Many-Electron Atom Confinement by a

Penetrable Spherical Box

C. DÍAZ-GARCÍA, S. A. CRUZ
Physics Department, Universidad Autónoma Metropolitana-Iztapalapa, Apartado Postal 55 534,
09340 México, DF, México

Received 30 January 2008; accepted 18 February 2008

Published online 2 April 2008 in Wiley InterScience (www.interscience.wiley.com)
DOI 10.1002/qua.21670

ABSTRACT: A confinement model for many-electron atoms enclosed by a spherical

boundary with finite-barrier potential height is presented. The model is based on the
Thomas–Fermi–Dirac–Weizsäcker (TFD␭W) functional formalism using known properties of
the orbital electron densities and constitutes a natural extension of a previously published
report for the case of infinitely hard walls [Cruz et al., Int J Quantum Chem, 2005, 102, 897].
The confining barrier potential is considered as a step-like function of finite height V0. This
assumption demands of the appropriate description of the TFD␭W energy functional for
both the interior and exterior regions together with corresponding ansatz orbital density
representations, subject to continuity boundary conditions at the wall. For a given cage
radius R and confining barrier height V0, the total ground-state energy is variationally
optimized with respect to the characteristic parameters defining the interior and exterior
orbital densities. The total ground-state energy and corresponding electronic density are
obtained as function of barrier height and cage radius for many-electron atoms and ions.
The model is explicitly applied to He, Li, C, and Ne and various ionic species for barrier
heights (atomic units) V0 ⫽ 0, 5, and ⬁. Given a barrier height V0, the results are presented
for the critical cage size to produce one or more unbound electrons—yet, confined by the
box— until reaching threshold size values for which electron escape from the confinement
region take place. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem 108: 1572–1588, 2008

Key words: confined atom; Thomas–Fermi–Dirac–Weizsäcker; density functional

theory; finite barrier height; electron escape; variational optimization; high pressures

develop new technologies. This has been recog-

1. Introduction nized in semiconductor technology, where confin-
ing quantum-well models have been developed to

N anostructured materials have low-dimension-

ality components as a common characteristic,
whose novel physical properties are a key aspect to
address the behavior of electrons and excitons in
thin layers of material or small crystallites [1, 2].
Quantum confinement due to the reduced dimen-
sions of the system is the major source of the ob-
Correspondence to: S. A. Cruz; e-mail: cruz@xanum.uam.mx served new physical properties.

International Journal of Quantum Chemistry, Vol 108, 1572–1588 (2008)

© 2008 Wiley Periodicals, Inc.
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

Spatial limitation of atoms and molecules also within an infinitely hard spherical cavity of varying
produces remarkable differences in physical and radius. After the pioneering work by Guimarc, spa-
chemical properties between the confined system tial confinement effects on helium-like systems
and its free-counterpart, revealing a wealth of po- have been studied using a variety of approximate
tential applications for the synthesis of new mate- techniques and focused mainly to the case of infi-
rials [3]. Examples of this type of systems are donor nitely hard closed boundaries with different sym-
hydrogenic impurities at the surface of semicon- metries [20, 41– 47] and the effect of cavity size and
ductors [4 –9], atoms and molecules enclosed by shape on the ground-state energy evolution. These
nanocavities like fullerene cages [10 –13] and theoretical studies have been extended more re-
nanochannels, like carbon nanotubes and zeolites cently to low-lying excited states and spectroscopic
[14, 15] to mention a few. Indeed, when an atom or properties [42– 44, 48] and only a few papers have
molecule is embedded in a condensed host me- been devoted to helium confinement by a hard-
dium, changes in the spatial limitation imposed by open boundary [49 –51].
its neighboring environment may be related with The ground-state energy evolution of many-elec-
an external pressure. Changes in total internal en- tron atoms confined within hard spherical cavities
ergy and electronic structure because of an external of varying size has been addressed in the past
pressure may be envisaged through spatial confine- through different approaches, ranging from ab ini-
ment. Hence, confinement effects also play an im- tio Hartree–Fock (HF) procedures [52, 53], density
portant role in studies of atomic and molecular functional Kohn–Sham theory [54, 55], and Tho-
compressibility [16, 17] and matter under high pres- mas–Fermi–Dirac–Weizsäcker (TFD␭W) statistical
sures [3, 16 –18]. Recent years have seen an increas- atomic models based on an orbital density decom-
ing research interest on this topic, with the proposal position [56]. A common feature in these models is
of confinement models based on different forms of the use of a rigid spherical enclosing cage, whereby
external confining potentials. The interested reader Dirichlet boundary conditions must be satisfied by
is kindly referred to extensive accounts on these the different orbital components. In spite of their
studies reviewed by Fröman et al. [19], Jaskolski inherent level of difficulty, a general qualitative and
[20], and Dolmatov et al. [12]. In the following, we quantitative agreement among these models has
shall refer specifically to atomic spatial confinement been observed for the total ground-state energy
based on the boxed-in-atom model. evolution as a function of cage-size.
The effect of spatial limitation on the electronic It is well known, however, that the use of an
properties of one and two-electron atoms has been infinitely hard confining wall leads to an overesti-
extensively studied in the past through use of ap- mate of the energy evolution as the confinement
propriate— open and closed— confining bound- volume is reduced. This is in addition to the unre-
aries with different geometries. In the case of hy- alistic permanent retention—within the confine-
drogenic systems, most of these studies have dealt ment volume– of the already unbound electrons,
with infinitely hard [4 –9, 21–28] and soft [29, 30] whose kinetic energy yields a high enough value to
limiting open surfaces and cavities with different overcome an otherwise finite confining barrier po-
shapes with hard and soft walls [19 –20]. In many of tential [57]. In spite of this, soft-wall confinement of
these situations, exact solutions to the Schrodinger the simplest of many-electron atoms (helium) has
equation have been found to account for the evolu- been only scarcely explored, particularly for cavi-
tion of ground and excited states in terms of the ties with spherical geometry [36, 57–59].
degree of confinement [4 – 8, 22, 23, 25, 31–34]. Confinement of many-electron atoms by spheri-
These exact calculations have served as important cal cavities with a finite potential barrier height has
reference to calibrate corresponding—simpler—ap- been addressed by Connerade et al. both in their HF
proximate treatments [6, 27–30, 35–39]. [53] and Dirac–Fock [16] studies of shell collapse of
Helium— being the next element after hydrogen third and fourth row atoms in the periodic table
in the Periodic Table— constitutes an important and Cs, respectively. In both cases, a finite barrier
subject of study to survey confinement effects on height was used mainly for the purposes of numer-
atomic systems with more than one electron, where ical calculation. In the former case, a barrier height
electron– electron interaction and correlation en- of 10 a.u. was used to mimic an infinitely hard wall,
ergy appear for the first time. This was first realized while in the latter case a barrier height of 5 a.u. was
by Guimarc [40], who studied the behavior of the found to be high enough to retain the 5d and 6s Cs
electron correlation energy of helium enclosed electrons within the cavity. Further studies on

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1573
DÍAZ-GARCÍA AND CRUZ

properties of endohedrally confined atoms in C60 The paper is organized as follows. In section 2,
by Connerade et al. resort to a confining potential the model as well as the relevant assumptions in the
shell of finite barrier height to represent the C60 method of calculation are presented. The results of
endohedral environment [60, 61]. In spite of these this work and a discussion are then given in section
important studies, no further analysis on the total 3. Finally, section 4 is devoted to the conclusions of
energy evolution as function of cage size and bar- this study. Hartree atomic units are used through-
rier-height was pursued and—to the authors out, unless stated otherwise.
knowledge—no such studies have been reported
for many-electron atoms so far.
The aim of this work is to present a more realistic 2. Method
description of confinement by enclosing the many-
electron system within a spherical cage with pene- Consider an N-electron atomic system confined
trable walls. This constitutes a natural extension of by a spherical cage of radius R with a confining
a previously published paper where the TFD␭W barrier potential Vc, such that
formalism based on known properties of the orbital

再
electron densities was used for the case of many-
0 0 ⱕ ri ⬍ R
electron atoms enclosed by infinitely hard walls V c ⫽ V 共i兲 ⫽ V R ⱕ r ⬍ ⬁, i ⫽ 1, .., N, (1)
o o i
[56]. Here, the confining barrier potential is consid-
ered as a step-like function of finite height V0. This
assumption demands of the appropriate descrip- where ri denotes the radial position of electron “i”
tion of the TFD␭W energy functional for both the relative to the nucleus of atomic number Z located
interior and exterior regions together with the cor- at the origin, and Vo共i兲 ⫽ Vo the height of the
responding ansatz orbital density representations potential barrier felt by each electron outside the
subject to continuity boundary conditions at the cage. At this stage, we make the following simpli-
wall. For a given cage radius R and confining bar- fying assumption. Outside the confinement region,
rier height V0, the total ground-state energy is vari- the total energy will be composed of the kinetic
ationally optimized with respect to the characteris- energy term plus the barrier potential height. This
tic parameters defining the interior and exterior would correspond to considering an effective con-
orbital densities. Accordingly, the total ground- stant potential acting on each electron once outside
state energy E(R, V0) and corresponding electronic the cage.
density ␳(R, V0) are obtained as function of barrier Since we are interested in the variational optimi-
height and cage radius for many-electron atoms zation of the TFD␭W energy density functional for
this system subject to the conditions imposed by Eq.
and ions. To the authors’ knowledge, this kind of
(1), let us first briefly describe the construction of
study is the first reported so far for many-electron
such functional. The finite barrier height of the
atoms (other than helium) under finite barrier
confining potential allows for a nonzero probability
height confinement.
for the electron to be found outside the confinement
As mentioned before, many-electron atom con-
region. Interpreting the probability amplitudes for
finement by a finite barrier height potential allows
the interior and exterior regions in terms of the
for a more realistic description of the internal evo-
corresponding radial electron density distributions,
lution of the system. Accordingly, given a barrier
we note first that different variational representa-
height V0, the results are presented for the critical tions (and variational parameters 兵␰j其, 兵␤j其) for the
cage size to produce one or more unbound elec- electronic charge density ␳int共␰j; r兲, ␳ext共␤j; r兲 are re-
trons—yet confined by the box— until reaching quired for the internal and external region, respec-
threshold size values for which electron escape tively. Hence, the corresponding TFD␭W energy
from the confinement region takes place. Critical density functional may be generically written in
sizes for electron escape are found by analyzing the terms of an interior and exterior contribution as
cage-size evolution of the different ionization po-
tentials until they reach the barrier height. Al-
though the method proposed in this work has gen- E关R,V 0 ; ␰ j , ␤ j 兴 ⫽ E int关␳int, R兴 ⫹ Eext关␳ext, R, V0兴 (2)
eral applicability, specific results are presented for
the case of the He, Li, C, and Ne systems and where the following definitions are made in terms
various of their ionic states. of the kinetic energy (T), electron–nuclear (Ven),

1574 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

electron– electron (Vee), and barrier (Ebarrier) compo- Having constructed the energy density func-
nents: tional for the system, we now turn our attention to
the characteristics of the electron density function.
E int关␳int, R兴 ⫽ Tint关␳int, R兴 ⫹ Ven关␳int, R兴 ⫹ Vee关␳int, R兴, (3) Here we resort to the use of appropriate orbital
densities to construct the total atomic density for
and the interior ␳int共r兲 and exterior ␳ext共r兲 regions, i.e.

E ext关␳ext, R, V0兴 ⫽ Text关␳ext, R, V0兴 ⫹ Ebarrier关␳ext, R, V0兴.

冘␻ ␳
occ

(4) ␳ int共r兲 ⫽ i int,i共r兲, (9)

i⫽1

The first term in Eqs. (3) and (4) corresponds to

the first two contributions in the gradient expan-
冘␻ ␳
occ
sion of the kinetic energy functional [62– 65], ␳ ext共r兲 ⫽ 共r兲, (10)
i ext,i
namely the free-electron gas kinetic energy and the 1⫽1
Weizsäcker inhomogeinity correction [66] multi-
plied by a factor ␭ [56, 65]:
where ␻i is the electron population of orbital “i”,

冕 冕
␳int,i共r兲 and ␳ext,i共r兲 are the corresponding orbital den-
␭ ⵜ␳ 䡠 ⵜ␳
sities for the interior and exterior region, and the
T⫽␬ ␳ 5/3 d ␶ ⫹ d␶, (5)
8 ␳ sum is carried over all occupied orbitals.
⌫ ⌫
Finally, the interior and exterior densities and
their derivative must satisfy continuity boundary
with ␬ ⫽ 共3/10兲共3␲2兲2/3 and the ␭ factor to be
conditions, which may be imposed on each of the
chosen so that the free-atom energies correspond as
corresponding orbital components as
closely as possible to HF values [56].
Also, the electron–nuclear Ven and electron– elec-
tron Vee interaction energies appearing in Eq. (3) ␳ int,i兩r⫽R ⫽ ␳ext,i兩r⫽R (11)
are given, respectively, as
⭸ ␳ int,i ⭸␳ext,i

冕
V en ⫽ ⫺ Z ␳intr⫺1d␶
⌫
(6)
⭸r r⫽R
兩 ⫽
⭸r r⫽R
兩 (12)

as well as the orbital normalization condition

and

V ee ⫽
1
冕␳ ␸ d␶ ⫺ ␩ ␳int4/3d␶,
2 int int 冕 (7)
冕0
R
␳ int,i共r兲d␶ ⫹ 冕 ⬁

R
␳ext,i共r兲d␶ ⫽ ␻i (13)

⌫ ⌫

such that for a total number of N electrons

with Z the nuclear charge, ␸int the electrostatic po-
tential associated to charge density ␳int, and the

冘␻ ⫽ N.
occ
second term in Eq. (7) being the Dirac exchange
energy [67] with ␩ ⫽ 共3/4兲共3/␲兲1/3. Finally, the i (14)
i⫽1
second term in Eq. (4) corresponds to the energy
contribution due to the confining barrier:
As mentioned previously, the distinction be-

冕
E barrier ⫽ V0 ␳extd␶
⌫
(8)
tween an interior and exterior region demands ap-
propriate variational ansatz representations for the
interior and exterior orbital density distributions
defined by corresponding sets of variational param-
The symbol ⌫ appearing in Eqs. (5)–(8) denotes eters to be found after optimization of the total
the domain of definition for either the interior or energy given by Eq. (2).
exterior region. For the ansatz radial orbital density in the exter-

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1575
DÍAZ-GARCÍA AND CRUZ

TABLE I ______________________________________________________________________________________________
Ground-state energy values ETFD␭W and optimized orbital parameters (␰1s, ␥) obtained in this work for He as a
function of confinement radius for various barrier heights.

Helium (␭ ⫽ 0.02544)

V⫽⬁
R 6 4 3 2 1.5 1 0.5
Ea ⫺2.8426 ⫺2.8302 ⫺2.7935 ⫺2.5285 ⫺1.8456 1.0626 22.9229
Eb ⫺2.8615 ⫺2.8585 ⫺2.8308 ⫺2.5625 ⫺1.8642 1.0612 22.7909
Ec ⫺2.9033 ⫺2.8997 ⫺2.8718 ⫺2.6036 ⫺1.9067 1.0159
ETF␭DW ⫺2.8554 ⫺2.8430 ⫺2.8120 ⫺2.6110 ⫺2.1160 ⫺0.0610 14.8020
␰1s 1.64510 1.58690 1.53137 1.47146 1.48693 1.62231 2.14355

V⫽5
R 6 4 2 1.5 1 0.5 0.3
Ea ⫺2.8341 ⫺2.8054 ⫺2.6179 ⫺2.4201 ⫺1.4621 4.6722
Ed ⫺2.8477 ⫺2.8476 ⫺2.8126 ⫺2.6254 ⫺1.6288 4.6434 9.6342
␮ 1.68749 1.68760 1.71293 1.61287 1.37566 0.97889 0.08518
␯ 0.00012 0.00006 0.00003 0.32274 0.55641 0.58961 0.55397
ETF␭DW ⫺2.8617 ⫺2.8606 ⫺2.6682 ⫺2.2903 ⫺0.9427 4.2054 7.9439
␰1s 1.74170 1.74545 1.57763 1.60348 1.89030 2.95121 3.93380
␥ 0.00003 0.00015 0.84918 0.85822 0.75316 0.31777 0.00002

V⫽0
R 6 4 3 2 1.5 1 0.5
Ea ⫺2.8341 ⫺2.8054 ⫺2.7579 ⫺2.6184 ⫺2.5086 ⫺2.0522 ⫺0.2412
Ed ⫺2.8477 ⫺2.8476 ⫺2.8460 ⫺2.8277 ⫺2.7556 ⫺2.2171 ⫺0.2450
␮ 1.68749 1.68760 1.68716 1.66542 1.68600 1.64689 0.15158
␯ 0.00012 0.00006 0.00035 0.000002 0.00006 0.26069 0.56099
ETF␭DW ⫺2.8617 ⫺2.8616 ⫺2.8605 ⫺2.8343 ⫺2.7439 ⫺2.3962 ⫺1.3044
␰1s 1.74159 1.74182 1.74486 1.78480 1.86624 2.03851 2.53907
␥ 0.00032 0.00072 0.00013 0.00029 0.00026 0.00021 0.00002

Also shown are corresponding energies reported in the literature. The variational energies together with the variational parameters
(␮,␯)-not explicitly reported in Ref. [57] are also shown. All values in atomic units.
a
Ref. [36].
b
Ref. [52].
c
Ref. [41].
d
Ref. [57].

nal region resort is done to a functional form de- fined by hard walls [56], we propose here the ansatz
rived from exact solutions to the Schrodinger equa- radial orbital density for the interior region as
tion for the hydrogen atom confined by penetrable
spherical boxes [32], i.e. ␳ int,i共r兲 ⫽ Nint,ir2ni⫺2e⫺2␰ir共1 ⫺ ␥r/R兲, (16)

␳ ext,i共r兲 ⫽ Next,ir⫺2li⫺2e⫺2␤ir (15)

where the first two radial factors are derived from the
square of angularly averaged Slater-type orbitals [68],
where li stands for the angular momentum quan- with ni corresponding to the principal quantum num-
tum number of orbital “i” and ␤i a corresponding ber associated to orbital “i”, ␰i is a variational param-
variational parameter. Next,i is a normalizing factor eter and Nint,i a normalizing factor to satisfy Eq. (13)
defined by Eq. (13), once the interior orbital density together with Next,i. In contrast with the impenetrable
is defined as done as follows. case discussed in Ref. [56], the factor 共1 ⫺ ␥r/R兲 in
Following a parallel reasoning to a previous Eq. (16) becomes now a matching term between the
TFD␭W treatment for many-electron atoms con- interior and exterior orbital densities. This factor de-

1576 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

FIGURE 1. Ground-state energy evolution of He as a function of confinement radius for barrier heights V0 ⫽ 0, 5, and
⬁. Solid lines: TFD␭W calculations of this work. Dotted lines: variational calculations using the method of Ref. [57]. Sym-
bols correspond to calculations by other authors as follows. (V0 ⫽ ⬁) : (䊐) SCF by Ludeña [52]; (⫻) variational by Marin
and Cruz [36]; (E) variational Hylleraas-type by Aquino et al. [41] (the dashed line is shown to guide the eye). (V0 ⫽ 5): (‚)
variational by Marin and Cruz [36] (V0 ⫽ 0): (⽧) variational by Marin and Cruz [36]. The inset shows the behavior of the
TFD␭W calculations for V0 ⫽ ⬁ (E) as compared to that of two electrons in a box (F) for strong confinement.

pends on a third variational parameter ␥, which—for and since ␤i ⬎ 0, the following condition must be
simplicity—is assumed to be the same for all orbital satisfied for the values of ␰i and ␥:
densities and such that 0 ⱕ ␥ ⱕ 1.
The variational parameters 共␰i, ␤i, ␥兲 for the ex-
共2n i ⫹ 2l i ⫹ 1兲 ␥ ⫹ 2 ␰ i R共1 ⫺ ␥ 兲 ⬎ 2共n i ⫹ l i 兲. (18)
ternal and internal regions are coupled through the
boundary conditions [Eqs. (11) and (12)] as
Also, the values for the normalizing factors Nint,i
␥ ni ⫹ li and Next,i may be readily obtained through use of
␤i ⫽ ␰i ⫹ ⫺ (17)
2 R共1 ⫺ ␥ 兲 R Eqs. (11) and (13).

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1577
DÍAZ-GARCÍA AND CRUZ

TABLE II ______________________________________________________________________________________________
Ground-state energy values ETFD␭W and optimized orbital parameters (␰ns, ␥) obtained in this work for C as a
function of confinement radius for various barrier heights.

Carbon (␭ ⫽ 0.12479)

V⫽⬁
R 10 7.5 5 3 1.5 1 0.5
Ea ⫺37.6681 ⫺37.2570 ⫺30.2169 ⫺10.9178
ETF␭DW ⫺37.6855 ⫺37.6724 ⫺37.5728 ⫺36.9769 ⫺30.4799 ⫺15.3853 79.7298
␰1s 5.52577 5.50835 5.47464 5.41492 5.35835 5.15093 4.11941
␰2s 2.65327 2.62579 2.52874 1.95669 2.54204 3.29502 5.83853
␰2p 1.18381 1.18744 1.29366 1.95602 2.5419 3.29507 5.83853

V⫽5
R 10 7.5 5 3 1.5 1 0.9
ETF␭DW ⫺37.6887 ⫺37.6886 ⫺37.6816 ⫺37.5087 ⫺34.6715 ⫺27.6684 ⫺24.5788
␰1s 5.57240 5.57118 5.57055 5.53207 5.54526 5.53578 5.52044
␰2s 2.70332 2.69767 2.69080 2.50011 2.84624 3.31621 3.37894
␰2p 1.23706 1.23516 1.26942 1.58735 2.42967 3.37110 3.77518
␥ 0.085755 0.084761 0.065039 0.295323 0.374704 0.348139 0.329385

V⫽0
R 10 7.5 5 3 2.5 2 1.9
ETF␭DW ⫺37.6887 ⫺37.6886 ⫺37.6835 ⫺37.5626 ⫺37.4402 ⫺37.1591 ⫺37.0578
␰1s 5.57240 5.57226 5.57192 5.56861 5.57766 5.54004 5.53842
␰2s 2.70332 2.70391 2.69678 2.58416 2.47602 2.33261 2.36648
␰2p 1.23706 1.23607 1.26203 1.52909 1.74506 1.97073 1.98085
␥ 0.085755 0.068065 0.053405 0.073177 0.020734 0.210561 0.224810

Also shown are corresponding energies reported in the literature for V0 ⫽ ⬁. All values in atomic units.
a
Ref. [52].

Having defined the characteristics of the orbital using this model for different cavity radii and bar-
densities for the interior and exterior regions, we note rier heights, as an example. As a first step, the ␭
at this stage that—according to the assumptions in the factor appearing in Eq. (5) was set so that the
model—the electrostatic potential ␸int appearing in TFD␭W free-atom energies (ETFD␭W) would corre-
Eq. (7) needs to be evaluated only in the interior spond to three decimal digits accuracy with those
region through use of Poisson’s equation for the den- from Clementi and Roetti [68]. This was done to
sity distribution given by Eqs. (9) and (16) following guarantee the correct HF limit when R 3 ⬁, in con-
the same criterion established in Ref. [56] to obtain the trast with the value ␭ ⫽ 1/8 suggested in Ref. [56]
correct behavior for the whole range of R values. for all atoms.
The subsidiary conditions given by Eqs. (17) and Tables I–III display—as an example—the
(18), together with Eqs. (2)–(6) allow for the calcu- ground-state energies obtained in this work
lation of the total energy functional E共␰i, ␤i, ␥; R, V0兲 (ETFD␭W) for He, C, and Ne for selected values of R
[Eq. (2) ], which is variationally optimized for a and barrier heights V0 ⫽ 0, 5, and ⬁ and compared
given value of R and V0 by requiring that with other theoretical calculations, where available.
⭸E ⭸E The optimal ␭ values used are shown at the top of
⫽ ⫽ 0;共i ⫽ 1,. . .,occ兲. (19) each table within parenthesis. Also included in
⭸␰i ⭸␥
these tables are corresponding orbital variational
parameters (␰i,␥) obtained after total energy mini-
3. Results and Discussion mization according to Eq. (19) [the value of ␤i may
be extracted from Eq. (17)].
The ground-state energy evolution of spherically Table I and Figure 1 correspond to the helium
confined He, Li, C, and Ne has been estimated case, for which wider information is available for

1578 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

FIGURE 2. Ground-state energy evolution of C as a function of confinement radius for barrier heights V0
⫽ 0, 5, and ⬁. The symbols and inset have the same meaning as in Figure 1 considering four “s” and two “p” elec-
trons in a box.

proper comparison for the different barrier heights. as that of two s-electrons in a box, as may be gath-
For hard-wall confinement (V0 ⫽ ⬁), the results of ered from the inset in Figure 1. For soft-wall con-
this work are compared to HF calculations by Lu- finement, comparison is done with corresponding
deña [52], variational calculations by Marin and variational calculations by Marin and Cruz [36]—
Cruz [36], and recent accurate correlated Hylleraas- who used a single variational parameter for the
type calculations by Aquino et al. [41]. According to interior and exterior wavefunctions. Comparison is
Figure 1, our calculations show reasonable qualita- also done with calculations by Dı́az-Garcı́a and
tive and quantitative agreement with the other ref- Cruz [57], who extended the work of the former
erence values for R ⱖ 1.5, while clearly an under- authors by using three variational parameters, i.e.,
estimate of the total energy is observed for 0.5 two parameters (␮, ␯) for the interior one-electron
ⱕ R ⱕ 1.5. Interestingly, for strong confinement wavefunction ␸int共r兲 ⬇ exp共 ⫺ ␮r兲共1 ⫺ ␯r/R兲 and
conditions, the total energy has the correct behavior one (␴) for the exterior wavefunction ␸ext ⬇

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1579
DÍAZ-GARCÍA AND CRUZ

TABLE III _____________________________________________________________________________________________

Ground-state energy values ETFD␭W and optimized orbital parameters (␰ns, ␥) obtained in this work for Ne as a
function of confinement radius for various barrier heights.

Neon (␭ ⫽ 0.12331)

V⫽⬁
R 10 7.5 4.5 3 1.5 1 0.55
Ea ⫺128.5351 ⫺128.4145 ⫺123.3101 ⫺102.9430 35.7008
ETF␭DW ⫺128.5412 ⫺128.5330 ⫺128.3816 ⫺127.3772 ⫺115.1697 ⫺85.4709 75.4193
␰1s 9.63937 9.62219 9.57864 9.53626 9.46417 9.60340 9.59250
␰2s 5.43786 5.41989 5.36636 5.26616 3.08773 3.71898 5.42775
␰2p 2.00466 1.98347 1.95048 2.02517 3.08774 3.71898 5.42775

V⫽5
R 10 5 3 2 1.5 1 0.92
ETF␭DW ⫺128.5470 ⫺128.5468 ⫺128.4837 ⫺127.3952 ⫺124.3938 ⫺112.6710 ⫺107.9840
␰1s 9.68857 9.68693 9.68818 9.64287 9.65584 9.74341 9.78191
␰2s 5.48778 5.48614 5.47968 5.33561 5.00465 3.77988 3.65734
␰2p 2.05990 2.05820 2.09157 2.27738 2.66031 3.75327 4.03143
␥ 0.032221 0.032280 0.030814 0.296317 0.396977 0.292388 0.295157

V⫽0
R 10 4 3 2.5 2 1.6 1.54
ETF␭DW ⫺128.5470 ⫺128.5453 ⫺128.5020 ⫺128.3463 ⫺127.7867 ⫺126.5723 ⫺126.2849
␰1s 9.68857 9.68614 9.68734 9.68984 9.65128 9.65134 9.65170
␰2s 5.48778 5.48493 5.48076 5.46930 5.38557 5.30210 5.28300
␰2p 2.05990 2.05869 2.08188 2.13689 2.20710 2.36314 2.39236
␥ 0.032221 0.032246 0.031065 0.038822 0.229603 0.230958 0.228966

Also shown are corresponding energies reported in the literature for V0 ⫽ ⬁. All values in atomic units. aRef. [52].

exp(⫺␴r)/r, where a similar relation to Eq. (17) was Figure 2—the TFD␭W and SCF calculations for this
used. For completeness, the values of the so-ob- case present good agreement for confinement radii
tained variational parameters (␮, ␯) and energies R ⱖ 1.5, whereas for smaller values of R, the
are included in Table I for barrier heights V0 TFD␭W values lie systematically below the SCF
⫽ 0, 5. This is useful for quantitative reference, ones, with relative differences up to about 40%.
since they were not reported numerically in Ref. Note also that, for strong confinement conditions,
[57] and constitute a significant improvement to the the TFD␭W calculations have the correct tendency
values reported in Ref. [36]. Inspection of Figure 1 as compared with estimates for the energy of four
and Table I for the energy values obtained in this s-electrons and two p-electrons in a hard box, as
work for finite barrier heights indicates a reason- may be verified from the inset in Figure 2.
able qualitative and quantitative agreement with Hence—as in the case of helium—the model satis-
the corresponding variational calculations for a fies the limiting conditions when R 3 0 and R 3 ⬁
wide range of R. The TFD␭W values become sensi- for hard-wall confinement. We now turn our atten-
bly lower for smaller confinement radii—particu- tion to the soft-confinement situation for carbon.
larly for V0 ⫽ 0. This behavior, as well as the From the results displayed in Table II and with the
differences with the hard-wall case, can be better help of Figure 2, we note that—as the barrier height
appreciated from Figure 1. is reduced—the ground-state energy shift as func-
The TFD␭W results for carbon for the selected tion of cavity size is lower than in the hard-wall
barrier heights are shown in Table II and Figure 2. case. Moreover, a critical cage-size below which
For hard-wall confinement, comparison is done neutral carbon cannot further exist is found at R
with corresponding HF values by Ludeña [52]. ⬇ 0.9 for V0 ⫽ 5 and at R ⬇ 1.9 for V0 ⫽ 0. This
Again—as may be gathered from this table and is an important general characteristic arising from

1580 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

FIGURE 3. Ground-state energy evolution of Ne as a function of confinement radius for barrier heights V0 ⫽ 0, 5,
and ⬁. The symbols and inset have the same meaning as in Figures 1 and 2 considering four “s” and six “p” elec-
trons in a box.

finite barrier-height confinement, as we shall see ous cases, for finite barrier heights V0 ⫽ 5 and V0
further later. ⫽ 0, the critical radii below which neon cannot be
For Neon under hard-wall confinement, the sustained as a neutral system are R ⬇ 0.92 and R
TFD␭W calculations lie between 10 and 20% above ⬇ 1.54, respectively. The reasons for this behavior
the corresponding SCF calculations by Ludeña [52] will be now analyzed.
in the region 1 ⱕ R ⱕ 1.5 with a steeper energy From the previous discussion, we deem that the
increase for smaller confinement radii, as may be model proposed here allows to explore properties
verified from Table III and Figure 3. Again, the of the system not foreseen by hard-wall confine-
TFD␭W values for very small values of R corre- ment. Namely, the reach of a critical radius where
spond well to those of four s-electrons and six the confining capacity of the box is superseded and
p-electrons in a hard box, as may be gathered from an otherwise neutral atom cannot exist longer. This
the inset in Figure 3. Furthermore, as in the previ- important consequence will now be analyzed in

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1581
DÍAZ-GARCÍA AND CRUZ

more detail to explore the conditions for which a

many-electron atom and its different ionic species
cannot further survive as the confinement radius
reaches a critical value for a given barrier height.
We begin our discussion by considering the sim-
plest confined many-electron atom: helium, for
which recent variational calculations have been re-
ported when submitted to a soft-wall confining
cage with V0 ⫽ 5 [57] and where the idea of electron
escape is put forward. In that article, we claim that
electron escape takes place for cage-sizes where the
ionization potential per electron reaches the barrier
height, i.e., the point where He cannot be longer
neutral. Moreover, a partition scheme is proposed,
whereby the two-electron Hamiltonian for the con-
fined system is split, so that one part corresponds to FIGURE 4. Cage-size evolution of the first (EI) and
the first ionization potential and the other to the second (EII) ionization potentials for He obtained
second ionization potential. Hence, the same Ham- through variational calculations for V0 ⫽ 5 following
iltonian for the total system should be used consis- the method of Ref. [57] and extended to show the point
tently at all stages. Comparison with the superposi- of electron escape. The dashed lines correspond to EI
tion method—whereby the first ionization potential and EII using the partition method, while the continuous
is constructed by substracting the He⫹ energy from lines correspond to He and He⫹ used in the superposi-
that of He— both independently calculated for the tion method (see text).
same confining conditions—yields some difference
in the critical radius to create unbound electrons,
yet confined by the cage. Here we have extended very closely that of the variational calculations [EII,
the calculations reported in Ref. [57], finding that indicated by crosses in Fig. 5(a)] for a wide range of
the critical radius for electron escape does not values of R up to R ⬇ 0.5, below which a departure
change appreciably by using either scheme, as is observed. On the other hand, the TFD␭W first
I
shown by Figure 4. In this figure, EI and EII repre- ionization potential ETFD ␭W follows a similar quali-
sent the first and second ionization potentials, re- tative trend as its variational counterpart [EI, indi-
spectively, calculated within the partition scheme, cated by open circles in Fig. 5(a)] and resembles
and He⫹共1s兲 corresponds to the second ionization quantitatively an average of the latter showing a
II
potential used in the superposition method. Elec- merging tendency to ETFD ␭W. A crossover with the
tron escape takes place when each ionization po- ETFD␭W curve takes place at R ⬇ 0.3, which is not of
II

tential reaches the barrier height at R ⬇ 0.3, where numerical computation origin. This behavior may
clearly no appreciable difference between both be related to inherent limitations of the superposi-
schemes appears to define this critical point. Taking tion method for such small radii and a few number
this into consideration, we have used the superpo- of electrons. To assess further knowledge on the
sition scheme for the TFD␭W calculation of the first adequacy and limitations of the model, we now
and second ionization potential for helium for the make a similar analysis for a slightly larger system
same barrier height (V0 ⫽ 5) to compare with the as Li.
aforementioned variational calculations. Table IV Table IV shows the TFD␭W ground state energy
displays the HF ground-state energy of He⫹ for a of Li, Li⫹, and Li2⫹ for a confinement barrier height
set of confinement radii for this barrier height. In V0 ⫽ 5 and various cage radii. As in the previous
this case, we have set ␭ ⫽ 0.32448 so that ETFD␭W cases, for numerical reference, corresponding vari-
corresponds to the ground-state energy of the free ational parameters and energies calculated accord-
He⫹. Using corresponding values for the neutral ing to Ref. [57] are also shown for Li⫹ and Li2⫹, as
species in Table I yields quantitative reference for well as the appropriate ␭ parameters. Figure 5(b)
I
Figure 5(a), which shows the results of this calcu- shows the cage-size evolution of the first (ETFD ␭W),
II III
lation. second (ETFD␭W) and third (ETFD␭W) ionization poten-
Interestingly, the cage-size evolution of the tial for this system, calculated using the superposi-
TFD␭W second ionization potential ETFD II
␭W follows tion method. Also shown are the second (crosses)

1582 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

TABLE IV _____________________________________________________________________________________________
Ground-state energy values ETFD␭W and optimized orbital parameters (␰1s, ␥) obtained in this work for Heⴙ, Li,
Liⴙ, and Li2ⴙ as a function of confinement radius for barrier height V0 ⴝ 5.

V0 ⫽ 5

R 6 4 2 1.5 1 0.5 0.3

He⫹ (␭ ⫽ 0.32448)
Ea ⫺1.9999 ⫺1.9999 ⫺1.9685 ⫺1.8661 ⫺1.3852 1.3969 4.6855
␮ 1.97252 1.91313 1.48317 1.32568 1.14026 0.79414 0.42093
␯ 0.16165 0.32663 0.80031 0.80299 0.77094 0.66138 0.52663
ETF␭DW ⫺1.9999 ⫺1.9999 ⫺1.9261 ⫺1.8626 ⫺1.3878 1.2794 3.9469
␰1s 2.10502 2.10535 1.84861 1.77908 1.82510 2.56830 4.13915
␥ 0.00006 0.00006 0.86591 0.89235 0.85497 0.60373 0.00003

R 6 4 2 1.5 1 0.7 0.4

Li (␭ ⫽ 0.061215)
ETF␭DW ⫺7.4180 ⫺7.3249 ⫺6.6229 ⫺5.8903 ⫺3.6986 ⫺0.0122
␰1s 2.66802 2.60518 2.51184 2.58460 3.35586 3.95030
␰2s 1.09721 1.22142 2.05696 2.52781 2.72828 3.13655
␥ 0.56199 0.83636 0.59755 0.49231 0.43488 0.32073
Li⫹ (␭ ⫽ 0.04745)
Ea ⫺7.2227 ⫺7.2227 ⫺7.2211 ⫺7.2085 ⫺6.9749 ⫺5.6623 1.3396
␮ 2.6875 2.68750 2.68644 2.67565 2.79331 2.33975 1.77400
␯ 2.9 ⫻ 10⫺7 3.6 ⫻ 10⫺7 1.4 ⫻ 10⫺6 10⫺6 1.6 ⫻ 10⫺5 0.44172 0.54748
ETF␭DW ⫺7.2362 ⫺7.2362 ⫺7.2216 ⫺7.1104 ⫺6.4107 ⫺4.6836 0.9592
␰1s 2.73778 2.73784 2.76210 2.87304 2.59840 2.92835 3.97860
␥ 0.00009 0.00074 0.00019 0.00010 0.71044 0.60614 0.234804
Li2⫹ (␭ ⫽ 0.3565)
Ea ⫺4.4999 ⫺4.4999 ⫺4.4973 ⫺4.4750 ⫺4.2708 ⫺3.5875 ⫺0.4715
␮ 2.96281 2.92658 2.68560 2.41340 2.07627 1.82650 1.43712
␯ 0.21884 0.28068 0.55085 0.70885 0.74289 0.71871 0.63637
ETF␭DW ⫺4.4993 ⫺4.4993 ⫺4.4969 ⫺4.4695 ⫺4.2517 ⫺3.5582 ⫺0.5576
␰1s 3.10271 3.10270 3.11084 3.17458 2.65347 2.67989 3.44915
␥ 0.00006 0.00009 0.00007 3 ⫻ 10⫺6 0.82627 0.79171 0.56460

The variational energies for He⫹, Li⫹ and Li2⫹ together with the variational parameters (␮, ␯) are also shown. All values in atomic units.
a
Variational method [57].

and third (open circles) ionization potentials de- scheme. Accordingly, in the following we shall con-
rived from the variational calculations according to sider the superposition scheme as a reasonable ap-
Table IV. Interestingly enough, the critical radius proximation to explore the evolution of the various
below which neutral Li cannot further exist is ionization potentials for confined many-electron at-
clearly attained at R ⬇ 0.66 indicated by the point oms within the TFD␭W formalism.
at which the first ionization potential reaches the The important consequences of soft-confinement
barrier height. Note also the strikingly good corre- effects on the ground-state properties of many-elec-
III
spondence between the ETFD ␭W curve and the third tron atoms will now be further explored by consid-
ionization potential curve derived from variational ering the specific cases of carbon and neon enclosed
energies. Also, as in the He case, a crossover be- by spherical cavities with V0 ⫽ 5 and 0. To illus-
II III
tween the ETFD ␭W and ETFD␭W curves takes place for trate the various stages at which electron escape
R ⬇ 0.2, which are constructed from the helium- takes place as the cavity size is reduced for a fixed
and hydrogen-like configurations. It seems, how- barrier height, we choose V0 ⫽ 5 for carbon and its
ever, that as the nuclear charge increases, this cross- ionic species C⫹, C2⫹, C3⫹and C4⫹ and invoke the
over will take place for smaller confinement radii, superposition method. Table V displays the
and thus cage-size effects on lower-order ionization ground-state energies corresponding to the afore-
potentials may be confidently analyzed within this mentioned ionic species for the same set of selected

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1583
DÍAZ-GARCÍA AND CRUZ

the corresponding evolution of the various ioniza-

tion potentials calculated as En ⫽ E共C共n⫺1兲⫹兲
⫺ E共Cn⫹兲. The solid vertical lines indicate the
points at which an unbound electron condition—
yet confined by the cage—is attained. The dotted
vertical lines indicate the point at which an already
unbound electron reaches the barrier height and
leaves the confinement cage, thus preventing the
parent atom (ion) to exist as such for smaller cage
sizes. Physically, the interpretation of the results
shown in this figure is as follows. Starting with
neutral carbon for large cage sizes, as the confine-
ment radius is reduced, the first ionization potential
steadily increases until reaching the ionization
threshold at R1 ⬇ 2.33. Then we have a C⫹ ⫹ e
system still confined by the cage marked as region
“A” in Figure 6(a). As the confinement radius is
further reduced, the second ionization potential at-
tains its threshold value at R2 ⬇ 1.5, whereby now
a system C2⫹ ⫹ 2e is formed but still confined and
marked as region “B” in Figure 6(a). Further reduc-
tion of cage-size until R ⬇ 1.05 leads to a third
unbound electron so that now the system C3⫹
⫹ 3e is formed and yet confined, indicated as
region “C” in Figure 6(a). When the first ionization
potential reaches the barrier height at Rc1 ⬇ 0.85,
the confinement capacity of the box is not enough to
retain an electron, and hence the first electron es-
cape takes place, leaving the system now as C3⫹
FIGURE 5. Comparison of the cage-size evolution of ⫹ 2e. This transition is indicated by the first arrow
the ionization potentials for He and Li obtained in this in Figure 6(a), where now the energy evolution
work for V0 ⫽ 5. (a) First (ETFD
I II
␭W) and second (ETFD␭W) follows the C⫹ energy curve. This system survives
ionization potential of He. Corresponding variational [region “D” in Fig. 6(a)] until further cage reduction
calculations using the method of [57]: (E) first ionization
leads to another unbound electron, as the fourth
potential; ( ⫻ ) second ionization potential. (b) First
I
(ETFD II III ionization potential reaches its threshold value at
␭W), second (ETFD␭W), and third (ETFD␭W) ionization
potentials for Li. Variational calculations using the R4 ⬇ 0.8 and then becomes C4⫹ ⫹ 3e. A small
method of [57]: (E) second ionization potential; (⫻) third reduction in R [ region “E” in Fig. 6(a)] leads then to
ionization potential. attainment of the second electron escape at R2c
⬇ 0.75 and thus a transition to the C2⫹ curve indi-
cated by the second arrow in Figure 6(a) takes
values of R as those given in Table II for the corre- place, indicating now the total energy of the re-
sponding case of neutral carbon for quantitative maining C4⫹ ⫹ 2e system in region “F”. The next
reference. Also shown are the associated ␭-values electron escapes when the third ionization potential
used and optimized parameters for each case. reaches the barrier height at R3c ⬇ 0.55. The system
Again for completeness, the energies and varia- then suffers a transition from C4⫹ ⫹ e to the C3⫹
tional parameters (␮,␯) for the helium-like system curve, as shown by the third arrow in Figure 6(a).
C4⫹ are also shown and calculated according to the This system survives in region “G” until the next
procedure given in Ref. [57]. Incidentally, note the electron escapes at R4c ⬇ 0.45, thus becoming a
reasonable correspondence between the latter cal- purely confined C4⫹.
culation and the TFD␭W values. A similar reasoning as that discussed for carbon
For the purpose of discussion, we have plotted in may be followed for other many-electron atoms
Figure 6(a) the ground-state evolution of the vari- and other barrier heights. Figure 7 shows, as an
ous systems as a function of R, and in Figure 6(b), example, the cage-size evolution of the first ioniza-

1584 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

TABLE V ______________________________________________________________________________________________
Ground-state energy values ETFD␭W and optimized orbital parameters (␰nl, ␥) obtained in this work for the ionic
species Cmⴙ as a function of confinement radius for a barrier height V0 ⴝ 5.

V0 ⫽ 5
R 10 7.5 5 3 1.5 1 0.9

C⫹ (␭ ⫽ 0.129856)
ETF␭DW ⫺37.2922 ⫺37.2922 ⫺37.2922 ⫺37.2710 ⫺35.6749 ⫺31.1653 ⫺29.1544
␰1s 5.55108 5.54970 5.54992 5.55205 5.46457 5.42481 5.40648
␰2s 2.59191 2.58903 2.58984 2.51664 2.91580 3.49567 3.65549
␰2p 1.83579 1.83705 1.83716 2.08042 2.62147 3.56441 3.95821
␥ 0.03012 0.03853 0.02446 0.02936 0.44562 0.40005 0.37484
C2⫹ (␭ ⫽ 0.128807)
ETF␭DW ⫺36.4084 ⫺36.4084 ⫺36.4084 ⫺36.4047 ⫺35.6598 ⫺33.2532 ⫺32.1797
␰1s 5.54775 5.54813 5.54318 5.54602 5.38124 5.32190 5.31595
␰2s 2.73081 2.73135 2.72946 2.73647 3.01549 3.70219 3.93895
␥ 0.00557 0.00119 0.00834 0.01962 0.55026 0.45953 0.42123
C3⫹ (␭ ⫽ 0.114839)
ETF␭DW ⫺34.7260 ⫺34.7260 ⫺34.7260 ⫺34.7258 ⫺34.5295 ⫺33.6038 ⫺33.1381
␰1s 5.56991 5.57264 5.57226 5.57175 5.36210 5.27906 5.28796
␰2s 3.19841 3.20122 3.20121 3.20075 3.28022 3.95886 4.25581
␥ 0.05616 0.00088 0.00276 0.00731 0.59002 0.51587 0.45166
C4⫹ (␭ ⫽ 0.066096)
Ea ⫺32.3477 ⫺32.3477 ⫺32.3477 ⫺32.3477 ⫺32.3476 ⫺32.3456 ⫺32.3426
␮ 5.68775 5.68824 5.68741 5.68570 5.68746 5.68674 5.67975
␯ 0.00256 0.00561 0.00025 0.00533 0.00005 0.00210 0.00016
ETF␭DW ⫺32.3611 ⫺32.3611 ⫺32.3611 ⫺32.3611 ⫺32.3609 ⫺32.3453 ⫺32.3184
␰1s 5.73469 5.73469 5.73466 5.73473 5.73481 5.74797 5.76635
␥ 0.00001 0.00004 0.00018 0.00001 0.00009 0.00028 0.00011

The variational energies for C4⫹ together with the variational parameters are also shown. All values in atomic units.
a
Variational method [57].

tion potential for Ne, with V0 ⫽ 5 as well as the ation of the ionization potentials when the barrier
effect of lowering the barrier height (V0 ⫽ 0) on height is reduced.
this quantity for Ne and C. These quantities were Note that all of the previous analysis is based
obtained using the superposition method. For on the fact that—while electrons become un-
quantitative reference, Table VI displays the energy bound to their parent atom (ion) as the confine-
values and relevant orbital parameters for Ne⫹ and ment radius is reduced—if they are still retained
C⫹ for these two barrier heights, and for the same R by the confining box, the total system energy is
values, as those given in Tables II and III for the described by the corresponding full-electron
corresponding neutral species. Clearly, reduction of composition until the one-electron ionization en-
the barrier height leads to larger values for the ergy reaches the barrier height. Furthermore,
critical cage radius for electron escape. Inspection since cage-size reduction is related to increasing
of Figures 6 and 7 for the first critical radius leads to pressure, the different stages at which electron
C
R1c ⬇ 0.85, R1c
Ne
⬇ 0.92共V0 ⫽ 5兲, and R1c C
⬇ 1.9, escape takes place for many-electron atoms may
R1c ⬇ 1.54 (V0 ⫽ 0) for C and Ne, respectively.
Ne
be a source of explanation of charge accumula-
Interestingly, while R1c is quite similar for C and Ne tion during build-up of tectonic stresses prior to
for V0 ⫽ 5, a much smaller value of R1c is required seismic events [69, 70]. This question was also
for Ne than for C to produce the first electron surveyed by Ley-Koo and Garcia-Castelan [22] in
escape when V0 ⫽ 0. This may be related with their studies of the hydrogen atom limited by a
the—initially shallower—first ionization potential hard paraboloidal boundary, pointing to the need
of C compared to Ne and the lower cage-size vari- of further analysis. Since many-electron atoms

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1585
DÍAZ-GARCÍA AND CRUZ

ously used ansatz variational wavefunctions. Work

is in progress to explore the use of this alternative
coupling expression for the improvement of the
energy values.

4. Conclusions

The TFD␭W statistical atomic model with

known properties of the orbital electron densities
has been extended in this work to the study of
many-electron atoms confined by spherical cavi-
ties with penetrable boundaries. Explicit calcula-
tions have been shown for He, Li, C, Ne and some
of their ionic species. To the authors’ knowledge,
no available reference material of such study ex-
ists in the literature for atoms other than hydro-
gen and helium. Hence care has been taken to
present both, quantitatively as well as qualita-
tively, results for the TFD ␭ W ground-state en-
ergy evolution of the aforementioned example
systems enclosed within cavities with different
finite barrier heights. Also, as important reference
on the capabilities and limitations of the model
proposed here, comparison with available theo-
FIGURE 6. (a) Ground-state energy evolution of C retical results for He enclosed by equivalent finite
and four ionic species as a function of confinement ra- and infinite height barriers and for C and Ne
dius for V0 ⫽ 5. (b) Cage-size evolution of the first four within infinitely hard walls has been done.
ionization potentials of C obtained in this work.The ver- Although the advantages of the TFD␭W method
tical continuous lines correspond to cage sizes where to study hard-wall confinement of many-electron
an electron is unbound. The different regions (A. . . G) atoms have been reported previously by these au-
marked in (a) indicate the various stages where un-
bound electrons coexist within the confinement region
until electron escape takes place (indicated by vertical
dotted lines) and a new ionic confined species is
formed (shown by the vertical arrows).

have different thresholds for electron escape it

might be interesting to pursue in the study of
pressure-induced electron emission from highly
compressed materials in the light of the model
proposed in this work. The existing experimental
information on exoelectron emission from rock
fracture and the associated light emission (also
known as mechanoluminescence) [71] may be one
of the few available sources of information to test
the predictions by this model for electron escape.
Finally, before ending this section, we point out
that in this work we have used the simple expres- FIGURE 7. Cage-size evolution of the first ionization
sion 1 ⫺ ␥r/R for the coupling term in Eq. (16) for potential for Ne (V0 ⫽ 5, 0) and C (V0 ⫽ 0). The critical
simplicity and as a natural extension of previous cage radius for first electron escape in each case cor-
work [56]. However, a coupling term of the form responds to the point where the ionization potential
共1 ⫺ ␥r/R兲2 would be more consistent with previ- reaches the barrier height.

1586 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9
 MANY-ELECTRON ATOM CONFINEMENT BY A PENETRABLE SPHERICAL BOX

TABLE VI _____________________________________________________________________________________________
Ground-state ETFD␭W energy evolution as a function of cage size for Neⴙ and Cⴙ for V0 ⴝ 5 and 0.

V0 ⫽ 5
Ne⫹ (␭ ⫽ 0.13309)
R 10 5 3 2 1.5 1 0.92
ETF␭DW ⫺127.8174 ⫺127.8173 ⫺127.7974 ⫺127.2031 ⫺125.2050 ⫺116.5393 ⫺112.8430
␰1s 9.61376 9.60957 9.61311 9.55849 9.56426 9.64219 9.67465
␰2s 5.41921 5.41439 5.41515 5.24847 4.83978 3.90590 3.90500
␰2p 2.30544 2.30062 2.32063 2.45459 2.85700 3.93672 4.18152
␥ 0.09994 0.09628 0.03486 0.31858 0.31785 0.32417 0.32726

V0 ⫽ 0
C⫹ (␭ ⫽ 0.129856)
R 10 7.5 5 3 2.5 2 1.9
ETF␭DW ⫺37.2922 ⫺37.2922 ⫺37.2922 ⫺37.2827 ⫺37.2556 ⫺37.1192 ⫺37.0568
␰1s 5.55108 5.54950 5.55018 5.55247 5.55164 5.49381 5.55040
␰2s 2.59191 2.59030 2.59035 2.47054 2.40573 2.41098 2.50718
␰2p 1.83579 1.83406 1.83658 2.13203 2.34929 2.37476 2.46538
␥ 0.03012 0.04683 0.02319 0.01184 0.02095 0.29060 0.08554

Ne⫹ (␭ ⫽ 0.13309)
R 10 4 3 2.5 2 1.6 1.54
ETF␭DW ⫺127.8174 ⫺127.8170 ⫺127.8029 ⫺127.7315 ⫺127.3944 ⫺126.5041 ⫺126.2743
␰1s 9.61376 9.60999 9.61573 9.61810 9.56573 9.57691 9.56654
␰2s 5.41921 5.41891 5.42095 5.40310 5.29459 5.15652 5.12888
␰2p 2.30544 2.30463 2.31586 2.35731 2.40512 2.58836 2.62828
␥ 0.09994 0.05733 0.04845 0.02763 0.26761 0.27042 0.26456

All values in atomic units.

thors [56] here, further quantitative evidence has within this scheme, and it is deemed to have im-
been given, particularly for the case of strong-con- portant consequences to be surveyed in pressure-
finement behavior as compared to the limiting sit- induced mechanoluminescence phenomena.
uation of noninteracting electrons in-a-hard-box. Finally, the results of this work point to the
This, together with the ad hoc choice of the ␭-pa- adequacy of the TFD␭W method to study soft- and
rameter appearing in the Weizsäcker term to fulfill hard-wall confined many-electron systems. We
the HF values for the free-atom constitute two im- hope that the results presented here will stimulate
portant asymptotic limiting conditions satisfied for the use of more powerful methods to address the
a plausible physical description of the system under important effects hereby discussed.
study.
For He and Li within soft walls the TFD␭W
method represents a reasonable average behavior References
for the energy evolution as a function of cage size,
although much better agreement is obtained for 1. Marin, J. L.; Riera, R.; Cruz, S. A. J Phys C 1998, 10, 1349; and
higher-Z helium-like ions as in the case of C4⫹. references therein.
For soft-wall confinement effects on many-elec- 2. Hawrylak, P. Phys Rev B 1999, 60, 5597.
tron atoms, it has been shown that as the confine- 3. Hemley, R. J. Annu Rev Phys Chem 2000, 51, 763.
ment radius is decreased, several electrons may be 4. Levine, J. D. Phys Rev A 1965, 140, 586.
unbound and yet confined within the cage. Once 5. Satpathy, S. Phys Rev B 1983, 28, 4585.
the one-electron ionization potential reaches the 6. Liu, Z.; Lin, D. L. Phys Rev B 1983, 28, 4413.
barrier-height value at a certain critical cage radius, 7. Shan, Y.; Jiang, T. F.; Lee, T. C. Phys Rev B 1985, 31, 5487.
the confining capacity of the enclosing cavity is 8. Tseng, H. C.; Shan, Y. J. Phys C 1989, 1, 2225.
superseded and electron escape takes place. This 9. Shen, Z. J.; Yuan, X. Z.; Yang, B. C.; Shen, Y. Phys Rev B 1993,
important result had not been addressed before 48, 1977.

VOL. 108, NO. 9 DOI 10.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 1587
DÍAZ-GARCÍA AND CRUZ

10. Cioslowski, J. J Am Chem Soc 1991, 113, 4139. 42. Aquino, N.; Garza, J.; Flores-Riveros, A.; Rivas-Silva, J. F.;
11. Shameema, O.; Ramachandran, C. N.; Sathyamurthy, N. J Sen, K. D. J Chem Phys 2006, 124, 054311.
Phys Chem A 2006, 110, 2. 43. Mitnik, D. M. Phys Rev A 2004, 70, 022703.
12. Dolmatov, V. K.; Baltenkov, A. S.; Connerade, J. P.; Manson, 44. Banerjee, A.; Kamal, C.; Chowdhury, A. Phys Lett A 2006,
S. T. Radiat Phys Chem 2004, 70, 417. 350, 121.
13. Madjet, M. E.; Chakraborty, H. S.; Manson, S. T. Phys Rev 45. Ley-Koo, E.; Flores-Flores, A. Int J Quantum Chem 1998, 66,
Lett 2007, 99, 243003. 123.
14. Kaczmarek, A.; Zalesny, R.; Bartkowiak, W. Chem Phys Lett 46. Xie, W. F. Chin Phys Lett 2006, 23, 1742.
2007, 449, 314; and references therein. 47. Corella-Madueno, A.; Rosas, R. A.; Marin, J. L.; Riera, R. Int
15. Yurenev, P. V.; Scherbinin, A. V.; Pupyshev, V. I. Int J J Quantum Chem 2000, 77, 509.
Quantum Chem 2006, 106, 2201. 48. Varshni, Y. P. Eur Phys J D 2003, 22, 229.
16. Connerade, J. P.; Semaoune, R. J Phys B 2000, 33, 3467. 49. Le Sech, C.; Hadinger, G.; Aubert-Frecon Z Phys D 1994, 32,
17. Cruz, S. A.; Soullard, J. Chem Phys Lett 2004, 391, 138. 219.
18. Guillot, T. Planet Space Sci 1999, 47, 1183. 50. Ley-Koo, E.; Volke-Sepúlveda, K. P. Int J Quantum Chem
19. Fröman, P. O.; Yngve, S.; Fröman, N. J Math Phys 1987, 28, 1997, 65, 269.
1813. 51. Cruz, S. A.; Ley-Koo, E.; Cabrera-Trujillo, R. AIP Conf Proc
20. Jaskolski, W. Phys Rep 1996, 1, 271. 2007, 963, 175.
21. You, J. H.; Ye, Z. G.; Du, M. L. Phys Rev B 1990, 41, 8180. 52. Ludeña, E. V. J Chem Phys 1978, 69, 1770.
22. Ley-Koo, E.; Garcia-Castelan, R. M. G. J Phys A 1991, 24, 53. Connerade, J. P.; Dolmatov, V. K.; Lakshmi, P. A. J Phys B
1481. 2000, 33, 251.
23. Ley-Koo, E.; Mateos-Cortes, S. Int J Quantum Chem 1993, 46, 54. Garza, J.; Vargas, R.; Vela, A.; Sen, K. D. J Mol Struct (Theo-
609. chem) 2000, 501/502, 183.
24. Cruz, S. A.; Ley-Koo, E.; Marin, J. L.; Taylor-Armitage, A. Int 55. Garza, J.; Vargas, R.; Aquino, N.; Sen, K. D. J Chem Sci 2005,
J Quantum Chem 1995, 54, 3. 117, 379.
25. Krämer, D. S.; Schleich, W. P.; Yakovlev, V. P. J Phys A 1998, 56. Cruz, S. A.; Dı́az-Garcı́a, C.; Covarrubias, G. Int J Quantum
31, 4493. Chem 2005, 102, 897.
26. Serna-Salazar, J. D.; Machecha-Gomez, J. Phys Chem Chem 57. Diaz-Garcia, C.; Cruz, S. A. Phys Lett A 2006, 353, 332.
Phys 2000, 2, 4061. 58. Gorecki, J.; Byers Brown, W. J Phys B 1988, 21, 403.
27. Lee, H. C.; Tseng, H. C. Chin J Phys 2000, 38, 49. 59. Zorrilla Cuenca, D.; Sánchez Márquez, J.; Fernández Nuñez,
28. Patil, S. H. Z Naturforsch A 2004, 59, 455. M.; Rodráguez Huertas, R. Int J Quantum Chem 2007, 107,
29. Shan, Y. J Phys B 1990, 23, L1. 879.
30. Kovalenko, A. F.; Holovko, M. F. J Phys B 1992, 25, L233. 60. Connerade, J. P.; Dolmatov, V. K.; Manson, S. T. J Phys B
31. Aquino, N.; Campoy, G.; Montgomery, H. F. Int J Quantum 1999, 32, L395.
Chem 2007, 107, 1548. 61. Connerade, J. P.; Dolmatov, V. K.; Manson, S. T. J Phys B
32. Ley-Koo, E.; Rubinstein, S. J Chem Phys 1979, 71, 351. 2000, 33, 2279.
33. Ley-Koo, E.; Cruz, S. A. J Chem Phys 1981, 74, 4603. 62. Wang, W. P.; Parr, R. G. Phys Rev A 1977, 16, 891.
34. Burrows, B. L.; Cohen, M. Int J Quantum Chem 2006, 106, 63. Wang, W. P. Phys Rev A 1982, 25, 2901.
478. 64. Hernández, E.; Gázquez, J. L. Phys Rev A 1982, 25, 107.
35. Marin, J. L.; Cruz, S. A. J Phys B 1991, 24, 2899. 65. Yang, W. Phys Rev A 1986, 34, 4575.
36. Marin, J. L.; Cruz, S. A. J Phys B 1992, 25, 4365. 66. Weizsäcker, C. F. Z Phys 1935, 96, 431.
37. Varshni, Y. P. Z Naturforsch A 2002, 57, 915. 67. Dirac, P. A. M. Proc R Soc Lond A 1926, 112, 661.
38. Patil, S. H.; Varshni, Y. P. Can J Phys 2004, 82, 647. 68. Clementi, E.; Roetti, C. At Nucl Data Tables 1974, 14, 177.
39. Changa, M. E.; Scherbinin, A. V.; Pupyshev, V. I. Int J Quan- 69. Brady, B. T.; Rowell, G. A. Nature 1986, 321, 488.
tum Chem 2004, 96, 167. 70. St. Laurent, F.; Derr, J. S.; Freund, F. T. Phys Chem Earth
40. Guimarc, B. M. J Chem Phys 1967, 47, 5110. 2006, 31, 305.
41. Aquino, N.; Flores-Riveros, A.; Rivas-Silva, J. F. Phys Lett A 71. Eddingsaas, N. C.; Suslick, K. S. Phys Rev Lett 2007, 99,
2003, 307, 326; and references therein. 234301.

1588 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.1002/qua VOL. 108, NO. 9