The Laplacian of the charge density and its relationship to the shell structure of

atoms and ions

Robin P. Sagar, Andrew C. T. Ku, Vedene H. Smith Jr., and Alfredo M. Simas

Citation: The Journal of Chemical Physics 88, 4367 (1988); doi: 10.1063/1.453796
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The Laplacian of the charge density and its relationship to the shell structure
of atoms and ions
Robin P. Sagar, Andrew C. T. Ku, and Vedene H. Smith, Jr.
Departmento/Chemistry, u e e n ~ University, Kingston, OntarioK7L 3N6, Canada
Alfredo M. Simas
Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, 50000-Recife, PE, Brazil
(Received 10 October 1986; accepted 3 December 1987)
The Laplacian of the spherically averaged charge density rp"p(r) has been computed from
nonrelativistic SCF wave functions for the neutral atoms from hydrogen to uranium, and the
singly positive ions, from helium to barium and lutetium to radium, in order to examine the
shell structure. V
2
p(r) exhibits a number of extremal points and zeros with the absolute value
of the function becoming smaller at each successive extremal point. The zeros, in particular the
odd numbered zeros, are shown to exhibit good correlation with the Bohr theory of an atom
while the extremal points correlate to a lesser extent. At most five shells are seen in the studied
atomic cases based on the fact that the odd numbered zeros are the topological feature of
V
2
p (r) most indicative of a shell.
INTRODUCTION
The charge density p(r), which is indirectly accessible
through x ray I and fast electron
2
scattering, has been used to
gain qualitative insights into the nature of chemical phenom-
ena.
Although a formal proof is not yet available,
3
numerical
studies4-6 have shown that for an atom or singly positive
atomic ion in the ground state, the spherically averaged
charge density, p(r),
p(r) = (41T)-J p(r)dfi
r
(1)
is a monotonically decreasing function of the nucleus-elec-
tron coordinate r. This is in contrast to the analogous func-
tion in momentum space, i.e., the spherically averaged mo-
mentum density ll(p), which is nonmonotonic for certain
atoms and positive ions.
7
Nevertheless, suitable transforma-
tions or mathematical operations performed on an atomic
per) can reveal interesting features such as those found in a
In p (r) vs r plot, in which slope breaks at various values of r
were revealed.
8
From per), one can construct the radial distribution
function D(r) = 41Trp(r), which has been the subject of a
recent study.4 D(r)dr represents the probability of finding
an electron in the volume between two spheres centered at
the nucleus, one of radius r and the other of radius r + dr.
9
D(r) has been studied in attempts to examine the shell struc-
ture of atoms and ions.
4
.
10

11
Within the framework of the
independent particle model, a shell is defined as a set of
orbitals having the same principal quantum number. The
maxima in D(r) are the result of contributions from orbitals
sharing the same principal quantum number. As functions of
the atomic number Z these maxima exhibit a functional
form similar to that predicted by the Bohr theory, although
it was found that all shells do not have expression as maxima
inD(r).4.1O.11
The fact that all occupied shells are not revealed in D (r)
as maxima, but only the innermost ones (lowest principal
quantum numbers), prompted a studyl2 to examine the mo-
mentum space analog of D(r), the radial momentum distri-
bution function I(p) = 41Tp
2
ll(p). I(p) also does not reveal
all occupied shells, but only the innermost ones in momen-
tum space (highest principal quantum numbers) which cor-
respond to the outermost ones in position space. As a result
the authors
l2
concluded that both position and momentum
space must be examined in order to reveal the complete shell
structure of an atom or an ion.
Recently there has been considerable interest
13

14
in the
Laplacian of the charge density V
2
p(r) since analysis of this
function offers a physically viable method of determining
regions oflocal charge accumulation and local charge deple-
tion.
13
Bader and co-workers 13. 14 have indicated that V
2
p(r)
is the three-dimensional function from which one can ex-
tract shell structure, as one does from D(r) in the one-di-
mensional case, with the shell structure present in V
2
p (r) for
an atom becoming disturbed upon chemical combination in a
molecule.
The physical interpretation of the Laplacian of a scalar
function was first given meaning by Maxwell in his Treatise
on Electricity and Magnetism
l5
when he stated without
proof
16
that if the value of per) at the center ra of a small
sphere of radius 1'isp(r
a
), andpav (r
a
) is the mean value for
all points within the small sphere, then
From this equation one can see that when the value of the
function at a particular point is greater than the average
value of the function at neighboring points, a situation corre-
sponding to concentration, the Laplacian of the function at
that point will be negative. Conversely when the value of the
function at a point is less than the average value of the func-
tion at neighboring points, a situation of depletion, the La-
placian of the function will be positive.
Furthermore, it is the Laplacian of p (r) that exhibits
local charge concentration and depletion, while D(r) does
J. Chern. Phys. 88 (7), 1 April 1988 0021-9606/88/074367-08$02.10 @ 1988 American Institute of PhySics 4367
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4368 Sagar et al.: Shell structure of atoms
not illustrate charge accumulation, which invalidates a
popular misconception that the maxima in D (r) are due to
regions of charge buildup.4.s Thus, V
2
p(r) can be utilized in
studies of molecular geometry, as well as the positions of
electrophilic and nucleophilic substitution in a molecule. 14
Furthermore, there is correspondence between V
2
p (r), an ap-
proach based on the observable p(r), and Frontier orbital
theory17 since maximizing the overlap between the HOMO
and LUMO of two reactants is equivalent to correlating the
region of charge concentration [negative V
2
p (r) ] in one reac-
tant, with the region of charge depletion [positive V
2
p(r)] in
the other. IS Through this, general theories of chemical reac-
tivity can be developed by using the observable charge den-
sity per) via V
2
p(r), and thus circumventing the need to em-
ploy the purely arbitrary mathematical construct of the
orbital. 13
The purpose of the present study is to consider in a com-
prehensive manner the proposition that the Laplacian of the
charge density reveals the shell structure of an atom as was
previously hypothesized. 13,14 Indeed such a study is needed
because these authors did not comment on the totality of the
shell structure present, or on atoms larger than neon.
The physically meaningful charge density for atoms is
spherical because an ensemble average must be taken over
degenerate states. As a result, we shall focus our attention on
per) and V2p(r). We will attemptto answer the question ofthe
existence of shell structure in V
2
p (r) for an atom or a positive
ion by critically examining the contributions to the total
550.0,----------,
Mn
- 550.0
0.0 0.14
100.0,----------------,
Ct+
,
:L
,
,
,
,
:
,
,
,
, ,
, '
'/
-180.0
0
.
07
\
'.'
,
Mn
function from those orbitals having the same principal quan-
tum number. We will also examine which of the topological
features (zeros, extrema) ofV
2
jHr) are most intimately relat-
ed to the concept of a shell within the independent particle
model, by comparing these topological features with those
predicted by the Bohr theory of an atom. Thus, we shall show
that suitable criteria for the characterization of shells may
be determined within the framework of V
2
p (r).
RESULTS AND DISCUSSION
We shall examine the shell structure of the atoms from
helium to radium and the singly positive ions from helium to
barium and lutetium to radium, by computing V
2
p(r) from
the nonrelativistic self-consistent-field wave functions of
Clementi and Roetti
19
and of McLean and McLean.
20
Pub-
lished wave functions for the singly positive ions with open!
shells could not be found.
The Laplacian operator V
2
, in spherical polar coordi-
nates, is
+ I 1
r sin Or aO
r
r aO
r
r sin
2
Or at/J; ,
(3)
Since the spherically averaged charge density per) does not
have a dependence on the angular variables Or and t/Jr' the
Laplacian operating on it may be simplified to
0.58
20.0 ,
,
\L
\
,
:NV
I /
I /
I I
/
I 1M
I
I I
I I
I I
\/
-80.0
0.42
-
Mn
1.7
150.0
1
,-, --,--------
Cl'
'M
-100.0 0
o.
- 250.0 __ __ ___l
- 2
0.2 0.1 0.7 0.7
2.7
FIG. 1. Shell (dotted lines) and total (solid line) contributions to the Laplacian of the spherically averaged charge density forthe manganese (Z = 25) atom
and the singly positive chlorine ion (Z = 17), respectively, computed from the nonrelativistic SCF wave functions of Clementi and Roetti. 19 Note that in this
figure the sections of each plot represent different regions of ,./a
o
, all drawn to different scales.
J. Chern. Phys., Vol. 88, No. 7,1 April 1988
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Sagar et a/.: Shell structure of atoms 4369
V
2
p(r) = a_: per) +
ar r ar
(4)
This equation indicates that V
2
p(r) is not simply the curva-
ture of per), but differs by the additional term (2/r) (a /
ar)p (r). Sincep (r) is a monotonically decreasing function of
rfor the systems considered in this study,4 the term (2/r) (a /
ar)p (r) is negative. Since the regions of charge accumulation
and charge depletion are related to the sign of V
2
p (r) as dis-
cussed before, the curvature is positive in regions of charge
depletion and may be of either sign in regions of charge accu-
mulation.
Figures 1-3 contain plots of V
2
p(r) for the atoms Mn
(Z = 25), Zn (Z = 30), As (Z = 33), and the singly posi-
tiveion Cl+ (Z = 17). The dotted lines representthe contri-
butions from the respective shells, where a shell is defined
within the independent particle model as the set of orbitals
having the same principal quantum number n. The shells are
labeled according to the convention that the first, n = 1 shell
is the K shell, with successive shells denoted as L, M, N, ... ,
etc.
As can be inferred from Eq. (4) and from the fact that
the MacLaurin expansion for the exact atomic per) is
per) = p(O) (1- 2ZCenr] + OCr),
where Cen is the electron-nucleus cusp rati0
21
C
- l' e'er)
en-- 1m ,
r_O 2zp(r)
(5)
(6)
V
2
p(r) is negative infinite at the origin and rises as r in-
creases. Moreover, V
2
p(r) exhibits a number of zeros and
extremal points, with the absolute value of the function be-
coming smaller at each successive critical point. The mini-
mum at the origin shall be designated as the zeroth extre-
mum and zeroth minimum. Due to the known asymptotic
behavior ofp(r) for an atomic system,22
p(r)-zkrPe-
ar
, k>O, 0>0, and,8<;O, (7)
V
2
p(r) asymptotically approaches zero from above.
Inspection of Figs. 1-3 reveals that beginning with the
first zero, each alternate zero ofV
2
p(r) is much closer to the
corresponding zero of a particular shell contribution, than to
the corresponding zeros of the remainder ofthe shell contri-
butions. The first zero ofV2p (r) is closest to the zero of the K
shell contribution while the third zero ofV
2
p(r) is closest to
the third zero of the L shell contribution, etc. The zeros can
be divided into two types: (a) the odd zeros which are due to
200.0 200.0
Zn
/,
IN /:
I
I:
I :
I 1
I I :
I :
- 100.0 __
0.0 ria 0.1
o
100.0
1
1
1
1
v2p(rl
1
1
-5
I
0
1
\
Zn
\
\
I
\-,"/M
-400.0
0.30 1.05
o
Zn
-600.0
0.05 ria 0.35
o
150.0
I
\
I
I
\
1M
I
\
\
\
\

v
2
p(rl.10
3
\

-5
(10
\
- /
\
......... /
N
Zn
- 150.0
1.0 ric 4.0
0
J. Chern. Phys., Vol. 88, No.7, 1 April 1988
FIG. 2. Shell (dotted lines) and
total (solid line) contributions to
the Laplacian of the spherically
averaged charge density for the
zinc atom (Z = 30), computed
from the nonrelativistic SCF
wave function of Clementi and
Roetti (Ref. 19). Note that in
this figure the sections of each
plot represent different regions
of r/ao. all drawn to different
scales.
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4370 Sagar et al.: Shell structure of atoms
25.0 r----+--+-----+---+--, 100.0
As
,
,
,
'-,
" - L
2 5 I , M_ -'.
'il P ( r I . I 0- .""."""'---. _";::."" .
/ /1
0
0 -5 IN I :
f
I:
I '
I
I :
, ,
I , i
, :
I
I
I
I
I
I
I
,
I I
\.'
,
,
,
,
'L
,
,
,
As
- 25.0 L..I...-1-,.......J._-+-_--+ ___ +__----J

FIG. 3. Shell (dotted lines)
and total (solid line) contribu-
tions to the Laplacian of the
spherically averaged charge
density for the arsenic atom
(Z= 33). computed from the
nonrelativistic SCF wave func-
tion of Clementi and Roetti
(Ref. 19). Note that in this fig-
ure the sections of each plot
represent dift'erent regions of r/
Q
o
all drawn to different scales.
0.0 0.1
0.05 0.35
100.0 .-,........,....--+----1----+---,
500.0 .......
\
,
,
,
I
,
,
,
,
,'M
I
, ,
'j
As
\
I
\
I
\
I
I
I
I
\
I
I
I
IJ
1M
I
I
I r
mox
=2.330
0
\
I
\
Y\
\
\
\
r min= 2.1700 ,
/
I
I
I
I
IN As
I
-600.0
- 500.0
0.30 1.05
a major contribution from a particular shell; (b) the even
zeros which are due to the combination of a strong negative
influence from a particular shell, in combination with a posi-
tive contribution from the next innermost shell. The zinc
(Fig. 1) and arsenic (Fig. 3) atoms are also representative of
the two types of topology ofV
2
p(r), i.e., (1) those atoms and
ions for which the number of extrema is equal to the number
ofzeros,'and (2) the atoms and ions which have two more
extrema than zeros.
Bader and co_workers
I3

14
have indicated that the criti-
cal points of V
2
p(r) are related to regions where electronic
charge is locally concentrated or depleted, and that the zeros
of V
2
p(r) are related to shell structure. However, they did
not conclusively examine which topological feature is most
indicative of a shell nor did they consider the shell contribu-
tions to the total function V
2
p (r). These authors 14 also com-
mented that the first node in V
2
p(r) for a one-electron atom
occurs at r = liZ (where Z is the atomic number), but did
not note that this is precisely the value of r at which the radial
distribution function D(r) is a maximum for the one-elec-
tron atom. They also compared the values of r, for the atoms
Li-Ne, at which the second node in V
2
p(r) occurs, with
previous definitions of core radii and concluded that the re-
sults obtained from V
2
p(r) by analysis of the nodes, were
similar to those obtained from the previous definitions.
Bader et al.
14
have also reported that there are pairs of
ns
'lao
regions, one positive and one negative for each shell, based
on the analysis of the function V
2
p(r), without any recourse
to an examination of the contributions from each shell, i.e.,
the sum of the contributions from all orbitals with the same
principal quantum number. From the plots in Figs. 1 and 2
which show the contrib'Jtions from the individual shells, it is
seen that starting with the L shell, there is more than one pair
of regions where V
2
p(r) for that particular shell is negative
and positive. The L shell exhibits two pairs of regions and the
M shell three pairs. It is clear from these plots that each zero,
maximum and minimum in the total function V
2
p(r) is the
result of contributions from each shell, with every shell con-
tributing to that particular topological feature in varying de-
grees. However, the examination of the plots shows that it is
not the absolute magnitude that a particular shell contrib-
utes to the total function, but rather the relative amount in
relation to the contribution from the other shells, which is
the interesting feature. Thus, for each shell, there is a region
(positive and negative) where the behavior of the total func-
tion is governed by the contribution of that particular shell.
This region is the one that is indicative of the said shell. In
the plots for the atoms Mn, Zn, and As in Figs. 1-3, it can be
seen that although crossing at larger values of r, there is no
region of space where the N shell contribution dominates the
behavior of the total, thus the presence of the N shell is not
represented by V
2
p (r) in these plots. On the other hand,
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Sagar 6t sl.: Shell structure of atoms 4371
NEUTRAL ATOMS


10 20 30 40 50 60 70 80 90
ATOMIC NUMBER
FIG. 4. The positions of the zeros of the Laplacian of the spherically aver-
aged charge density for the neutral atoms as a function of atomic number Z,
where those values belonging to a particular zero (i.e., first, second, third,
etc.) have been connected. The thicker lines connect those r values for the
odd numbered zeros (first, third. etc.) which have been classified according
to each shell (e.g., K, L. M .... ) while the thinner ones connect the even num-
bered zeros (second, fourth, etc.) and have been classified according to each
intershe11 region (e.g . KL. LM, MN, etc.). Note that in this and all following
figures the lines joining the points have no physical significance and are
merely meant to guide the eye.
inspection of the CI + plots in Fig. 1 indicate that all the
shells present are correctly represented by V
2
p(r). It can be
seen from Figs. 1-3 that while the maxima are the result of
generally positive contributions from the shells, with a par-
ticular shell contribution dominating, the minima are the
result of negative as well as positive contributions from the
various shells. As a resUlt, no single shell contribution is
really very similar to the total. Minima, therefore. are related
to a lesser extent to the shell structure.
In order to understand which type of critical point could
be best interpreted as being a boundary for shell structure
analysis, we rewrite Eq. (2) as
_r_
I'lo
o
I ,
SINGLY POSITIVE IONS'
I ,
,
,---

5
2 10 20 30 40 50 60 70 80
ATOMIC NUMBER
FIG. 5. The positions of the zeros of the Laplacian of the spherically aver-
aged charge density for the singly positive ions as a function of atomic num-
ber Z, where those values belonging to a particular zero (i.e., first. second,
third, etc.) have been connected. The thicker lines connect those ,.values for
the odd numbered zeros (first. third. etc.) which have been classified accord-
ing to each shell (e.g . K. L. M .... ) while the thinner ones connect the even
numbered zeros (second, fourth, etc.) and have been classified according to
eachintershell region (e.g., KL,LM,MN, etc.). Note that the gap 57 <.Z<.70
is due to the unavailability of published wave functions for ions with openf
shells.
L
Q -I
0
100
90
80
70
60
50
40
30
20
10
0
NEUTRAL ATOMS
10 20 30 40 SO 60 70 80 90
ATOMIC NUMBER
FIG. 6. The inverse of the positions of the zeros in the Laplacian of the
spherically averaged charge density for the neutral atoms as a function of
atomic number Z, where those values belonging to a particular zero (i.e.,
first. second. third, etc.) have been connected. The thicker lines connect
those rvalues for the odd numbered zeros (first, third, etc.) which have been
classified according to each shell (e.g., K, L, M, ... ) while the thinner ones
connect the even numbered zeros (second. fourth, etc.) and have been classi-
fied according to each intershell region (e.g., KL, LM. MN, etc.).
Clearly, when the Laplacian is negative, its absolute value is
the accumulation in the sense of charge buildup rather than
the amount of charge itself. In fact, isnega-
tive, charge is being accumulated and that is so until V
2
p(r)
becomes zero and then depletion starts. Thus, the charge is
maximally concentrated at the odd zeros (the zeros after the
accumulation region) and not at the minima iIi (r). Con-
versely, charge is maximally depleted at the even zeros after
which V
2
p (r) becomes negative signaling that accumulation
100
90
80
70
.-L.
60
Q
o
-I
50
40
30
20
10
0
SINGL Y lONS:/
I I
I ,
I I
,

'.J----
I LM
FJli
N
2 10 20 30 40 50 60 70 80
ATOMIC NUMBER
FIG. 7. The inverse of the positions of the zeros in the Laplacian of the
spherically averaged charge density for the singly positive ions as a function
of atomic number Z, where those values belonging to a particular zero (i.e.,
first, second. third, etc.) have been connected. The thicker lines connect
those rvalues for the odd numbered zeros (first. third, etc.) which have been
classified according to each shell (e.g . K. L. M, ... ) while the thinner ones
connect the even numbered zeros (second, fourth, etc.) and have been classi-
fied according to each intershell region (e.g., KL. LM, MN, etc.). Note that
the gap 57<.Z<.70 is due to the unavailability of published wave functions
for ions with openfshells.
J. Chern. Phys., Vol. 88, No.7, 1 April 1988
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4372 Sagar et al.: Shell structure of atoms
TABLE I. Data
a
obtained from a linear least-squares fit of the data points
in the curves of Fig. 6 for the neutral atoms.
Zero
ofV
2
p(r) A B
R2
Y Syx
First 1.05 - 0.528 1.00 48.1 0.0993
Second 0.331 -1.04 1.00 14.7 0.124
Third 0.208 - 0.793 1.00 9.08 0.104
Fourth 0.112 -1.05 0.999 4.72 0.0654
Fifth 0.0817 -0.909 0.997 3.30 0.0984
Sixth 0.0549 - 1.25 0.999 2.27 0.0215
Seventh 0.0379 - 0.813 0.997 1.61 0.0366
Eighth 0.0382 - 2.01 0.997 1.30 0.00741
Ninth 0.0230 -0.902 0.992 1.08 0.00794
a The following definitions have been used: slope, A; y intercept, B; square of
the correlation coefficient, R 2; average y value, Y; standard deviation, Syx'
has started. In theI(p) andD(r) cases, where a local maxi-
mum was considered as the reflection of a shell, the local
minimum corresponding to regions of space between two ad-
jacent shells was defined as an indication of an intershell
region.
4

12
Similarly, in the present study we will consider
the even numbered zeros as the topographical feature indica-
tive of intershell regions since they represent the position
where charge is maximally depleted.
To establish suitable criteria for the characterization of
a shell, we shall employ a projection technique that has been
used elsewhere
4

12
to condense all the information pertinent
to the V
2
p(r) plots for all the atoms studied, into a series of
two-dimensional plots. In Figs. 4 and 5 may be found plots
for the atoms and singly positive ions, respectively, in which
are shown the values of r at which V
2
p(r) = 0 for the first,
second, third, etc., zeros as functions of Z, the atomic num-
ber. The points related to the same zero have been connected
only to guide the eye. The roughly first order hyperbolas can
be explained by the use of the Bohr theory of an atom which
specifies shells with orbit radii equal to
(n
2
/Z) [Ir/(mec)], where me and e are the mass and the
charge of the electron, respectively, and Ii is the Planck-
Dirac constant. These figures have been labeled so that the
shells are represented by the thicker lines and single letter
corresponding to the shell, while the intershell regions are
denoted by the thinner lines with double letters correspond-
ing to the two shells between which the intershell region is
TABLE II. Data" obtained from a linear least-squares fit of the data points
in the curves of Fig. 7 for the singly positive ions.
Zero
ofV
2
p(r) A B
R2
Y Syx
First 1.05 -0.531 1.00 42.8 0.0970
Second 0.331 - 1.05 1.00 13.1 0.120
Third 0.208 -0.796 1.00 8.04 0.106
Fourth 0.112 - 1.05 0.999 4.27 0.0688
Fifth 0.0817 -0.916 0.997 2.97 0.101
Sixth 0.0547 - 1.24 1.00 2.09 0.0191
Seventh 0.0373 -0.770 0.997 1.49 0.347
Eighth 0.0420 - 2.33 0.998 1.20 0.00551
Ninth 0.0231 - 0.913 0.988 1.03 0.00736
"The same definitions have been used as in Table I.
TABLE III. Data" obtained from a linear least-squares fit of the slopes in
Table I against the inverse of the square ofthe principal quantum number'
for the neutral atoms.
Zero
ofV
2
p(r) A B
R2
Y Syx
First, third, fifth, 1.08 -0.0362 0.999 0.279 0.0207
seventh, ninth
Second, fourth, 0.309 0.0241 0.997 0.134 0.00912
sixth, eighth
"The same definitions have been used as in Table I.
b For an odd zero the principal quantum number n has been computed ac-
cording to the formula n = (j + 1 )/2, where j is the number of the zero,
while for the even zeros it has been computed according to the formula
n=j/2.
located. When Figs. 4 and 5 are examined on the criteria
previously established, at most five shells are apparent
which interestingly is the maximum number of shells as re-
vealed by the radial distribution function D(r), as was pre-
viously reported.
4
In Figs. 6 and 7 the inverses of the values
in Figs. 4 and 5 are plotted, respectively, against the atomic
number Z. The linearity of these plots is supportive of the
fact that there is a correlation between the radii of the shells
from the Bohr theory, and the zeros of the Laplacian ofthe
spherically averaged charge density. A least-squares fit was
performed on the data points in Figs. 6 and 7 with the results
tabulated in Tables I and II for the atoms and ions, respec-
tively. The values of close to unity for the square of the
correlation coefficient serve to substantiate the linearity of
the curves in Figs. 6 and 7. Table III (IV) consists ofa least-
squares fit of the inverse of the shell number (i.e., K = 1,
L = 2, etc.) squared as in the Bohr theory of an atom, against
the slopes in Table I (II), for the neutral atoms (singly posi-
tive ions). The value of the slope for the odd zeros of very
nearly unity, combined with a comparatively large deviation
from unity in the slope for the even zeros, indicates that the
correlation between the Bohr theory of an atom, and the
zeros of V
2
p (r) is greater in the case of the odd zeros. This
result suggests that the odd zeros are more intimately relat-
ed to the Bohr theory of an atom, and are, therefore, more
suitable as the topological feature within V
2
p(r), which is
most characteristic of a shell.
TABLE IV. Data" obtained from a linear least-squares fit of the slopes in
Table II against the inverse of the square of the principal quantum number'
for the singly positive ions.
Zero
ofV
2
p(r) A B
R2
Y SyX
First, third, fifth, 1.08 -0.0363 0.999 0.280 0.Dl87
seventh, ninth
Second, fourth, 0.307 0.0257 0.998 0.135 0.00906
sixth, eighth
a The same definitions have been used as in Table I.
b For an odd zero the principal quantum number n has been computed ac-
cording to the formula n = (j + 1 )/2, where j is the number of the zero,
while for the even zeros it has been computed according to the formula
n =j/2.
J. Chern. Phys., Vol. 88, No.7, 1 April 1988
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Sagar et al.: Shell structure of atoms 4373
re
-I
00-
1
80
70
60
50
40
30
20
10
0
NEUTRAL ATOMS
10 20 30 40 50 60 70 80 90
ATOMIC NUMBER
I. 6 [T"""l"""""""""--"-'---'--"--'-""--"""""--"---'--"""""'''''''''''--''-'''
1.4
1.2
1.0
r -I
e
00-1 0.8
0.6
0.4
0.2
0.0
NEUTRAL ATOMS
(b)
,.;;
5
5
4'
4'::1
5' f :=:; 5
6
6',
7
10 20 30 40 50 60 70 80 90
ATOMIC NUMBER
FIG. 8. The inverse of the positions of the extrema in the Laplacian of the
spherically averaged charge density for the neutral atoms as a function of
atomic number Z, where those values belonging to a particular extremum
(i.e., first, second, third, etc.) have been connected. The thicker lines con-
nect those r values for the maxima (first, second, third, etc.) while the thin-
nerones connect the minima (first, second, third, etc. ). Note that the minima
have been labeled with primes. Plot (a) contains the first four maxima and
first three minima. Plot (b) contains the fifth and sixth maxima and fourth
and fifth minima.
In Figs. 8 and 9 are shown the inverses of the r values at
which the first, second, third, etc., extrema in V
2
p(r) occur
as functions of the atomic number Z. The nonlinearity in the
curves for the outer extrema Figs. 8(b) and 9(b) illustrates
that the maxima and minima in V
2
p(r) exhibit a compara-
tively lesser degree of correlation with the Bohr theory of an
atom than in the case of the zeros. Furthermore, the breaks
in these curves, i.e., a particular extremum being present at
an atomic number Z, but then not being present for some
higher atomic number Z', makes it impossible to assign a
particular extremum to a particular shell for all the studied
cases.
CONCLUSIONS
Of the topological features examined in V
2
p(r), the
zeros, and in particular the odd numbered zeros, were shown
to exhibit good correlations with the Bohr theory of an atom.
On the other hand, the extrema were shown to exhibit devia-
tions from the Bohr theory and also breaks in the plots of the
inverses of the positions of the respective extrema against
atomic number. Based on these facts the extrema would
r
e
-
I
o -I
0
70
60
50
40
30
20
10
0
SINGLY
I '/
POSITIVE IONS !/
(0) I,
I
1
1
:----
,
,
2:--
2' :_
3,
3 I
4,
2 10 20 30 40 50 60 70 80
ATOMIC NUMBER
1.4 fT'"'I.....,.....,,......, ...... ,.......,..........-or-....-............. , ..,-..,-..,...-....-...-......-,
,
1.2
SINGLY POSITIVE IONS
1.0
(b)
4' ;':
5' /
5 ..II
6 .;
4'
I
4'
5
I
I
5
0.4
0.2
0.0
1.
2 10 20 30 40 50 60 70 80
ATOMIC NUMBER
FIG. 9. The inverse of the positions of the extrema in the Laplacian of the
spherically averaged charge density for the singly positive ions as a function
of atomic number Z, where those values belonging to a particular extremum
(i.e., first, second, third, etc.) have been connected. The thicker lines con-
nect those r values for the maxima (first, second, third, etc.) while the thin-
ner ones connect the minima (first, second, third, etc.). Note that the gap
57 <Z< 70 is due to the unavailability of published wave functions for ions
with open/shells. Note that the minima have been labeled with primes. Plot
(a) contains the first four maxima and first three minima. Plot (b) contains
the fifth and sixth maxima and fourth and fifth minima.
seem to be a poor choice for the topological feature in V
2
p (r)
most indicative of a shell. In our opinion the odd numbered
roots in V
2
p (r) are clearly most indicative of shell structure.
Finally, it should be noted that recent studies
23

24
have
indicated that in the Schrodinger equation for the electron
density, the potential energy function that arises is
] ], and as such provides a means of pre-
dicting regions of space where the electron is classically al-
lowed or forbidden. This potential energy function will be
the subject of a future study25 to examine the claim that it
displays the shell structure of atoms.
ACKNOWLEDGMENTS
This research was supported in part by the Natural Sci-
ences and Engineering Research Council of Canada
(NSERCC) and also by the Conselho Nacional de Desenvol-
vimento Cientifico e Tecnol6gico (CNPq-Brasil).
J. Chern. Phys., Vol. 88, No.7, 1 April 1988
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4374 Sagar 61 al.: Shell structure of atoms
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(1981).
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J. Chern. Phys., Vol. 88, No.7, 1 April 1988
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