Professional Documents
Culture Documents
-
Prepored under the sponsorship of
The Advisory Council on College Chemistry
F. Albert Cotton
Massachusetts Institute of Technology
Cambridge, Mass.
Ligand Field Theory
The presentation of ligand field theory in causes, but for most undergraduate courseeand cer-
the first college ehemistry course cannot be said to be tainly for the introductory course--such rigor and wm-
essential. If time is limited, or if the ability of the prehensiveness are unnecessary.
students and/or their interest in chemistry as a pure
science rather than as a branch of useful knowledge are Causes of Inner Orbital Spitting$
not well above average, I believe there are many other The possibility that the degeneracy of atomic orbitals
topics which can be more profitably discussed. There will be sigxZ6oantly split when an ion is placed in a
is time enough in later years of the chemistry cur- chemical environment was fist suggested by Bec-
riculum for those who do elect chemistry as a major querel (1) and the problem was then examined in con-
subject to tackle this aspect of it. However, in a siderable detail by Bethe (2). Bethe's work consists
thorough sort of course, taught to a select, science- of two parts: first, in one of the earliest applications of
oriented group of students, the subject of ligand field symmetry arguments to a chemical problem, Bethe
theory might form an interesting and stimulating part. determined the qualitative nature of the orbital split-
Certainly it is an important part of the "vocabulary" tings for various important geometries. These quali-
of modern theory which teachers should know so that tative results are correct whatever the mechanism
their presentation not be erroneously simplified a t any (electrostatic, or covalent, as discussed presently)
level. I t is important, however, to present it in such which brings them about. For d orbitals, in several
a way as to avoid creating false impressions about important geometrical situations, they are as follows:
the nature of ligand-to-metal bonds; this requires of the
In both octahedral and tetrahedral surroundings, the dw,
teacher, first, an awareness and understanding of the d, and dvz orbitals remain equivalent, as do d ~ * - and~ %dis
dangers and, sewnd, the possession of some concrete orbit&.
ideas about how to avoid them. This article presents In square surroundings, the drz and 6.orbitale remain equiva-
an outline of ligand field theory in its present state and imr, but the d,,, d,,-,I and d.1 orb~talssrenot equivalent toany
a t an introductory level; it suggests, partly in precept othem.
and partly in example, a presentation of this subject Bethe obtained these and other results by formal,
which is primarily intended to be appropriate in the group-theoretical methods, but they can also be ob-
general chemistry course, but it also raises some points tained, or at least their correctness strongly suggested,
which will be of wncern to those introducing ligand
field theory to students at any level.
"Resource Papers" is a series being prepared under the
Ligand field theory can be defined as the theory of (1) sponsorship of the Adviaory Council on College Chemistry
the origins and (2) the consequences of the splitting of aa one of the activities of the Teaching Aids Panel. The
inner orbitals of ions by their surroundings in chemical Advisory Council on College Chemistry (ACI)is supported
compounds. In this article we shall restrict attention by the National ScienceFoundation. Profeasor Charles C.
primarily to penultimate d orbitals, i.e., the 3d orbitals Price, of the University of Pennsylvania, Philadelphia,
Penna. 19104, ia the chairman.
for ions of the first transition series, 4d and 5d orbitals
for ions of the sewnd and third transition series. To a Single copy reprinta of this paper are being sent to
ohemiatry department chairmen of every US.institution
considerable degree, it is possible to deal with the two offering college ehemistry coumes and to others on the mail-
parts of ligand field theory separately; this has the im- ing list for the AC1 Newsletter. Additional single copies
portant consequence that many of the significant and will be sent free to d l interested individuals who make
relatively straightforward results of d-arbital splittings, request to the Editor of the AC1 Newsletter:
e.g., ligand field stabilization energies, stereochemical Professor E. L. Haenisoh
preferences and, of course, spectroscopic and magnetic Department of Chemistry
Wabash College
behavior, can be discussed pragmatically without neces- Crawfordsville, Indiana 47933
sarily going very far into the inherently &&cult and Multiple copy orders (in lota of.110) can be filled if
tedious question of what causes the splittings. Of accompanied by remittance of $1.50 per unit of 10 copies.
course, a truly rigorous discurnion of all the wnse- Orders m s t be add~essedto Professor H m i s c h , mt to the
quenoes of inner orbital splittimgs could not be given Jozmml of Chemieol Educatiun.
without intimately interweaving an examination of the
d ~ ~ z ~ 2 . ~ 2 iz2
Figure 2. Drawings showing how the d'z orbit01 consids of o ond
o d.2-,r orbital in equal proportions.
Actual populations 0 0 0
i 0 1 2
0
3
1
3
2
3
2
4
2
5
2
6
3
6
4
6
Stability differences 0 / / / ah 0 %/( */I %/I 0
more stable t,, orbitals. Since there are differences in mental points for the do, dS, and dlo ions, that is, to
the occupation of the more and less stable orbitals, the values which would be interpolated for other ions,
there are differences in the energies of the "uniform" if those ions had "uniformly" filled &like orbitals.
and the actual configurations. This is only a first approximation, however, since there
For the dl case, to go from the uniform to the actual are other effects, such as the non-uniform variation of
configuration, 2/6 electron is transferred from the e, ionic radii, to be discussed shortly, which must be
to the tz, orbitals. There is thus a stability increase considered; these effects are not believed to be large
(energy decrease) of 2/6An. Again, for the d' case, (8).
, .
electron is transferred from e, to t,, orbitals, caus- Similar results are obtained for lattice energies and
ing an increase of 4/sAo in the stability. The stability for the energies of other processes where complexes
differences so obtained for all the dn ions are listed, are formed; see George and McClure for general
in units of An for each ion, in Table 2. background and reference (9) for some more recent
results. By reasoning analogous to that embodied
Table 2. Ligand Field Stabilization Energies in Octahedral in Table 1, the LFSE's for tetrahedral complexes can
and Tetrahedral Liaand Fields be deduced. These are also given in Table 2.
No. of -LFSE'-
electrons Oct Tetra
--
a At i s generally < d.for a. given ion with common ligands.
Wave-Length, Angstroms
0
2000 4000 6000 8000 ioooo 1200
I I I I I
25.000 20.000 15,000
Frequency, c m - '
Figure 14. The visible obrorption spectrum of [ T ~ ( H z O ) ~ ~ ~ + .
approximation, or as a half truth which further study (8) HUSH,N. S., AND PRYW,N. H. L., J. Chem. Phys., 28,
would not contradict, but merely qualify and enlarge 244 (1958).
upon. I believe that most teachers a t some time find it (9) BLAKE,A. B., AND COTTON,F. A., Inorg. Chem., 3, 5
(1964).
necessary to use the general approach of beginning a
(10) MCCLURE,D. S., P h y ~Chem. Solida, 3, 311 (1957); Du-
topic with a facile half truth and that this is fair prac- NITZ, J. D., AND ORGEL,L. E.,Phys. Chem. Solids, 3,
tice. I do not believe, however, that it is ever justified 318 (1957).