GUEST AUTHOR Textbook Errors, 58
J. J. Zuckerrnan
Cornell University
Ithaca, New York
Crystal Field Splitting Diagrams
It is now over a decade since the tlieo-
retinal treatment of transition metal complexes which
goes by the general name Crystal Field or Ligand Field
Theory came into general acceptance in inorganic chem-
istry. {In current usage these terms are interchange-
able, but more specifically the crystal field theory does
not consider the role played by the ligands further than
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to credit them with producing an electrostatic field,
while the ligand field theory includes molecular orbital
considerations. Our discussion relates to electrostatic
crystal field theory only.) Its use as part of course
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work in inorganic chemistry is now well established, and
simplified explanations based upon the usual Crystal
Field Splitting Diagram are about to filter down into
the freshman curriculum. This article is written in an
attempt to bring this much used diagram into better
agreement with the realities of the situation.1
Central to the idea of the crystal field approach is
that the energies of the d-orbitals of a metal ion in a
transition metal complex split in the presence of per-
turbation by the surrounding ligands. This effect in
crystal lattices was discussed by Bethe in 1929.2 In a
field of any given geometry, certain of the d-orbitals find
themselves oriented more in the direction of the field of
the ligands than others, and the energies of these or-
bitals are raised by the electrostatic repulsions of the
ligands while the energies of the other d-orbitals are
affected to a smaller extent.
It is usual to illustrate the splitting of the five de-
generate d-orbitals of a transition metal ion for the case
of three representative symmetries: octahedral, tetra-
hedral, and square planar. A single energy diagram is
frequently used to show all three types of splittings with
reference to the free ion or field-free ion as the five-fold
degenerate ground state of the d-orbitals is usually
labeled. This standard Crystal Field or Ligand Field
Splitting Diagram must by now be familiar to both
students and teachers.
A new diagram, (p. 316), is recommended to replace
the one now in use. Consider the case of the octahedral
field first. If a complex is formed by bringing six
identical ligands along x, y, and z axes so as to form a
Suggestions of material suitable for this column, and guest
columns suitable for publication directly, should be sent with as
many details as possible, and particularly with references to
modern textbooks, to Karol J. Mysels, Department of Chem-
istry, University of Southern California, Los Angeles 7, California.
! Since the
purpose of this column is to prevent the spread
and continuation of errors and not the evaluation of individual
texts, the source of errors discussed will not be cited. In order
to be presented, an error must occur in at. least two independent
recent standard books.
2
Bethe, H., Ann. Physik. 3, 133 (1929).
regular octahedron about the metal ion, the charges on
the ligands will repel an electron to a greater extent if it
is in a dz2 or dX2-y2 orbital than if it is in a dxy, dxz, or
dyz orbital, since the former point toward the ligands
and the latter point between the axes of approach.
(The ligands either possess a net negative charge, i.e.,
are anions, or align themselves so that a negative re-
gion of charge is nearest the central atom. In electro-
static theory, the ligands can be considered as point
charges or point dipoles.) Thus for the field-free ion or
atom in vacuo, the d-orbitals are energetically degener-
ate, but their energies become differentiated in a con-
certed process as the energies of all the orbitals are
raised with the approach of the ligands. In the case of
octahedral symmetry the original degeneracy is de-
stroyed, and the energies are split into two groups with
the dzi and dxt-v-t orbitals assuming a higher energy and
the dxy, dxz, and dyz orbitals at a lower energy. The
two higher energy orbitals are called dy according to
van Vleck, e„ according to Mulliken, and y-.-, in Bethe’s
original notation. The three lower energy orbitals are
called dt by van Vleck, t2„ by Mulliken, and 75 by
Bethe.3
The fact that all the d-orbital energy levels are raised
by the repulsion of the ligands is emphasized. In fact
the differentiation of the d-orbital energy levels is a
relatively small effect superimposed on the much
larger repulsive effect of the crystal field on the orbitals.
This repulsion of the negative electron cloud about the
metal ion by the negative charge or dipole of the ligand
is in its turn small by comparison with the overall
attraction of the positive metal ion for the ligands.
These repulsions are contained in the lattice energy of a
crystal or the ligation energy of a metal complex. [For
example, in octahedral Ti (H20)e3+ the splitting of the
two sets of d-orbitals is of the order of 60 kcal/mole
while the hydration energy of Ti3+ is approximately
1000 kcal/mole.] The d-orbital energy level splitting
is measured in terms of a parameter A, 10 Dq or Ei-E2,
whose magnitude is assumed to be proportional to the
strength of the crystal field: the stronger the field, the
larger the value of A or Dq or E\-E2.
The center of gravity of the d-orbital energies repre-
sents the energy the five d-orbitals would have in the
presence of a spherically symmetric field. It is the
weighted mean energy of the d-orbitais in the presence
of the ligands. In another view, if we may break the
concerted process of raising the energy and differenti-
ating into two steps, then this is the energy to which the
3
See footnote 7 in the Resource Paper I, “Ligand Field
Theory,” by F, A. Cotton, this Journal 41, 466 (1964).
Volume 42, Number 6, June 1965 / 315
 Table 1. The d-Orbital Energy Levels in Crystal Fields of Different Symmetries
C.N. Structure dx*.. y« dx. dx

1 ..." -3A4Dq 5A4Dq -3A4Dq 0.57 Dq 0.57 Dq

2 linear" -6.28 10.28 -6.28 1.14 1.14
3 trigonal1’ 5.46 -3.21 5.46 -3.86 -3.86
4 tetrahedral -2.67 -2.67 1.78 1.78 1.78
4 square planar6 12.28 -4.28 2.28 -5.14 -5.14
5 trigonal bipyramid' —0.82 7.07 -0.82 —2.72 —2.72
5 square pyramid' 9.14 0.86 —0.86 —4,57 —4.57
6 octahedron 6.00 6.00 -

4.00 -

4.00 -

4,00
7 pentagonal bypyrimid' 2.82 4.93 2.82 —5.28 —5.28
“
Bonds lie along z axis. ‘
Pyramid base in xy plane.
i
Bonds in the xy plane. Only electrostatic perturbations are considered.

five degenerate d-orbitals would be raised before split-
ting took place. It is the zero of energy in the per-
turbed system, and the algebraic sum of all energy
shifts from this level is zero. This is a simple statement
of the "preservation of the center of gravity” rule from
quantum mechanics. The rule is quite general for all
splittings where the forces are purely electrostatic and
where only the sets of levels being split is considered.
To take the octahedral case where the total splitting is
Aoct, the upper two orbitals lie 3/=, Aoct above and the
lower three lie Vs A„t below the energy the orbitals
would have in a spherically symmetric field. Note
that this zero level is not the free ion or field-free ion
energy which is much lower.
By analogous and by now familiar argument the
splittings for the tetrahedral and square planar cases
are worked out.4 In the presence of a tetrahedral field
the orbitals most affected in the octahedral example are
least raised, and vice versa. Here the upper three
orbitals lie at 2/5 At8t above the center of gravity and the
lower two at 3/s Ate, below. Further, it can be shown
that, all else being equal (cation, ligands, cation-ligand
distance, etc.), the total tetrahedral splitting, A™,., is
4/9 of Aoct, so that the magnitude of the crystal field
splitting in an octahedral complex will bo over twice
Splitting diagrams for the linear, trigonal, trigonal bipyrami-
4
dal, and cubic fields have been recently given by A. L. Com-
panion and M. A. Komarynsky, in this Journal 41, 257
(1964).
d;3 dn-y3
that in a tetrahedral complex with the same charge per
ligand and the same bond distances as in the octahedral
one. d-Orbital energy levels in crystal fields of various
symmetries can be calculated, and some results of single
electron energies are listed in Table l,6 These values
were used in constructing the figure.
A further note to Figure 1 concerns the positions of
the centers of gravity for each of the three types of
fields commonly represented. Since the center of
gravity of each of the splittings represents the condition
of the ion in the presence of a spherically symmetric
field of the same strength (all other factors being held
constant) as the actual field of the ligands, then it can
be seen that for identical ligands the field strength will
be a simple function of the number of ligands, i.e., of
the coordination number of the complex. Thus for
similar ligands the center of gravity of an octahedral
complex will lie at higher energy than that of a tetra-
hedral or square planar complex, and these last two
will have identical centers of gravity. This is shown in
the figure.
The actual magnitude of the splitting (we have called
A in the figure) is proportional in the first instance to
the strength of the crystal field generated by tire ligands
which depends upon the charge or dipole moment, as
well as size, polarizability and ability to form Tr-bonds.6
In addition, the following generalizations can be made:
(1) Auct is approximately 45% larger when 4d orbitals
are used and 75% larger for 5d (assuming metal of
identical valence in the same periodic group).
(2) Aoct is 40-80% larger for the trivalent. ion than
the divalent ion of the same metal.
(3) AMt varies roughly between 20-40 kcal/mole for
most divalent hexacoordinated 3d complexes.
(4) The common ligands may be arranged in a se-
quence of regular increase of A0ct values for
their complexes with any given metal ion.
This dependence of A„,t values on the identity
of the ligands is known as the spectrochem-
ical series.

fi
Basolo, F., and Pearson, It., “Mechanisms
of Inorganic Reactions,” John Wiley & Sons, New
York, 1958, p. 55.
6
“It seems noteworthy, although not a point to
be stressed unduly, that by taking into account, both
types of crystal field parameters—shifts in the cen-
ter of gravity for d-orbitals as well as splittings of
plonor their energies—the diagram in the figure de-
nation
scribes qualitatively the results of even the most
sophisticated molecular orbital studies of the energy
levels for the d-like orbitals of transition metal
complex ions and molecules.” (Private communi-
Free Ion cation, Dr. G. L, Goodman, 1964.)

316 / Journal of Chemical Education

 A note on the limitations in the use of Crystal Field
Splitting Diagrams is in order in conclusion. First,
the differentiation of the d-orbital energy levels, as
important as it may be for explaining differences be-
tween various complexes makes up only a small frac-
tion (5 -10%) of the total binding energy of the com-
plex. A much more serious limitation comes about be-
cause the d-orbital energy levels for various crystal
fields are readily obtained only for the case of a single
d-eleetron, and diagrams such as Figure 1 are strictly
applicable, therefore, only to the one electron case.
Systems with more than one d-electron are complicated
by electron-electron interactions. It turns out that the
diagrams can be used equally well for the d’ and d6
cases (for reasons which we will not go into), and also to
approximate the d* and d9 cases. The diagrams for
configurations d2 and d1 and d3 and ds are much more
complex. The changes in the diagrams as one goes
through the configurations d1 to d9 are quite drastic,
involving not only changes in the relative magnitudes of
the splittings, but the appearance of additional split-
tings and even reversals hi the energies of the d-orbitals
as well. The situation is further complicated by dis-
tortions from perfect octahedral or other geometry.
These distortions are quite common and produce addi-
tional splittings. Thus to represent correctly the situa-
tion in each of the wide range of possible electronic and
geometric configurations in transition metal complexes
would require a family of Crystal Field Splitting Dia-
grams. Any one diagram which attempts to serve all
situations must be used with care.
Acknowledgment
The author thanks Professor R. C. Fay of this uni-
versity for helpful discussions.
Volume 42, Number 6, June 1965 j 317