M.

Kilner and
J. M. Smith' d' Energy Level Diagram
University of Durham
Durham City, England A n experiment for advanced students

Lectures on theories of bonding in transi- understanding and saves recourse to lecture notes in
tion metal complexes are playing an ever increasing t.his first instance.
role in the teaching of transition metal chemistry to
The Script
undergraduates. For example, the concepts of crystal
and ligand field theory are used in discussions of the Introduction
spectral and magnetic properties of complexes, and
students are expected to have some understanding of Because of the differing symmetry properties of d
energy level diagrams and how these are used to inter- orbitals, their initial degeneracy is removed when they
pret spectra and spectral changes brought about by are brought under the influence of external fields other
variations of the central metal ion and ligands. than a uniform spherically symmetrical one. Similarly,
I n order to provide practical experience in the use of the Russell-Saunders states associated with the various
energy level diagrams, an experiment was devised and d orbital configurations are also split. I n the case of
has been in use here for two years as part of the third an electronic configuration dl, the 2D state is split by
year (final) honors inorganic chemistry course. A r e the octahedral (Oh)field into %T2and 2E states (Fig. 1).
cent paper (I), based on the spectra of Cr(II1) com- This also applies to the d8 configuration case, which by
plexes, is concerned primarily with the spectrochemical application of the "hole formalism" we may write as the
series. Students prepare samples of three complexes, inverse of the d' diagram (Fig. 1). (Note that both d'
measure the spectra and (since the low energy transi- and d ghave ground states.)
tion gives a direct measure of A, the crystal field split-
ting energy) arrange the ligands in order of increasing
A (the spectrochemical series). We have used a dif-
ferent approach in designing the present experiment.
The spectra of six complexes, samples of which are
provided, are recorded, and the results used to plot an
energy level diagram. The experimental work is fol-
lowed by a series of questions, based upon the derived
diagram, which do not require additional information
beyond that obtained by the student himself. The
aim of the questions is to give the student experience
in the use of energy level diagrams, and to illustrate
some fundamental points of transition metal spectra.
The list of supplementary questions is not normally
used as it involves knowledge of topics not at present
covered in the lecture course. However it illustrates
the amount of information which may be obtained from
the basic experiment.
The experiment is designed for a specialist course in
transition metal chemistry, either at a final under-
graduate level, or preferably at a graduate level when
Figure 1. Energy level diagram ford' and d Qconfigurations.
the supplementary questions could be used to ad-
vantage.
Throughout the experiment students are expected Other multi-electron systems are more complicated
to consult their lecture notes and textbooks (9, 3,) for because the interaction of several electrons gives rise
background information, to read review articles (4-6), to a series of Russell-Saunders states, D, F , P, G
original papers of direct interest (7-9), and more ad- etc., which are affected differently by the Oh field. For
vanced hooks (10,II). example, the dZ configuration gives rise t o 3F, 'D,3P,
The Experiment
'0, and ' S states (see ref. (5)), which are split by the
ligand field according to Figure 2.
The script given to the students is reproduced below. Now for d8, the relative energies of the Russell-
The introductory section contains sufficient theory to Saunders terms in the free ion are also 3F, ID,3P, etc.
enable the student to conduct the experiment with (in order of increasing energy), hut the splitting of the
LPresent address: Sunderland Technical College, County individual terms will be the inverse of those for the d2
Durham, England. energy diagram (Fig. 2).
94 / Journctl of Chemical Educofion
 ing the various states. Alternatively, given that the
d8 OCt. free ion T - -P separation is 15,836 cm-I (1.9) and that
the energy of the aA2ground state varies with A ac-
cording to

construct the Orgel diagram for Ni(I1).

Care should be taken in assigning transitions to the
various absorption maxima. The shoulders observed
on absorption peaks for several complexes can he ig-
nored in this treatment of the spectra. However, it
is most important not to confuse a shoulder which is
part of the "fine structure" of a given transition with

Figure 2. Energy level di0gr.m. for d2 and d B configuroiionr
Origin of Spectra
When an electron undergoes a transition from the
ground state to an excited state, thc molecule must
absorb energy. I n the case of the d-d transitions the
absorption bands occur in the near uv, visible, and the
near ir. To a first approximation, the observed d d
transitions are forbidden, but more refined theory allows
them to occur to give weak absorptions, as the Laporte
selection rule is broken down. The spin selection rule
may also be overcome, and when it is we observe very
weak bands ~vithan intensity of about that oh-
served for spin allowed transitions. The absorption
bands expected in the spectra of d8complexes are
Jll?
--- (F)
a.42 =T,(P)
- -
an absorption due to a transition between different
states (e.g., in some spectra, there is a shoulder on the
side of the 3Az 3T1(F) transition which should not
be confused with the 3A, absorption which may
be found at much lower frequencies). Difficulties of
this type will occur in complex 1 in the 800 mF region,
and in complexes 4 and 6 in the 700 mp region.
Questions
1. Give assignmeuts lo the two bauds in the spectrom of
eompomd 5, and estimate the freqlrency of the missing
hand.
-
2. Estimate Lhe frequency of the ahsorption maximum far the
qA.3T,(P) trarrsition in complex 1. Why is i t not possible
to get this directly from the spectrum?
3. Predict the posit,ion of the absorption maxima fur Ni(o-
phen).804.01120 (16)and KNiFa (14, 17) and with the aid of
Figure 3, dedilce t,he color of these compo~ulds. KNiFa
in the solid state has the perovskite structure with the
Ni(I1) iurm oetahedrally surrounded by fluoride ions.
-
1 1
Near1 1 1
1
InfraredRed Orange Yellow Green Rlue Violet cm.-'
13,300 15,400 17,000 19,000 20,400 23,800 25,600

-
and possibly some spin forbidden triplet-singlet bands. Figure 3. The visible region of h e spectrum.
The transition energy for the lowest energy absorption
(3A2 3T2)for the d8 case gives the value of A directly 4. Arrange the various ligands in the spectroehemical series
for the complex under investigation. It is therefore in order of increasing A.
possible to derive an energy level diagram for the var-
ious states, based upon the ground state 3A2as the
energy zero for all values of A. If, however, the varia-
-
5 . Suggest an explanation for the presence of the shoulder on
the low frequency side of the $A2 ST,(F) transition in
complex 4.
6. Discuss the differences in the spectra of the complex6 when
tion in energy of the 3A2ground state with A is known, in acet,one and aqueous KNCS. A diffuse reflectance
an Orgel diagram may be constructed. A knowledge
-
soectmm of solid KaNi(NCSh.4H,O eave the followine
of the 3F- BPfree ion separation enables a more precise
diagram to be constructed as it avoids the need for
extrapolation to A = 0.
-
ibbsorption maxima: -25,800
em-' (=Aa >T,(F)) and 9600 ern-' (8A1
@A;- I T , ( P ) ) 15,95i
ITl). G ~ v e
reasons for the differences between the spectra when de-
termined in aqmous KNCS and in the solid state.
7. Calculate extind.ion coefficients for the absorption peaks in
Object of the Experiment one spectrum. Comment upon the difference between these
To construct the energy level diagram for Ni(I1)
(within the limits dictated by the various A values for
the ligands) from the spectra obtained for the series Solvent and
of complexes, and to use this to derive spectral and Complexa Blank Concentration
other information on nickel complexes in general. Wnter
20% en
Method Aqueous N131
Water
Weigh sufficient material to prepare 10 ml of a M/20 U.M.S.0.
solution of each complex listed in the table, and record
its spectrum in the region 30&1000 mF. Plot the Acetone M/400 and M/1600
IOM KNCS nr/zo
energy level diagram E versus A based upon the ground in water
state 3Az as the energy zero for all values of A (E and bipy = 2,2'-bipyridyl, en = ethylenedismine, D.M.S.O. =
A in units of cm-') for the complexes 1-4, clearly label- dimethylsdfoxide.

Volume 45, Number 2, February 1968 / 95

 in the 300-700 mfi region
using a Unicam SPSOO spec-
COMPLEX
trophotometer and the region
-= 1 700-1000 mfi is scanned man-
..... = 2 SEE TEXT
.---- ually using an SP600 instru-
-.-r. = 4
SOLVENTS ment. A sample spectrum of
the absorption at 1175 mfifor
[Ni(HpO)6]SOa is given to the
student. Xormally, the re-
sults (Fig. 4) are used to plot
an energy level diagram
based upon the ground state
3A2as the energy zero (Fig. 5)
and the student then pro-
WAVELENGTH ceeds with the questions 1-7.
Alternatively, using eqn. (I),
the Orgel diagram (Fig. 6)
Figure 4. Absorption rpectro of the compiexe, in the region 300-1.000 m p
may be obtained.

values and those for d-d transitions in tetrahedral con>-
plexes, e.g., NiCL1- (t = 200) and for charge transfer traosi-
tions (C = lo4 - lo5) e.g., iUnO+-.
Supplementary Questions
8. Use eqn. (1) to constmot the Orgel diagram.
9. Using eqn. (l),determine the mean energy (E) (Fig. 2)
of the T state, relative to the aAA.ground state, for com-
~ l e x e 2-6.
s Use the diffuse reflectance data for com~lex6.
Calculate the energy (aT,(P) - E) for each value of A ; this
gives E.,, of eqn. (2).
10. Substitute for E., in the following equstion and obtain
P for each complex.
Notes o n the Script and Experiment
Of the many possible transition metal ions which
could have been chosen for the experiment, the trivial
d'/d9 cases were not considered, nor the d4, d5, d6
cases where there is the possibility of a change in ground
state terms for different complexes (although such cases
would make an excellent experiment in conjunction
with magnetic measurements). Ni(1I) was considered
to be a good choice from the remaining possibilities
as there are many octahedral Ni(I1) complexes afford-
ing a wide range of A values. Furthermore, the spectral
properties of Ni(I1) complexes have been extensively
studied so that such information is readily available (7,
9-12) as are preparative details (8, 12, 17). The spec-

This equation (18) relates the energy of the T, terms l o the
crystal field splitting A, and the =F- -'P term separation, P.
Assuming that the 3F - IP separation in the complexes is
the same as in the free ion, the equation can he solved for
values of E, far a. given A. The Lwo solutions refer to the
energ* of t.he aTI(F) and STI(,P)states. Thus using eqns.
(I), (2), and the energy relatranship
-
tral results from this system are very suitable for inter-
pretation by students because A values are obtained
directly from the spectra (3A2 3T2) and complica-
tions due to spin orbital interactions are kept to a mini-
mum.
For the spectral determinations, we found it necessary

the Orgel diagram can be constructed from theoretical

principles.
Since complexes deviate from the paint charge electro-
static model, and orbital interaction between the metal
and ligands occurs, the experimental energies of the various
states differ from those calculated. Alt,ernat,ively, b>
snbstituting one experimental value (for STI(F) or 3T1(P))
in eqn. (Z),a calculated value of P, the aF - 3Pterm sepa-
ration in the complex, can be obtained.
11. Obtain the Racah parameter. B, for each ligand. The
Racsh parameter, B, - 3P term separation in complex
t aF- JPterm separation in the free ion) gives ameastre of
the orbital interaction between the metal and the ligands.
Far the gaseous Nix+ion, the 3F - =Pterm separation is
15,836 em-' (19).
12. Arrange the ligands in order of their decreasing B values.
This gives the nephelauxetic series.
13. Comment upon differences in order between the nepbelauxe-
tic and spectrochemical series.
14. Explain why the energy versus A correlations for SZ't(P)
and ST,(F) deviate from linearity.

Practical Details
Students are not required t o prepare the complexes,
but from given samples, they m k e up solutions to the Figure 5. Energy level diagrorn obtained from the measurements, taking
specified concentrations. The spectra are determined the ground state % 03 the energy zero for all valuer of A.

96 / Journal of Chemical Education


Figure 6. Orgel d i a g r a m obtained from tho measurements assuming
EIW = - 665 a.
to use 2 cm cells as the Unicam SP800 instrument gives
a display which is linear in absorbance units (G2.0)
(Fig. 4). For many complexes, it was not possible to
obtain a sufficiently concentrated solution, using 1 cm
cells, to give a satisfactory display of the spectra on the
paper. However, if results are presented in per cent
transmission, 1 cm cells may be used, or alternatively
2 cm cells with reduced concentrations. The latter
reduces the amount of sample used and facilitates dis-
solution of the complexes.
The basic experiment involves the construction of
an energy level diagram with the ground state 3Az as
the energy zero for all values of A. This diagram (Fig.
5) is quite sufficient for the student to carry out ques-
tions 1-7 without any further information being sup-
plied. However, the - 3Pseparation energy may be
incorporated on this diagram when the curvature of the
3T1(P) term becomes more apparent. Alternatively,
one may extrapolate the 3T1(P)level to A = 0 to obtain
a rough estimate of the 3F- 3Pterm separation which
is found to he between 14,000 and 17,000 cm-' (Fig.
5 ) . For questions 8-14 the given 3F-3Pterm separa-
tion should be used in conjunction with eqn. (1) to
obtain the Orgel diagram (Fig. 6).
If students first plot the data for complexes 2 , 3 , 4 for
which all the information is available, it is possible to
deduce the missing bands in complexes 1 and 5 simply
-
by attempting to fit the available points onto the graph
already obtained. The curvature of the a T ~ ( F plot, ) (19) MOORE,c.E., "Atomic Energy Levels," National Bureau of
giving a value of 19,200 om-' for 3Az 3T1(F) transi-
tion in complex 1 means that, for the student who is
not aware that bipyridyl is a strong ligand, some thought
must be given to the assignment of the two frequencies
available. It is, however, rather diicult to assign
complex 5 to other than a weak field position on the
diagrams. I n attempting an answer to question 5 ,
-
most students discuss effects of lowering of symmetry
on the absorption hands before arriving at an explana-
tion in terms of 'Az 'E transitions. Few students
without direction have discussed the ideas of Ballhausen
and co-workers (11) with regard to the appearance of a
double peak in the region under discussion. Question
6 is designed to bring the students' attention to the
problem of changes in ligand coordination and stereo-
chemistry upon dissolution of complexes. The spec-
trum of KNi(NCS)Beven in 10M KNCS is very dif-
ferent from that for the solid complex and in aqueous
solution without added KNCS it is similar to that for
Ni(H20)s2+.
Although the supplementary questions have been
written so that a student can work through them un-
aided, nevertheless it is intended that some discussion
of Racah parameters and interelectronic repulsions be
undertaken with the student at the time these questions
are attempted.
Literature Cited
(1) DUNNE,T. G., J. CHEM.Enuc., 44, 101 (1967).
(2) COTTON,F. A,, AND WILKINSON, G., "Advanced Inorganic
Chemistry" (2nd Ed), John Wiley & Sons, Inc., New York,
1966.
(3) L E ~ J.,
$ AND WILKINS,R., Editors, "Modern Co-ordina-
tion Chemistry," Interscience Publishers, London, 1960.
(4) COTTVN,F. A,, J. CHEM.EDUC.,41,466 (1964).
(5) S U ~ NL., E., J. CHEM.EDUC.,37,498 (1960).
(6) MANCH,W., AND FERNELIUS, W. C., J. CHEM.EDUC.,38,
D. W., DRAGO,
R. S., AND PIPER,T. S., Inorg. Chem.,
(9) FORSTER, D.,'ANDG O O D ~ MD.~ M.
, L., Imrg. Chem., 4 , 8 2 3
1196.5).
~ ~,
(10) J#RGENSEN, C. K., "Absorption, Spectra and Chemical
Bonding in Complexes,'' Pergamon Press, Inc., New York,
1067
(11) BALLHAUSEN, C. J., "Introduction to Ligand Field Theory,"
McGraw-Hill, London, 1962.
(12) MORGAN, G. T., AND BURSTALL, F. H., J. Chem. Soc., 2213
(1931).
, G., Editor, "InorganicSyntheses," 6,200(1960).
(13) ~ o ' c e o wE.
(14) PALMER,W. G., "Experimental Inorganic Chemistry,"
Cambridge University Press, 1959, p. 564-7.
(15) "Gmelin Handhuch der Anorganischen Chemie," Verlag
Chemie, 57, 1058 (1966).
(16) PFEIFFEH, P., AND NAKATSUKA, Y., Ber., 66, 415 (1933).
(17) ADAMS,D. M., AND RAYNOR, J. B., "Advanced Practical
Inorganic Chemistry," Wiley, London, 1965, p. 57.
(18) DRAGO, R. S., "Physical Methods in Inorganic Chemistry,"
Reinhold Publishing Corp., New York, 1965, p. 168 and
din
Standards, No. 467.
Volume 45, Number 2, February 1968 / 97