It is also evident from Fig. 6 that
the evolution from H atom to attractive spherical shell
level ordering proceeds in a rather complex manner.
Indeed, the energies of the 4s, 4p and 4d levels are shown
in the inset for small well depth, U0 ; and a multitude of
crossings are seen.
3.3. Selective orbital compression
An interesting phenomenon in the modification of an
orbital of a multielectron atom upon confining was
revealed by Connerade et al. (1999b) in model calcula-
425
tions of orbitals of confined @Ca from Ca@C60 on the
basis of a non-relativistic HF approximation modified
by the inclusion of the confining potential (5) in the
calculations. Calculated results for the ground-state 4s
orbital as well as for the excited 3d, 4d and 5d orbitals
(resulting from the 3p-nd transition) of free Ca are
compared with those of confined @Ca in Fig. 8.
It follows from Fig. 8 that the 4d orbital is largely
packed into the hollow cage of the confining shell, so
4 that it is now 4d, not 3d, which has the highest
amplitude and concentration of electron density near
the atomic core. The 4d electron charge density within
the hollow space of the cage behaves in contradiction
with common wisdom, according to which one normally
expects some charge density to be pulled out from the
inner region into the attractive shell. The observed
phenomenon was named (Connerade et al., 1999b)
‘‘selective orbital compression’’ (SOC). Note, SOC was
also witnessed (Connerade and Semauone, 2000b) for
the 5d orbital in the 5d6s2 ; 2 D3=2;5=2 ground-state of
@La from La@C60 :
3.4. Redistribution of oscillator strengths
SOC suggests the possibility that the spectral dis-
tribution of oscillator strengths fnl-n0 l 0 in confined atoms
can be altered even more dramatically than the energy
structure in comparison to free atoms. This, indeed, is
illustrated by Fig. 9 where calculated results for the 4s
photoionization cross section of @Ca from Ca@C60
(Connerade et al., 1999b) is compared with the 4s
photoionization of free Ca in a region of 3p-3d; 4d and
5d resonances. Calculations were performed with
account for interchannel interaction using the random
phase approximation with exchange (RPAE) (Amusia,
1990). Due to SOC, the 3p-4d resonance in @Ca
becomes incomparably broader, increases several times
in height and moves approximately 0:5 eV towards
higher photon energies, whereas the 3p-3d resonance is
noticeably narrowed and shifted only by a few
hundredths of eV, as compared to free Ca.
3.5. Confinement resonances
The photoionization spectra of atoms confined within
a fullerene cage have been a topical subject of theory for
some years now (Pushka and Niemenen, 1993; Wendin
and W.astberg, 1993; Baltenkov, 1999; Connerade et al.,
1999b, 2000b, c; Decleva et al., 1999; Stener et al., 2002;
Amusia et al., 2000; Baltenkov et al., 2001, 2002a, b). In
all these investigations, resonances in photoionization
cross sections of confined atoms brought about entirely
by the presence of the confining shell were uncovered.
These resonances were classified (Connerade et al.,
2000b) as ‘‘confinement resonances’’. In the same work,
the precise physical origin and nature of confinement
 ARTICLE IN PRESS
426 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433

0.2
0.4
@Ca(3d)
0.0

Ca(4s)
-0.2
0.2

@Ca(4s) Ca(3d)
Pnl (r) wavefunctions (a.u.)

-0.4

-0.6 0.0
0 5 10 15 20 0 5 10 15 20
(a) (b)
0.6
0.3 @Ca(5d)
@Ca(4d)
Ca(5d)
0.3 Ca(4d) 0.2

0.1

0.0
0.0

-0.1
-0.3

-0.2
0 5 10 15 20 0 102 03 04 05 0
(c) (d)
radius (a.u.)
Fig. 8. Radial orbitals Pnl (r) of free calcium (Ca) and endohedrally confined Ca@C60 calcium (@Ca). Note the collapse of the 4d
orbital of @Ca into a hollow cage of C60 but significant electron density transfer of the 3d orbital into the attractive shell of C60 :

resonances (CR’s) in case of a ‘‘structureless’’, i.e.,

6000 @Ca (3p 4d) smooth confining potential (5) was established.
@Ca(3p 3d)

3.5.1. Confinement resonances: the d-potential theory

4000 The d-potential theory (Baltenkov, 1999) of confine-
(Mb)

ment resonances in photoionization cross sections of

5d)

Ca(3p 4d) endohedral atoms is based on modelling the C60 cage by

σ4s

the d-potential V ðrÞ ¼ U0 dðr  RÞ ðU0 > 0Þ; as well as

Ca(3p

2000
Ca(3p 3d) on the assumption that wavefunctions of electrons
bound in an endohedral atom @A are the same as
those in the isolated atom A whose radius is much
0 smaller than the radius R of the C60 cage itself. The d-
33.2 33.6 35.2 35.6 36.0 potential modelling of the C60 cage is, obviously, a good
Photon energy (eV) approximation for inner-shell, near-threshold photoio-
Fig. 9. 4s photoionization cross section s4s of free Ca and nization of the atom @A; when a photoelectron
endohedral Ca@C60 calcium in regions of the 3p-nd auto- wavelength l is larger than both the distance between
ionizing resonances. the C atoms forming the fullerene cage and the thickness
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433 427

of the C60 cage. The problem is then reduced to solving et al. (2000b) by using the flexibility of a phenomen-
.
the one-dimensional Schrodinger equation in which the ological theory based on modelling the C60 shell by an
d-potential is added to the potential of an isolated atom attractive spherical short-range potential (5) with an
A: In the framework of the d-theory, the equation for the encapsulated atom being placed at the geometrical
photoionization cross section s@A
l71 ðeÞ of a confined atom centre of the potential. This model gives one the freedom
takes the form to investigate confinement resonances as a function of
the inner radius of the cage R; its thickness D and the
s@A 2 A
l71 ðeÞ ¼ Dl71 ðeÞsl71 ðeÞ: ð7Þ potential depth U0 : Calculated results of the reduced
sA dipole matrix element /1s jj r jj EpS of Li2þ as a function
Here, l71 ðeÞ
is the photoionization cross section of the
isolated atom, e is the photoelectron energy and Dl ðeÞ is of photoelectron energy, where the initial state is a
modulation function defined by frozen j1sS free electron orbital of Li2þ ; while the final
state is jEpS in the presence of the cage are depicted in
ðk=2U0 Þ2 Fig. 11.
D2l ðeÞ ¼ ; ð8Þ
½ukl ðRÞvkl ðRÞ þ k=2U0 2 þ u4kl ðRÞ The amplitude 1s-ep is seen to be dominated by
resonances—the confinement resonances—whose inten-
where k is the photoelectron momentum, R is the radius sities behave non-monotonically with increasing U0 :
of the C60 cage, ukl and vkl are the regular and irregular These features can be understood by noting that the
.
solutions of the radial Schrodinger equation, respec- amplitude in the inner region is the result of interference
tively. Obviously, the Dl ðeÞ have a resonance character between three photoelectron waves: the incident wave,
as a function of k (or of e). Therefore, there are and the waves reflected at each of the inner and outer
resonances—confinement resonances—in s@A l71 ðeÞ: shell boundaries, leading to the emergence of CR’s in the
As an illustration, calculated results (Baltenkov, 1999) photoionization amplitude of confined atoms. The
for 1s and 2s partial photoionization cross sections of resulting amplitude at the centre of the cage depends
free Ne and confined @Ne are depicted in Fig. 10 where on the precise phase relation between all these waves,
resonances in s@Ne are clearly seen. Since the continuum and the behaviour of the resulting interference reso-
wavefunctions in potential fields of the Ne atom with nances is therefore more complex than for a d-function
vacancies in 1s and 2s subshells are different, the shell, which has zero thickness, and only two waves
resonance behaviour of s@Ne 1s differs from that of s@Ne
2s : present within the shell.
Indeed, s@Ne
2s ; in contrast to s@Ne
1s ; has two resonance One can also vary the phase difference between the
peaks. The first of them is at the ionization threshold of returning reflected waves by altering the thickness of the
the 2s subshell, where s@Ne 2s is more than six times attractive shell. Calculated results (Connerade et al.,
greater than related photoionization cross section of the 2000b) for the evolution of CR’s in the photoionization
free Ne atom. At the second maximum s@Ne 2s is almost matrix element are shown in Fig. 12 as a function of the
three times greater than sNe 2s : photoelectron momentum k for a set of different values
of D at fixed R ¼ 5:8 a.u. and U0 ¼ 3 a.u.
3.5.2. Confinement resonances: the attractive spherical
short-range potential shell
3
Reduced matrix element (a.u.)

A better understanding of nature and origin of

0.32
confinement resonances was provided by Connerade
4 2

4.5
0.24
1.5
2
@Ne(2s)
0.16
σns (Mb)

@Ne(1s)

1 Ne(2s)
0.08

0 10 20 30
Ne (1s)
0 Photoelectron kinetic energy, ε (eV)
0 4 8 12 16
Photoelectron energy, ε (eV) Fig. 11. Confinement resonances in reduced photoionization
amplitudes j/1sjjrjjEpSj of Li2þ confined by an attractive shell
Fig. 10. 1s and 2s photoionization cross sections of free Ne and of inner radius R ¼ 5:8 a.u., thickness D ¼ 1:9 a.u. and varied
endohedral @Ne from Ne@C60 calculated within the d-theory. potential depth U0 ¼ 1:5; 2, 3, 4 and 4.5 a.u., as marked.

428 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
0.2
εp reduced matrix element (a.u.)
0.1
0.0
0.3
0.2
0.1
0.0
0.2
1s
0.1
0.0
0 1
Photoelectron momentum, k (a.u.)
Fig. 12. Confinement resonances in reduced photoionization
amplitudes j/1sjjrjjEpSj of Li2þ confined by an attractive shell
of inner radius R ¼ 5:8 a.u., depth U0 ¼ 3 a.u. and varied
thickness D ¼ 1; 2, and 6 a.u.
First, notice the presence of closely spaced maxima
and minima resulting from the condition for construc-
tive interference in the inner region between the incident
wave and the reflection from the inner edge of the
confining shell in the presence of Coulomb field of the
residual nucleus. Secondly, notice fluctuations of in-
tensity in the photoionization amplitude on a broader
scale (arrows in Fig. 12), due to ‘‘beating’’ between the
waves from the inner and outer reflection. Thirdly,
notice the sensitivity of near-threshold CR’s to the
thickness D of the confining shell. Not only do CR’s
have different magnitudes at small k’s as D increases, but
they even exhibit qualitatively different behaviour.
Thus, the nature and origin of CR’s in photoioniza-
tion of atoms surrounded by an attractive (with regard
to photoelectrons) potential is due to interference of
three waves: the original outgoing wave, and the waves
reflected at each of the inner and outer cavity
boundaries. Omitting this fact from consideration can,
in principle, be misleading in the interpretation of CR’s
spectra.
3.5.3. Repulsive spherical shell theory
In principle, the confining shell can be not only
attractive, but repulsive as well. This applies, e.g., to
photoionization of an atom or ion endohedrally
ARTICLE IN PRESS
∆ = 1 a.u.
1.5
2 rc = 5.8 a.u.
Reduced matrix element (a.u.)
∆ = 1.9 a.u.
1
1.0
qd-CR's
∆ = 2 a.u.
0.5 0.5
c-CR's
0.0
∆ = 6 a.u.
0 5 10 15 20 25 30 35
Photoelectron energy, ε (eV)
Fig. 13. Confinement resonances in reduced photoionization
amplitudes j/ 1sjjrjjepSj of Li2þ confined by a repulsive shell of
inner radius R ¼ 5:8 a.u., thickness D ¼ 1:9 a.u. and varied
potential height U0 ¼ 0:5; 1, and 2 a.u., as marked. In addition,
2 3 qd-CRs stands for quasi-discrete CRs, whereas c-CRs denotes
continuum CRs (see text for explanations).
confined in a negatively charged fullerene C60 (Smith
and Spanel, 1994), or to photoionization of a multi-
positronic system (see, e.g., Varga, 1999) which might be
trapped inside a neutral or positively charged fullerene.
As was shown by Giantruco and Lucchese (1999) the
potential seen by positrons confined inside a hollow
space of C60 is very repulsive at the location of the C60
cage.
Calculated results (Connerade et al., 2000b) for the
dipole photoionization amplitude /1sjjrjjepS of the Liþ2
centrally confined inside the repulsive shell are presented
in Fig. 13 as a function of photoelectron energy. The
photoionization amplitude is seen to possess confine-
ment resonances whose intensities strongly depend on
the height U0 of the repulsive potential barrier.
The resonance spectrum in the case of repulsive shells
is a combination of two different kinds of CR’s. CR’s of
the first kind are due to the three-wave-interference
effect, as with the attractive shell [which are referred to
as ‘‘continuum’’ CR’s, (c-CR’s)]. CR’s of the second kind
are due to quasi-discrete states present in spectra of
electrons surrounded by a repulsive environment [re-
ferred to here as the ‘‘quasi-discrete’’ CR’s (qd-CR’s)].
qd-CR’s are characteristics of the part of the photo-
ionization spectrum with photoelectron energies e
smaller than the ‘‘effective’’ potential height Ueff at the
outer edge of the shell, Ueff ¼ U0  Z=ðR þ DÞ (here Z is
the nuclear charge and R þ D is the radius of an outer
wall of the shell), when there exist only two interfering
waves inside the empty space of the cage, roR; namely
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433 429

the initial outgoing photoelectron wave and the wave 3.2

reflected by the inner wall of the shell. As the U 0 = 0.75 a.u.
γ1s(U 0)
photoelectron energy is increased and starts exceeding 2.4

non-dipole angular asymmetry parameter, γ1s

Ueff three interfering waves come into play resulting in 1.6
0.5

the appearance of c-CR’s.

0.25
The origin of CR’s in case of repulsive shells thus 0.8
depends on the ratio Ee =Ueff ; with the implication that
0.0
features of the photoionization spectra of different ions
trapped inside the same repulsive shell may actually
0.8 ∆ = 3.5 a.u. γ1s(∆)
originate from CR’s of different nature.

3.6. Magnified non-dipole effects 0.4 2.5 1.9

An outstanding finding of recent years is the discovery 0.0

of a noticeable significance of electric dipole–electric
quadrupole (E1–E2) interference in photoelectron angu-
lar distributions at low photon energies (see, e.g., the
review paper by Lindle et al. in this volume and
references therein). The effect arises from the first-order
correction ik~
~
r to the dipole approximation for a
photoionization matrix element between initial and final
states: Mif ¼ ðf jð1 þ ik~
~
rÞ~ pjaÞ; with k~ and ~
e
~ e being the
photon momentum and polarization vector, and ~ r and ~
p
being the electron position vector and the electron
momentum operator. The strength of the E1–E2
interference is defined as the non-dipole photoelectron
angular distribution parameters gnl ðoÞ and dnl ðoÞ
compared to the dipole photoelectron angular asymme-
try parameter bnl ðoÞ (Cooper, 1993). For photoioniza-
tion of ns electrons, bnl ðoÞ ¼ 2; whereas
Qns -Ed
gns ¼ dns ¼ 3k cos ðZd  Zp Þ; ð9Þ
Dns -Ep
with Zd and Zp being phase shifts of related partial Ed
and Ep photoelectron’s wavefunctions and Dns-Ep ¼
/EpjrjnsS and Qns-Ed ¼ /Edjr2 jnsS being radial
dipole and radial quadrupole matrix elements of pho-
toionization amplitudes, respectively. Numerically,
Dns-Ep BQns-Ed ; so that when no special conditions
are met g1s 51 at low photon energy (B1 a.u.) since g1s is
proportional to k and kBa ¼ 1=13751: It turns out,
however (Connerade et al., 2000c), that a transparent
repulsive confinement acts as a ‘‘magnifying glass with
adjustable refraction index’’ by making non-dipole
parameters in low photon energy photoionization of
confined atoms to be big, comparable to, or even bigger
than the dipole parameter bnl ðoÞ; as a result of the
existence of quasi-discrete virtual energy levels in the
continuous spectra of photoelectrons in such environ-
ment. This is illustrated by Fig. 14 where calculated
results (Connerade et al., 2000c) for g1s for 1s photo-
electrons emitted from a hydrogen atom centrally
confined by the transparent repulsive potential of form
(5) are depicted.
All resonance structures in g1s shown in Fig. 14 are
solely the result of resonances due to virtual states in the
rc = 7 a.u. 5 4 γ1s(rc)
0.2
0.1
0.0
15 20 25 30
Photon energy (eV)
Fig. 14. Quadrupole qd-CRs due to virtual states in the non-
dipole angular asymmetry parameter g1s of photoelectrons from
1s photoionization of the H atom confined by a repulsive
spherical shell (5). Upper panel: g1s for potential heights U0 ¼
0:25; 0:5 and 0:75 a.u., as marked, and fixed values of inner
radius R ¼ 5:8 a.u. and thickness D ¼ 1:9 a.u. of the shell.
Middle panel: g1s for thickness D ¼ 1:9; 2.5 and 3.5 a.u., as
marked, and fixed values of potential height U0 ¼ 0:75 a.u., and
inner radius R ¼ 5:8 a.u. Bottom panel: g1s for inner radius
R ¼ 4; 5 and 7 a.u., as marked, and fixed U0 ¼ 0:75 a.u., and
D ¼ 1:9 a.u.
quadrupole 1s-Ed photoionization amplitude. Reso-
nances in dipole photoionization amplitudes due to
virtual states do not result in resonances in non-dipole
parameters. Indeed, because non-dipole parameters
depend on a ratio of the quadrupole amplitude Q over
the dipole amplitude R; the effects of dipole resonances
(due to virtual states) in non-dipole parameters are
damped.
From the upper panel of Fig. 14, the peak values of
g1s ; in the vicinity of the quadrupole resonances, are seen
to increase dramatically with increasing U0 : For
instance, for U0 ¼ 0:75 a.u., the peak value of g1s at
15 eV exceeds 3, i.e., 150% of bns :
From the middle panel of Fig. 14, rapid enhancement
of g1s in the resonance region of about 16 eV is seen as D
increases. g1s increases from 0:2 at D ¼ 1:9 a.u. to 0:9
(more than 40% of bns ) at D ¼ 3:5 a.u. in that region.
From the bottom panel of Fig. 14, the evolution of
quadrupole resonances in g1s with increasing radius R of
 ARTICLE IN PRESS
430 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
the confinement, at fixed values of D and U0 is seen. The
resonances in g1s move significantly towards lower
energies achieving a peak value of more than 0.2 (more
than 10% compared to bns ) with increasing R: Similar
dependence of confinement resonances on the radius of
the shell was also found in the dipole photoionization
cross section of 5s electrons of @Xe from Xe@C60
(Amusia et al., 2000), in the framework of the d-
potential theory of confinement resonances.
The physics behind the behaviour of non-dipole
parameters seen in Fig. 14 is thoroughly explained in
the work of Connerade et al. (2000c).
Interesting variations in the resonance manifold in g1s
occur (Connerade et al., 2000c) when the confined H
atom is replaced by a hydrogen-like ion Aþz : The
calculated results for g1s for z varying from 0 to 3 are
shown in Fig. 15.
The fact that the resonances in g1s are located at
higher photon energies with increasing z is simply due to
ðz þ 1Þ2 scaling of binding energy in the ion. An
interesting feature, however, is that the number of
resonances seen in g1s within the same energy interval of
photon energies D_oE30 eV varies with increasing z:
This is because as z increases, the Coulomb well deepens
and the virtual levels move to lower energies. At
sufficiently high z they move below threshold and turn
into actual bound states in the strong Coulomb field of
the nucleus. The increase of z from 0 to 1 causes the
disappearance of the virtual level 1, and only two
resonances in g1s are seen for z ¼ 1: For z ¼ 2; both
virtual levels 1 and 2 have moved into the bound region,
and only one resonance, number 3, appears in g1s for
z=0 z=1 z=2 z=3
1 2
1
2
3 s@Ca
γ1s
3 energy region below to the 3p-3d resonance. The
3
3 25 eV is a confinement resonance. Of importance,
0 the ‘‘opposite direction’’ in @Ca as compared to free
0 50 100 150 200
Photon energy (eV)
Fig. 15. g1s in the vicinity of quadrupole resonances along the
isoelectronic sequence of hydrogenic ions Aþz with z ¼ 0; 1, 2
and 3, as marked, and fixed parameters for the repulsive
potential shell: U0 ¼ 0:75 a.u., D ¼ 1:9 and R ¼ 5:8 a.u. Note
the disappearance of a resonance #1 for z ¼ 1; of a resonance
#2 for z ¼ 2 and the appearance of a previously unseen
resonance #4 when z ¼ 3:
z ¼ 2: Note, that, at this value of z; virtual level 3 is
located farther from the threshold than level 1 at z ¼ 0
or level 2 at z ¼ 1: The subsequent increase of z from 2
to 3 shifts level 3 closer to the threshold, but the level
itself remains virtual. In addition, virtual level 4 comes
within range, so that, at z ¼ 3; two resonances, numbers
3 and 4, are seen. The resonance pattern of g1s thus
varies significantly along isoelectronic sequences of
confined ions, especially with regard to the resonance
widths and positions.
Obviously, the trends found in non-dipole parameters
apply not only to hydrogenic atoms but to all atoms of
the periodic table confined by a transparent repulsive
shell, since virtual quadrupole resonances are merely
result of the presence of the confining shell.
3.7. Modified electron correlation
The issue of how strongly the C60 -like confinement
can affect electron correlation in the atom, as well as
how strong the combined confinement+electron correla-
tion can change photoionization of a confined multi-
electron atom compared to the free atom fell under
theoretical scrutiny in the work by Connerade et al.
(1999b). They calculated and compared 4s photoioniza-
tion s@Ca
4s of confined @Ca from the Ca@C60 metallo-
fullerene with sCa
4s of free Ca. The Ca atom was chosen
because it is rather light but highly correlated atom, for
which non-relativistic calculations are appropriate, but a
many-body approach is required. In these calculations,
the atom was placed at the centre of the attractive
potential (5) whose parameters matched actual para-
meters of C60 : R ¼ 5:8 a.u., D ¼ 1:9 a.u. The potential
depth was put to U0 ¼ 8:2 eV to satisfy the experimen-
tally found electron affinity of 2:65 eV for C60 : The
found HF ground and excited energies and wavefunc-
tions of @Ca were then plugged in RPAE equations to
account for electron correlation in the photoionization
cross section s@Ca
4s of the atom. Calculated results for
4s and sCa
4s are depicted in Fig. 16 for the photon
oscillation in s@Ca
4s seen between approximately 10 and
4
however, is that electron correlation is seen to act in
Ca. Indeed, near the 4s threshold, the electron correla-
tion decreases the threshold magnitude of sCa 4s but
250 increases that of s@Ca
4s : In the same energy region, the
Cooper minimum seen in the photoionization cross
section of both the free and confined atom is moved
(from its HF position) by correlation to lower energies
in Ca but towards higher energies in @Ca. Beyond the
Cooper minimum the electron correlation noticeably
increases (compared to HF results) the magnitude of sCa 4s
but decreases that of s@Ca4s : All this is a clear indication
of qualitative changes in electron correlation in the
 ARTICLE IN PRESS
V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
@Ca
2 Ca
1.2
HF-L
1 (2000) and Ting-yun et al. (2000) who exemplified
σ4s (Mb)
RPAE
0.8
HF-V
0 of Connerade et al. (2001) for hydrogen confined
8 12 16 20
0.4
HF-V
HF-L RPAE
0.0
8 12 16 20 24
photon energy (eV)
Fig. 16. 4s photoionization cross section s@Ca
4s of @Ca (main
panel) and sCa
4s of Ca (inset) below to the 3p-3d resonance
calculated within RPAE and HF approximations, as marked.
HF-L and HF-V stands for the HF calculation of the
photoionization cross section in the ‘‘length’’ or ‘‘velocity’’
form, respectively. ‘‘Length’’ and ‘‘velocity’’ forms coincide
(Amusia, 1990) within the RPAE theory.
confined atom brought about by changes in the
electronic wavefunctions of the atom.
3.8. Conclusion
The above empirical models (5) and (6) neglect the
fact that, actually, the field of the C60 cage is a
multicentre field. Effects of ‘‘multicentricity’’ of the
C60 cage on photoionization of endohedral atoms was
spotted by Decleva et al. (1999), Stener et al. (2002) and
Baltenkov et al. (2002a). Anisotropy of the ‘‘granular’’
molecular potential of C60 resulted in additional sharp
resonance structures in 1s and 2p photoionization
cross sections of endohedral metallofullerenes M@C60
(M ¼ Li, Na, K, Be, Mg, Ca), with the encapsulated
atom being placed at the geometrical centre of C60 :
However, as was explained in the work of Baltenkov
et al. (2002a), where a new multicentre theory of
photoionization of endohedral atoms was developed
and tested, for sufficiently low energies of photoelec-
trons, the wavelength l is so large that it considerably
exceeds a distance d between the C atoms in the fullerene
cage. As a consequence, the photoelectron ‘‘sees’’ not a
‘‘granular’’ charge density of the C60 cage on its way out
but an effectively homogeneous, spherical charge density
distributed along a sphere of radius R: Consequently,
photoionization calculations of endohedral atoms using
spherical confinement potentials (5) and (6) are valid at
sufficiently low values of photoelectron energies.
Also, we have bypassed in this review paper the
problem of off-centre position of the encapsulated atom
in A@C60 which is a typical position of metal atoms M
in the ground state equilibrium configuration of M@C60
431
(Li and Tom!anek, 1994) (e.g., Li and K in Li@C60 and
(
K@C60 are shifted by approximately 1.5 and 0:25 A
from the centre, respectively). For off-centre effects the
reader is asked to refer to recent work by Changa et al.
such effects by the hydrogen atom in an impenet-
rable spherical cavity, as well as to a recent work
24
inside a prolate-shaped C60 fullerene cage and Baltenkov
et al. (2002a) for the Li atom inside a multicentre
environment.
4. Concluding remarks
If we try to draw together the threads of this research
to arrive at a general conclusion, it is perhaps the
following. Today, efforts are underway in many
laboratories to develop experimental studies relating to
various aspects of confined atoms. So far, their spectro-
scopy has been experimentally rather difficult to per-
form, and theoretical preditions have therefore
outstripped experiment. It is likely, however, that this
situation will change rather soon, and that the spectro-
scopy of confined atoms will become a new area of
investigation. Already, it has been suggested that
confinement could have some unique advantages in,
for example, isolating the atom from its environment,
and thereby providing a new building-block for the
qubits of the quantum computer (Harneit, 2002).
It is clear that a lot more remains to be done especially
as regards understanding the effects of this rather special
form of external screening by penetrable confining
surfaces. For example, when the confining surface is
penetrable, Rydberg states can continue to exist outside
it, although they gradually become isolated from the
confined atom as the transparency of the surface
decreases. Thus, the properties of Rydberg excitations
will depend rather critically on the properties of the
confining cage. At this point in time, nothing is really
known about external Rydberg states, but their proper-
ties will clearly be very interesting. Indeed, one can
surmise that new classes of interchannel phenomena will
also arise when ‘‘crossings’’ between Rydberg states and
cavity resonances are considered. There is clearly a rich
variety of new phenomena waiting to be uncovered,
which will provide a fascinating new insight into atomic
properties. The associated quantum defect theory will
have a number of unique features, involving the
coupling between eigenfunctions of short and of long-
range potentials.
Both experiment and theory for confined atoms are
likely to develop rapidly over coming years once the
problems involved in preparing targets for the laser-
based investigations have been solved and data on the
spectra of confined atoms in the cavity resonance range
 ARTICLE IN PRESS
432 V.K. Dolmatov et al. / Radiation Physics and Chemistry 70 (2004) 417–433
become more readily available. In the meantime, theory
will probably turn its attention to filling in aspects of the
problem which so far have been left aside, such as the
computation of Rydberg states for such systems under
conditions of incomplete screening.
Acknowledgements
This work was supported by the US Civilian Research
and Development Foundation for the Independent
States of the Former Soviet Union (CRDF), Grant
No. ZP1-2449-TA-02, NSF and NASA.
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