26 August 2002

Chemical Physics Letters 362 (2002) 362–364

www.elsevier.com/locate/cplett

Configuration irregularities: deviations from the

Madelung rule and inversion of orbital energy levels
Terry L. Meek a, Leland C. Allen b,*

a
Department of Biological and Chemical Sciences, University of the West Indies, Cave Hill, Barbados
b
Department of Chemistry, Princeton University, Princeton, NJ 08544, USA
Received 21 August 2001

Abstract

(a) The electron configurations of many atoms that do not obey the Madelung rule of orbital occupancy can be
explained by minimum-energy configurations obtained from the Dirac Hyper Hartree–Fock equations. The resulting
non-integral occupation of ns and (n
1)d orbitals (the usual interpretation for energy band calculations in solids)
explains eight of the ten ‘anomalous’ configurations. (b) All four d- and f-block atoms whose singly charged cations
result from the loss of an (n
1)d electron rather than an ns electron are shown to have (n
1)d rather than ns as
their highest occupied energy levels. Ó 2002 Published by Elsevier Science B.V.

1. Neutral atoms and the Madelung rule et al. [2], and the origin of the Madelung rule has
recently been elucidated [3].)
The filling of atomic orbitals in neutral atoms is For almost one-third of the 58 transition metals
said in most elementary and advanced textbooks – 10 in the d-block and 9 in the f-block – the
to follow the Madelung rule: 1 orbitals are occu- Madelung rule predicts ground state configurations
pied in order of increasing values of the sum of that differ from those determined experimentally
their n and l quantum numbers; for orbitals with [4]. Many of the exceptions can in fact be explained
the same values of ðn þ lÞ, the orbital with lowest n by exploitation of the Hyper Hartree–Fock meth-
is occupied first [1]. This rule generally predicts odology. In a recent article we noted [5] that the
correctly the order in which the energy levels of ns2 ðn
1Þdm and ns1 ðn
1Þdmþ1 configurations
neutral atoms are filled. (The preferential occupa- (and in some cases the ns0 ðn
1Þdmþ2 configura-
tion of the 4s orbital before the 3d level has been tion) lie very close to each other in total energy, and
comprehensively analyzed by Vanquickenborne that variation of the orbital occupancy as well as its
shape provides simple and useful insights into these
cases. The non-integral occupancy of the ns and
(n
1)d orbitals from our Dirac Hyper Hartree–
*
Corresponding author. Fax: +609-258-6746.
Fock solutions are listed in the last column of Table
1
Also known variously as the Klechkowsky rule, the Goud- 1. There it can be seen that, for 8 of the 10 d-block
smit rule and the Bose rule. elements with ‘non-Madelung’ ground state

0009-2614/02/$ - see front matter Ó 2002 Published by Elsevier Science B.V.

PII: S 0 0 0 9 - 2 6 1 4 ( 0 2 ) 0 0 9 1 9 - 3
 T.L. Meek, L.C. Allen / Chemical Physics Letters 362 (2002) 362–364 363

Table 1
Electron configurations of selected elements
Atom Ground state configuration Minimum-energy configuration [5]

Predicted Found
4
Cr 2
[Ar] 4s 3d [Ar] 4s1 3d5 [Ar] 4s1:779 3d4:221
Cu [Ar] 4s2 3d9 [Ar] 4s1 3d10 [Ar] 4s1:489 3d9:511
Nb [Kr] 5s2 4d3 [Kr] 5s1 4d4 [Kr] 5s1:735 4d3:265
Mo [Kr] 5s2 4d4 [Kr] 5s1 4d5 [Kr] 5s1:382 4d4:618
Ru [Kr] 5s2 4d6 [Kr] 5s1 4d7 [Kr] 5s0:772 4d7:228
Rh [Kr] 5s2 4d7 [Kr] 5s1 4d8 [Kr] 5s0:535 4d8:465
Pd [Kr] 5s2 4d8 [Kr] 4d10 [Kr] 5s0:333 4d9:667
Ag [Kr] 5s2 4d9 [Kr] 5s1 4d10 [Kr] 5s1 4d10
La [Xe] 6s2 4f 1 [Xe] 6s2 5d1
Ce [Xe] 6s2 4f 2 [Xe] 6s2 4f 1 5d1
Gd [Xe] 6s2 4f 8 [Xe] 6s2 4f 7 5d1
Pt [Xe] 6s2 5d8 [Xe] 6s1 5d9 [Xe] 6s0:791 5d9:209
Au [Xe] 6s2 5d9 [Xe] 6s1 5d10 [Xe] 6s1 5d10
Ac [Rn] 7s2 5f 1 [Rn] 7s2 6d1
Th [Rn] 7s2 5f 2 [Rn] 7s2 6d2
Pa [Rn] 7s2 5f 3 [Rn] 7s2 5f 2 6d1
U [Rn] 7s2 5f 4 [Rn] 7s2 5f 3 6d1
Np [Rn] 7s2 5f 5 [Rn] 7s2 5f 4 6d1
Cm [Rn] 7s2 5f 8 [Rn] 7s2 5f 7 6d1

Table 2
Unusual cation configurations
Element Configuration of M Configuration of Mþ
ens =R
eðn
1Þd =R
(a) Rearrangement
V [Ar] 4s2 3d3 [Ar] 3d4
Co [Ar] 4s2 3d7 [Ar] 3d8
Ni [Ar] 4s2 3d8 [Ar] 3d9
La [Xe] 6s2 5d1 [Xe] 5d2
Ce [Xe] 6s2 4f 1 5d1 [Xe] 4f 1 5d2
(b) Loss of nd
Y [Kr] 5s2 4d1 [Kr] 5s2 0.4926 0.4769
Lu [Xe] 6s2 4f 14 5d1 [Xe] 6s2 4f 14 0.5175 0.3882
Hf [Xe] 6s2 4f 14 5d2 [Xe] 6s2 4f 14 5d1 0.553 0.451
Ac [Rn] 7s2 6d1 [Rn] 7s2 0.4440 0.3678

configurations, the experimentally observed con- (Data for the f-block elements are not available to
figurations are in agreement with the Hyper Har- allow similar comparisons to be made for them.)
tree–Fock results rounded off to the nearest whole
numbers. The only d-block elements whose
‘anomalous’ configurations cannot be rationalized 2. Configurations of cations
by this criterion are chromium and niobium. 2
The Madelung energy ordering rule applies only
to neutral atoms. For the d-block metals, the
2
On the other hand, the Hyper Hartree–Fock criterion
configurations of cations have also been thor-
predicts that Tc, Os and Ir would have ns1 ðn
1Þdmþ1 oughly discussed by Vanquickenborne [2a]. The
configurations when they do not. stability order of the two lowest configurations
364 T.L. Meek, L.C. Allen / Chemical Physics Letters 362 (2002) 362–364

is reversed in the Mþ cations so that ns1 ðn
1Þ 3. Summary

dm < ns2 ðn
1Þdm
1 , and the s-electrons are the
first to be ionized. Thus the typical configuration (a) Exceptions to the Madelung rule are ex-
of a singly charged cation is ns1 ðn
1Þdm , and plained for neutral atoms of the d-block by con-
that of a doubly charged cation is ðn
1Þdm . sideration of the minimum-energy electron
For most atoms – even the ones with ‘non- configurations determined from the results of Di-
Madelung’ configurations – the M atom in its rac Hyper Hartree–Fock calculations. Only two of
ground state loses an ns electron to form the Mþ the ‘anomalous’ d-block elements have configura-
ion. (In fact, all of the M2þ ions have the expected tions not consistent with this criterion.
dm configurations.) (b) For singly charged cations, all four transi-
A total of 9 of the 58 Mþ transition metal ions tion metal Mþ ions which retain the ns2 configu-
(six in the d-block and three in the f-block) have ration are produced from atoms whose (n
1)d-
ground state configurations other than the ones orbitals are in fact the highest occupied orbitals of
which would result from the loss of an ns electron. the atoms.
These are shown in Table 2. For four of these (Yþ ,
Luþ , Hf þ , and Acþ ), the ionized electron is
ðn
1Þd rather than ns. This can be readily ex- References
plained by consideration of the one-electron en-
[1] E. Madelung, in: Die Matematischen Hilfsmittel des Phys-
ergies, enl , of these orbitals. We have calculated ikers, third ed., Springer, Berlin, 1936, p. 359.
values of enl from spectroscopic data [4], using the [2] (a) L.G. Vanquickenborne, K. Pierloot, D. Devoghel,
method described previously [5], for all four of J. Am. Chem. Soc. 28 (1989) 1805;
these atoms. In each case the ðn
1Þd orbitals are (b) L.G. Vanquickenborne, K. Pierloot, D. Devoghel,
higher (less negative) in energy than the ns orbitals, J. Chem. Educ. 71 (1994) 469.
[3] L.C. Allen, E.T. Knight, Int. J. Quant. Chem. (submitted
which explains the seeming anomaly. These orbital for publication in L€ owdin issue, Fall 2002).
energies are included in Table 2. 3 [4] C.E. Moore, Atomic Energy Levels ; NSRDS-NBS 35;
In the other five ions (Vþ , Coþ , Niþ , Laþ and Washington, DC, 1971; vols. I, II, III. The classic text which
þ
Ce ), the configuration is ðn
1Þdmþ1 rather than discusses atomic structure and spectra is R.M. Hochst-
ns1 ðn
1Þdm . Unfortunately the Dirac Hyper rasser’s Behavior of Electrons in Atoms, Benjamin, New
York, 1964. Also see R.M. Hochstrasser, J. Chem. Educ. 42
Hartree–Fock equations have not yet been applied (1965) 154.
to cations, so the minimum-energy configurations [5] J.B. Mann, T.L. Meek, E.T. Knight, J.F. Capitani, L.C.
of these ions cannot be determined at present. Allen, J. Am. Chem. Soc. 122 (2000) 5132.

3
The Ta atom ionizes by a loss of 6s electron, although the
multiplet averaged one-electron energy of the 5d orbital of Ta is
higher ()0.557R) than that of the 6s ()0.621R). We have shown
[5] that ed ¼ IG þ hs2 d2 i
hs2 d3 i, and several high-energy
excited states of the 6s2 5d2 configuration of Taþ contribute
heavily – due to their high multiplicity – to hs2 d2 i. This
accounts for the seeming anomaly of Ta ionizing by loss of an
electron from an energy level other than its least stable one. The
ground state of Taþ is a 5 F state arising from the 6s1 5d3
configuration.