On the Lanthanide and "Scandinide"l Contractions
D. R. Lloyd
Trinity College, Dublin, Ireland
The lanthanide contraction must receive a t least a men-
tion in all introductory university chemistry courses, as well
as further discussion with the chemistry of the f-block ele-
ments. Most textbooks of inorganic and general chemistry
indicate that contractions occur in all rows of the periodic
table, but, even so, in the emphasis on this contraction,
students can be left with an impression that the effect is
particularly large for the lanthanides. Inspection of ionic
radius tables2 should dispel this idea. The decrease across 15
elements La3+-Lu3+ (117.2-100.1 Dm) is less than that
across 1 1 elements in the third row if the 2t ions, of similar
size to the lanthanides. are chosen: Ca2--%n2- (1lPRR om).
Even if the much smaller 3+ ions are used, s c 3 + - ~ a ~ +
(88.5-76 Dm). the average absolute chance per element is
almost identical to that the lanthanide ions, and the per-
cent change is therefore greater in the "scandinide" contrac-
tion than-in the lanthaiide contraction. Similar remarks
apolv
.. . to the metallic radii.
'I'eats on inorganic chemistry give varying accounts of the
cause of the lanthanide contraction. Somedo not discuss the
- -
matter. others refer in a eeneral manner to shieldine effects.
and this is clearly correct if not very explicit. However, some
texts give an interpretation which can he generalized in a
form such as "Shielding of one 4f electron by another from
the nuclear charee is Door because of the shapes of the 4f
orbitals, so, as the nuclear charge increases, there is a reduc-
tion in size of these orbitals, and this is the origin of the
contraction". Some also draw a direct comparison with the
contraction acrois the Rd series. The various forms of the
statement have the following more or less direct, interrelat-
ed implications:
1 The "size" of the lanthanide atoms or ions is determined to a
substantial extent by the 4f' subshell, i.e., these are "outer-
most" electrons.
2 The contraction of the atoms or ions is a consequence of the
angular part of the 4f wavefunctions.
The first of these is a little surprising when the small size
of the experimentally observedcontr&tion is considered,
but, much more seriously, there is an inconsistency with the
interpretation usually given to the magnetic and spectro-
scopic properties of the ions LIP, that the 1f electrons are
well shielded from the chemical environment of the ion bv
the 5s2 5p6 configuration. If this is so, and the experiment&
evidence ~ o i n t in
s this direction. then im~lication(1) must
be incorrect, and the implied connectionkith d-orbital ef-
fects in the transition series is suspect.
Implication (2) has a similar incongruity, a t least in the
discussion of effects on the third transition series, where the
4f shell is complete. Since the closed shell 4p4 configuration
has spherical symmetry, there can be no angular effect here;
any effects must he due to the radial part of the appropriate
wavefunctions.
A very elementary approach to point (i) can he made by
using Slater's rules to calculate the radius R, of the maxi-
m& in a spherical charge density function (3). as R, =
~L*~Z'-' X 52.9 pm (Z* is the effective nuclear charge, n* the
effective quantum number). Taking Gd3+ as an example,
this gives values of R, as (5p6) 69 pm and (457) 24 pm. This
supports the idea that the 4f configuration is "deep inside"
the ion.
502 Journal of Chemical Education
More precise analysis is available from the detailed atomic
calculations of Waber and Cromer ( 4 ) , who have reported
values of R,. (here R, is the o r i n c i ~ aradial
l maximum) and
Herman an; skillman (5) w i o give tabulations of the wave-
functions. The Waber and Cromer R, values demonstrate
that the simple Slater approximation Gves remarkably good
estimates; for Gd3+ values are (5p6) 71.0 pm, (4f) 29.1 ~ m . ~
For the Gd atom, values are (6s) 182.6 pm, (5d1) 96.0 pm,
(5p6)71.0 pm, (4f) 29.1 pm. Similar values can be extracted
from the Herman-Skillman tables (5).The conclusion that
R, for the (4f") configuration is little more than one-third of
that for (5p6) is true for all the lanthanides, though the
percent change in radius of the f shell from Ce3+ t o Lu3+
(35.624.4 om. 32%) is substantiallv ereater than that for
isp" (80.(i63.2 pm;21%). Clearly, aithough the 4p subshell
contracts r a.~ i d.
l vwith %. it does so well inside the outermost
core electrons.
The contributions to the "size"of the atom are difficult t o
assess precisely, though it is clear from the above that any
contribution bv the 4f shell must be small. An attempt can
be made by calculating electron densities a t various-radii.
+
The total 4f" and (5p6 5s2) electron densities can readily he
obtainedfrom the Herman-Skillman tables. For Gd the ratio
+
of the densities 457 (5p6 5s2) is 0.21 a t R, (5p6) and falls to
0.07 a t the ionic radius. Thus, in the outer regions of the ion,
4f contributes of the order of 10% of the electron density.
While this is not a neeligible contribution to the size. to a
first approximation i t is reasonable to describe the (5si 5p6)
configuration as radius-deterrninir~g.~ I t may he noted that
the small contribution from 4f increases across the series,
since the f-shell occupancy increases faster than the f orbital
density a t the ionic radius decreases from the contraction, so
the small effects of the f electrons actually. oppose .. the con-
traction.
Since the a n d a r part of the 4f wavefunctions cannot be
significant, thereason for the contraction has to be sought in
the radial part of the functions. The 4f has only one radial
maximum. and so inside R.. I4n there will be onlv a small
shielding bf other electrons'bi4f electrons. The tables (5)
show that for all the lanthanides, the third radial maximum
of the 5p6 orbital, and the fourth maximum of the 59, are just
inside the maximum for 4f. Thus the 5s and 5p orbitals
penetrate the 4f shell quite effectively, and this is the sim-
olest interoretation of the sensitivitv of size to nuclear
charge. he lanthanide contraction could well be taught as
an unusuallv simple illustration of penetration effects on
size, together with the more usual discussion of penetration
effectn on orbital energies for polyelectronir atoms. Alterna-
tively, in terms of shielding, i t is true that the 4f electrons
provide poor shielding from the nuclear charge, hut the
' The name "scandinide contraction" has been suggested, though
not entirely seriously, by E. A. V. Ebsworlh, to emphasize that the
contraction of the lanthanides is not unique.
2F~liowingHuheey (0.the Shannon-Prewiti radii (2)are used:
values quoted are those for 6-coordination.
The calculations of ref 5are relativistic; values quoted for fshells
have been averaged appropriately, though the difference between the
f,,, and fi12 radii is not significant in the argument presented here.
* A statement of this point is made explicitly in the text by Day and
Selbin (6).
significant shielding is that for the (5s25 p 6 ) configuration
and not that for the other 4f electrons.
In contrast to the situation in the lanthanides, in the first
transition series 3d" electrons make a ven, substantial con-
tribution LO the ionic radius. R,values forihe Bdn configura-
tion aresliehtlv
" .-
ereater than those for the 30"et at the start
of the series, and both sets contract, but the 3d set contracts
faster so that the ~ o s i t i o nis reversed for the later members
(4). In the second transition series the more expanded 4d
orbitals extend slightly beyond the 4p configuration
throughout (4).Thus in the series of transition elements it is
reasonable to ascribe part of the observed contractions to
poor shielding of one electron by another in the same suh-
shell, but here also i t should be realized that contraction of
the outer core electrons is significant
Conclusions
I t can be shown from the literature that the radius of the
lanthanide ions is mainly determined by the outer ( 5 9 5 p 6 )
configuration and that the 4f electrons make very little di-
rect contribution to "size". The observed contraction across
thelanthanide series is a contraction of the (5.9 5p6)configu-
ration brought ahout by penetration of these outer electrons
inside the 4f radial maximum, and is not an effect of the
contraction nf the 4f shell itself. However, the contractions
ohserved in the transition series, such as the "scandinide"
contraction in the first series, are due t o contractions of both
the outer core electrons and the partially filled d shell; the
commonly discussed effect of poor shielding of one electron
by another in the same subshell is significant here, hut not
for the lanthanides.
Acknowledgment
The impetus for this note comes from students who have
driven me to clarify my own thoughts, the presentation here
has been improved by discussion with several colleagues,
particularly D. J. Cardin and M. E. Bridge.
(1) Huheey, J. E. "lnownie C h e m i W , 3rdsd.j Hsvpsr & Rosv: New York. 1983;p 72.
(2) Shannon,R.D.; Preett. C. T. Acta Cryat. B25,1969,926.Sb-on, R.D. A d o C v t .
--..,..--,
,176 rO9 711
(3) Purcell. K. F.: KO*.J. C. "borganio Chemiatry";Saundna:New York, 1917; p 42.
(4) Waber,J. T.;Cromer, D.T. J. Chem.Phys. I%&,42,4116.
(5) Herman. F.: Skillman, S. "Atomic Structure Cdeulationa": Prentiee-Hall: Enphood
Cliffs. NJ. 1963.
Volume 63 Number 6 June 1986 503