B A N D 27 b Z E I T S C H R I F T FÜR NATURFORSCHUNG HEFT 1

The Nephelauxetic Effect — Calculation and Accuracy

of the Interelectronic Repulsion Parameters
II. Application to d3 and d7 Single Crystal Spectra
at Cryogenic Temperatures *
E. KÖNIG

Institut für Physikalische Chemie II, Universität Erlangen-Nürnberg, 8520 Erlangen, Germany

(Z. Naturforsch. 27 b, 1—5 [1972] ; received September 28, 1971)

Expressions are reviewed which may be used to determine 10 Dq and B from the spin-allowed
bands in the optical spectra of d 3 and d 7 electron systems within octahedral and tetrahedral sym
metry. Application to low-temperature single crystal spectra demonstrates that (i) the semi-empiri-
cal ligand field theory reproduces transition energies with sufficient accuracy; (ii) differences in
the values of 10 Dq and B observed with different fitting methods may be attributed to the in-
accuracy of experimental data; (iii) there are generally valid values of B35 and /? 33 for each com-
plex ion.

The semi-empirical ligand field theory provides
means to completely determine the electronic d — d
spectra of transition metal ions of octahedral sym-
metry in terms of three parameters: the octahedral
splitting parameter 10 Dq ( = A) and the inter-
electronic repulsion parameters ( = Racah para-
meters) B and C which are linear combinations of
the C o n d o n - S h o r t l e y parameters F2 and
An analogous statement applies to tetrahedral sym-
metry and one or two additional parameters (e. g.
Ds and Dt in tetragonal environment) are required
if the symmetry is lower than cubic. In general, the
numerical values of the parameters B and C, as
determined from d — d spectra, are lower than the
values in a free transition metal ion. This observa-
tion is well known as the nephelauxetic effect 2' 3.
In the first part of this study 4 , the author has re-
cently reviewed and tested methods which may be
used to determine 10 Dq, B, and C from electronic
spectra. To focus the attention on the value of B,
these methods were applied to the spin-allowed d — d
bands in high-spin d 2 , d 3 , d 7 , and d8 complexes of
octahedral and tetrahedral microsymmetry. In the
expressions of the corresponding transition energies,
the parameter C does not occur 5 . In addition,
10 Dq may always be fixed by a suitable choice of
the calculation method. A convenient check on the
accuracy of the employed numerical procedure is
provided by calculating the extra band energy, if
those complex ions are considered where all three
spin-allowed d — d bands are observed. Room tem-
perature solution and single crystal spectra of al-
most fifty complexes and impurity ions of the
transition metals were subject of the analysis. The
results 4 may be summarized as follows:
(i) The accuracy of B and 10 Dq depends on the
1.
method adopted to their calculation. Conse-
quently, certain methods may be selected which
provide the "best" possible fit to the experi-
mental data;
(ii) Given a specific method of calculation, an un-
systematic variation in the deviations between
calculated and observed transition energies is
often encountered. It was suggested that this
is due to insufficient accuracy of the experi-
mental room temperature (solution) data.
In the present contribution, the same methods as
used previously 4 will be applied to single crystal
spectra measured at cryogenic temperatures. It will
be demonstrated that results somewhat different
from those of room temperature spectra are ob-
tained.
I. Ligand Field Theory of d3 and d7 Ions
in Cubic Fields
The general treatment of ligand field theory is
adequately covered in several textbooks 7 - 9 to which

Requests for reprints should be sent to Doz. Dr. E. KÖNIG, * For the first part of this study refer to E. KÖNIG, Struct.
Institut für Phys. Chem. II der Universität Erlangen-Nürn- Bonding 9, 175 [1971].
berg, D-8520 Erlangen, Fahrstr. 17.

G ZT-I'H)^
 E. K Ö N I G

reference is made here. With respect to the single (b) fitting the first and third band,
crystal data available at present, we will concentrate 10 Dq = 2 ?>! — j>3 + 15 B, (8)
primarily on the theory of d3 and d 7 ions in cubic
fields. The relevant energy expressions have been B = jo[-{2Vl~ ± ^~ + *»* + "1 >'3>,/!] ,
derived previously 4 . For convenience, we will
(c) fitting the second and third band,
briefly introduce those quantities and list explicitly
those expressions which will be needed in the sub- 10 Dq= I (2 v2 — v3) + 5 5 ,
sequent numerical calculations.
Thus in the octahedral d3 configuration three ß = 510 2) ±3{81r s 2 -16^(r2-ra)}''•].
spin-allowed transitions from the 4 A 2g ground state (9)
to the excited states 4 T 2 g , a 4 T l g , and b 4 T i g are
(d) fitting the difference between the first and
expected. Within the approximation considered
second band,
here, the energy of the lowest transition is always
determined as vx ( 4 A 2g —> 4 T 2g ) = 10 Dq. The ener- 10 Z)g = — J'i,
gies of the two higher transitions follow from B=(v2 + V3-3V1)/15. (10)

>'2,3= 2 (15B + 3O0<7)+-2 t( 1 5 ß - 1 0 ^) 2

II. Application to Single Crystal Spectra
+ 12 B • 10 Dq]1'1. (1)
In order to asses the accuracy of the parameter
The parameter B may then be obtained according
values of 10 Dq and B, the equations listed in sec-
to four different methods:
tion I will be applied below to some recent low tem-
(a) fitting the second band,
perature single crystal spectra. Following the first
5 = (2v12 + v22-3vlv2)/ (15 v2 — 21 vt), (2) part of this study 4 it will be assumed, for the sake
(b) fitting the third band, of argument, that the three-parameter (10 Dq, B, C)
B = (2 Vi2 + f 3 2 - 3 n r 3 ) / (15 v3 - 27 vt), (3) theory is valid exactly. The question then arises
about the significance of the calculated transition
(c) fitting the sum of the second and third band,
energies. In ligand field theory, all energy dif-
B=(v2 + r3-3v1)/15, (4) ferences are calculated at a constant value of 10 Dq
(d) fitting the difference between the second and (viz. "vertical" transitions in the T a n a b e - S u -
third band, g a no diagram). Since the relation 10 Dq ~ R~5
holds to a reasonable approximation 10 , this is equi-
B= ^ [3 f ! ± (25 0>3 - v2)2 - 1 6 V ) I / 2 ] • (5) valent to a fixed metal-ligand distance, R. In the
spin-allowed d — d transitions considered here, the
The expressions (1) to (5) apply to tetrahedral d 7
states involved originate in different strong field
ions as well.
configurations g eg and, consequently, the potential
In the octahedral d7 configuration, the ground
minima of the excited state and the ground state do
state is a 4 T l g and the excited quartest states are, in
not coincide. The calculated transition energy cor-
the order of increasing energy, 4 T 2 g , 4 A 2 g , and
responds, therefore, to the energy of a transition
b 4 T l g . The energy of the three spin-allowed transi-
from the zero-point vibrational level of the elec-
tions is determined according to
tronic ground state to an excited vibrational level
"i (a4Tig 4 T 2g ) = I (10 Dq - 1 5 B) + , of the excited state (cf. "vertical" transition ac-
cording to the F r a n c k - C o n d o n principle).
v2 (a 4 T ig -> 4 A 2g ) = vx +10 Dq , (6)
As far as the comparison between theoretical and
r 3 (a 4 T l g -^b 4 Ti g ) = [(10Z)q + 15 5 ) 2
experimental energies is concerned, two limiting
— 12 5 - 1 0 Dq]1/!.
conditions may be distinguished:
There are again four different methods which may (i) In centrosymmetric (e.g. octahedral) com-
be employed to obtain the parameters 10 Dq and B: plexes, all d — d transitions are rigorously forbidden
(a) fitting the first and second band, on the basis of parity. The forbidden electronic
10 Dq — v2 — vl, transitions may gain intensity through coupling
B= (2v12-v1v2)(Uv2-27 vt), (7) to odd vibrations (vibronic mechanism n ) . At low
 THE NEPHELAUXETIC EFFECT 3

temperatures, each band thus consists of a progres-
sion in one or more even vibrations superimposed
upon one quantum of the odd ("permitting") vibra-
tion. The no-phonon ( 0 " —> 0') band is absent or
of very weak intensity 12 . Therefore, within reason-
able approximation, the calculated vertical transition
energy should be associated with the maximum of
the vibronic band determined, in principle, at 0 °K.
(ii) In non-centrosymmetric (e. g. tetrahedral)
complexes, the d — d transitions become partly al-
lowed on account of mixing with odd-parity states
of the central ion (e.g. p states 11 ). One observes,
at low temperatures, a progression in the totally
symmetric vibrational mode originating in the no-
phonon (0"—>-0') band. Normally, the highest
intensity would be expected in one of the higher
vibrational sub-bands 0 " - > n / e v e i l . However, in
the example studied at present 13 ' 14 , the most pro-
minent band is associated with the no-phonon
transition. This situation is encountered if ground
and excited state potential minima occur at the same
internuclear distances12. It has been suggested 13 ,
therefore, that the geometry of the Co2® ion in the
relevant excited states is not greatly different from
that in the ground state. Here it may be more ap-
propriate to approximate the calculated vertical
transition energy by the average of the energies of
the no-phonon bands in the most intense spin-orbit
components determined again, in principle, at 0 °K.
If the temperature is increased, in both cases
higher vibrational levels of the electronic ground
state become successively populated and the cor-
responding band in the electronic spectrum is pro-
gressively shifted to lower energy 15 . The magnitude
of the shift is dependent on the distribution of the
vibrational levels in the electronic ground state and
on the intensity of the resulting hot bands and will
differ from compound to compound. Therefore, in
general, spectra measured at higher than cryogenic
temperatures cannot compare favorably with theory.
III. Results and Discussion
Results of the present analysis are compiled in
Tables 1 to 3. For each compound, experimental
transition energies determined according to sec-
tion II are listed in line 1. Subsequent lines contain
the calculated transition energies, their deviation
from the corresponding experimental value, dv —
''calc (in cm 1 and in percent), and the values
of the parameters B3- and ßS5 . In Table 2, values
of 10 Dq and of the deviation, (5(10Z)g), from the
value of v2 — vt are listed in addition. Each line ap-
plies to a different method marked with reference
to section I.
In the octahedral d3 configuration, the only well
evidenced low-temperature single crystal spectrum
where the 4 A 2g —> b 4 Ti g transition has been unequi-
vocally assigned is that of VC12 1 6 ' 1 7 . If the quasi-
molecular model is assumed type (i) behaviour
is expected. No fine structure has been observed in
the 4 A 2g —> 4 T 2g and 4 A 2g a 4 Ti g bands, and thus
the band maxima listed in Table 1 are associated
with the vertical transition energies. In the 4 A 2 g - >
b 4 T l g band where a vibrational progression in a
mode of ~ 234 c m - 1 is encountered, the first pro-
minent vibrational component (viz. 22,244 c m - 1 )
seems to well approximate the centroid of the band
(viz. Fig. 1 of 1. c . 1 8 ) . The parameter values calcu-
lated by KIM et al. 1 6 are incorrect, since applying
eq (1) the fit was based on the estimated energy of
the no-phonon transition. No suitable data on the
d 3 configuration in tetrahedral environment are
known.
Recently, low temperature single crystal spectra
of RbCoCl 3 and of the Co2® ion in several chloride
lattices became available 19 . The a 4 Ti g ground state
of the octahedral d 7 configuration is split by spin-
orbit interaction into the -T 6 , r 8 a , .T8b and .T7
levels in the order of increasing energy 20 . Since
and are K r a m e r s doublets, the a 4 Ti g term

Compound Method vi, c m - 1 j>2, c m - 1 cm-1 öv B35, c m - 1 ^35

4A 2 g 4T2g 4A2g^a4 T l g 4A2g—> b 4 T i g [cm-1] [%]

VC1 2 ( 2 2 ° K ) exp 9300 14,220 22,244

a 10 Dq flitted 22,231 - 7 0.03 570.1 0.74
b 10 Dq 14,226 fitted + 6 0.04 571.3 0.75
c 10 Dq 14,224 22,240 ± 4 0.02 570.9 0.75
d 10 Dq 14,231 22,255 + 11 0.06 572.3 0.75

Table 1. Observed and Calculated Transition Energies of Octahedral Vanadium(II) (B^*® = 766 c m - 1 ) .
4 E. KÖNIG

Compound Me- vi, c m - 1 i>2, e m - 1 j'3, c m - 1 6 V £35 ßäö 10 Dq d (10 Dq)

thod a4Tlg^4T2g a4Tlg->4A2g a4Tig->b4Tig [cm"1] [%] [cm-1] [%]
RbCoCls exp. 6450 13,500 17,210
b fitted 13,855 fitted + 355 2.56 781.0 0.80 7405 + 355 4.79
c 6278 fitted fitted - 172 2.74 791.8 0.82 7223 + 173 2.4.3
d 6134 13,184 fitted - 316 3.77 757.3 0.78 7050 0 0
K M g C l 3 : Co 2 © exp. 5740 12,000 16,475
b fitted 12,367 fitted + 367 2.97 774.8 0.80 6627 + 367 5.54
c 5563 fitted fitted - 177 3.18 785.8 0.81 6437 + 177 2.7.3
d 5415 11,675 fitted - 325 4.39 750.3 0.77 6260 0 0
CsMgCls: Co 2 © exp. 6450 13,300 17,190
b fitted 13,854 fitted + 554 3.99 779.6 0.80 7404 + 554 7.48
c 6181 fitted fitted - 269 4.35 796.5 0.82 7119 + 269 3.78
d 5957 12,807 fitted - 493 6.06 742.7 0.77 6850 0 0
MgClo : Co 2 © exp. 6450 13,570 17,025
b fitted 13,849 fitted + 279 2.01 768.2 0.79 7399 + 279 3.77
c 6314 fitted fitted - 136 2.15 776.8 0.80 7256 + 136 1.87
d 6202 13,322 fitted - 248 2.93 749.7 0.77 7120 0 0
C d C l 2 : Co 2 © exp. 6040 12,500 16,930
b fitted 13,001 fitted + 501 3.85 787.4 0.81 6961 + 501 7.20
c 5797 fitted fitted - 243 4.19 802.5 0.83 6702 + 242 3.61
d 5596 12,056 fitted - 444 5.81 754.0 0.78 6460 0 0
C s C d C l 3 : Co 2 © exp. 5263 11,236 16,400
b fitted 11,376 fitted + 140 1.23 799.1 0.82 6113 + 140 2.29
c 5196 fitted fitted - 67 1.29 803.2 0.83 6040 + 67 1.11
d 5140 11,113 fitted - 123 1.75 789.8 0.81 5973 0 0
L i C l : Co 2 © exp. 6386 13,570 17,300
b fitted 13,727 fitted + 157 1,14 791.2 0.82 7341 + 157 2.14
c 6310 fitted fitted - 76 1.20 796.0 0.82 7260 + 76 1.06
d 6247 13,431 fitted - 139 1.63 780.8 0.80 7184 0 0

Table 2. Observed and Calculated Transition Energies of Octahedral Cobalt (II) in Chloride Lattices at 5 °K
Co 2 ®
(ßfree = 9 7 1 c m - ) .

Compound Method v\, c m - 1 i>2, c m - 1 j% c m - 1 öv B35, c m - 1 ^35

4 A2-^4T2 4A2 a4Ti 4A2->b4Ti [cm"1] [%]

Z n O : Co 2 © exp. 4140 7186 15,384

(4.2°K) a 10 Dq fitted 17,108 + 1724 10.08 790.4 0.81
b 10 Dq 7106 fitted - 62 0.87 671.4 0.69
c 10Dq 7109 15,443 ± 59 0.61 675.5 0.70
d 10 Dq 7103 15,319 - 65 0.67 666.9 0.69
ZnAl204: Co 2 © e x p . 4015 6914 16,210
(1.8°K) a 10 Dq fitted 15,467 - 743 4.80 689.1 0.71
b 10 Dq 6940 fitted + 26 0.38 740.3 0.76
c 10 Dq 6939 16,185 ± 25 0.26 738.6 0.76
d 10 Dq 6941 16,237 + 27 0.28 742.2 0.76

Table 3. Observed and Calculated Transition Energies of Tetrahedral Cobalt (II) in Oxidic Lattices ( # f r e e — 971 cm *).

has been effectively stabilized against the action estimated. It should be observed that, due to its low
of the J a h n - T e l l e r effect. Thus, assuming type intensity ("two-electron jump"), a high experimen-
(i) conditions, the experimental energies included tal uncertainty should be assumed for the
in Table 2 were obtained directly from the reported a 4 T l g (t|g e 2 ) 4 A 2g ( 4 e 4 ) band.

spectra. If a vibrational structure was observed (viz. In the single crystal spectra of tetrahedrally co-
the a 4 T l g - > 4 T 2 g band in CsMgCl3 : Co2® and in ordinated Co 2 0 ions, type (ii) conditions are pre-
LiCl : Co 2 ®), the centroid of the vibronic band was valent and the experimental energies are determined
 THE N E P H E L A U X E T I C
accordingly. Thus, in ZnO: C o 2 0 , it is the energies
of the highest intensity (no-phonon) vibrational
bands which are listed in Table 3, since individual
vibrational components at higher energies are con-
siderably weaker in intensity14. In ZnAl 2 0 4 : Co 2 ®,
the transition energies employed in Table 3 are
mean values of the most intense no-phonon bands in
each of the electronic transitions13. It should be
kept in mind that, due to the complicated structure
of the bands, the totality of the weak vibrational
transitions may still contribute a significant fraction
to the overall transition energy 21 .
Inspection of the results which have been col-
lected in Tables 1, 2, and 3 reveals considerable
differences to the results from room temperature
(solution) spectra 4 . If those results are disregarded
which were obtained by the most unfavorable
methods [viz. (a) in Table 3], the agreement be-
tween calculated and observed transition energies is
surprisingly good. On the other hand, there is not
much that could be gained by choosing between
methods (b), (c), and (d) in octahedral d 3 and
tetrahedral d7 spectra. Most important, the deviation
between the values of B35 calculated by different
methods is negligible and that of ß35 is practically
non-existent. In Table 2, differences between results
obtained by methods (b), (c), and (d) are some-
what larger but still considerably smaller than in the
room temperature spectra 4 . In addition, the smallest
differences are encountered in those spectra where
the best resolution in the a 4 T l!? 4A2g. band has
been achieved, cf. CsCdCl3 : Co2® and LiCl : Co 2 ®.
Thus, if the complications inherent in the data are
1 E . U . CONDON a n d G . H . SHORTLEY, T h e T h e o r y o f
mic Spectra, Cambridge University Press, Cambridge
1959.
2 C. K. JORGENSEN, Progr. inorg. Chem. 4, 73 [1962].
3 C . E . SCHÄFFER a n d C. K . JORGENSEN, J . i n o r g .
Chem. 8, 143 [1958].
4 E. KÖNIG, Struct. Bonding 9, 175 [1971].
5 In this way certain problems associated with the treatment
of C are eliminated. Thus there is evidence that the para-
meter C is not susceptible to the nephelauxetic effect to the
same extent as B 6.
8 H. WITZKE, Theor. chim. Acta 20, 171 [1971].
7 C. J. BALLHAUSEN, Introduction to Ligand Field Theory,
McGraw-Hill, New York 1962.
8 J. S. GRIFFITH, The Theory of Transition Metal Ions,
University Press, Cambridge 1961.
9 H . L . SCHLÄFER U. G . G L I E M A N N E i n f ü h r u n g i n d i e
denfeldtheorie, Akademische Verlagsgesellschaft, Frank-
furt a. M. 1967.
10 E. KÖNIG and K. J. WATSON, Chem. physic. Letters 6, 457
[1970].
EFFECT 5
taken into account, the results of octahedral Co2®
ions are similar to those discussed above.
IV. Summary and Conclusions
We have reviewed expressions which were derived
previously, on the basis of the semi-empirical ligand
field theory, to determine 10 Dq and B from the
spin-allowed bands of d3 and d7 electron systems of
octahedral and tetrahedral stereochemistry. These
equations were applied to low-temperature single
crystal spectra of suitable compounds and the extra
band energy was calculated.
Provided the spectral data employed are repre-
sentative for most systems of the studied electron
configuration, the conclusions arrived at are as fol-
lows :
(i) the semi-empirical ligand field theory repro-
duces quite accurately the transition energies,
at least in spin-allowed bands of d 3 and d7
systems of cubic symmetry;
(ii) the differences in the parameter values 10 Dq
and B resulting from the application of dif-
ferent fitting methods are due essentially to in-
accuracy of the experimental data;
(iii) there exist generally valid values of the inter-
electronic repulsion and nephelauxetic para-
meters B35 and ß35 for each complex ion which,
however, may be determined only if sufficient-
ly accurate experimental data are available.
This study has been sponsored in part by research
grants of the Deutsche Forschungsgemeinschaft, the
Stiftung Volkswagenwerk, and the Fonds der Chemi-
schen Industrie whose support is gratefully appreciated.
Ato- 11 C. J. BALLHAUSEN, Progr. inorg. Chem. 2, 251 [ I 9 6 0 ] ,
12 G. HERZBERG, Molecular Spectra and Molecular Structure,
Vol. 3, Van Nostrand, New York 1966.
13 J. FERGUSON, D . L . W O O D , a n d L . G . V A N UITERT, J. c h e m .
nuclear P h y s i c s 51, 2 9 0 4 [1969].
14 R . PAPPALARDO, D . L . W O O D , a n d R . C . LINARES, J . c h e m .
Physics 35, 2041 [1961].
15 J. LEE and A. B. P. LEVER, J. molecular Spectroscopy 26,
189 [1968].
16 S. S. KIM, S. A. REED, and J. W. STOUT, Inorg. Chem. 9,
1584 [1970].
17 Recently, SMITH 18 likewise studied single crystal spectra
of V C l , and of the V 2 ® ion in several chloride lattices at
6 ° K . However, since quantitative energies were not re-
ported, these results could not be included into the present
study. SMITH 18 claims that ligand field theory fits his re-
Ligan- sults rather well. This would support and extend our pre-
sent conclusions.
18 W . E . SMITH, J. d i e m . S o c . [London] A 1969, 2677.
6 H. B R E U E R UND H.-H. P E R K A M P U S

19 F. C. GILMORE, US At. Energy Comm. ORNL-TM-2507 21 Apparently, the centers of gravity reported 14 or estimated 4
[1969], in these two tetrahedral cobalt (II) systems are not ap-
20 A. D. LIEHR, J. physic. Chem. 67, 314 [1963]. propriate to the present analysis.

Auswertung nmr-spektroskopischer Messungen

der Mischassoziation yon Nucleosid-Derivaten bei vergleichbaren
Konzentrationsverhältnissen
Evaluation of NMR-spectroscopical Results about Co-association of Nucleoside
Derivatives in Comparable Concentrations
H . BREUER * u n d H . - H . PERKAMPUS

Institut für Physikalische Chemie der Universität Düsseldorf

(Z. Naturforsch. 27 b , 6—12 [1972] ; eingegangen am 31. August 1971)

In this paper we described a method how to calculate from N M R the association — caused by
H-bonds — of two components. These components may be present in equal concentration and
may be partially self-associated.
The may act as H-donors and acceptors. The method is demonstrated using some nucleoside
derivatives as examples.

In einer vorangehenden Arbeit haben wir über schiedener Umgebung, es müssen also auch zwei
NMR-spektroskopische Untersuchungen zur Misch- verschiedene chemische Verschiebungen für das
assoziation von vier Nucleosid-Derivaten berichtet1. „reine" Mischassoziat existieren, die jeweils die
Die Auswertung erfolgte mit Hilfe einer modifizier- Lage der zwei beobachteten Signale beeinflussen. Sie
ten B e n e s i - H i l d e b r a n d - Auftragung: gehen dabei mit dem einfachen Gewicht der Misch-
i . i i assoziations-Konzentration ein, wenn ein 1 : 1 -
V b ~ Vmb V x b — Vmb
+ (t>xb~i>mb) '^x Cma Mischassoziat vorliegt. Die folgende Abb. 1 veran-
Hierin bedeuten: v^ gemessene chemische Verschie- schaulicht dies. Dabei bedeuten die gestrichelten
bung der Komponente b, i>mb extrapolierte chemische Linien die hypothetischen Signale der einzelnen
Verschiebung des Monomeren b, f x b berechnete che- Spezies, und die ausgezogenen Linien entsprechen
mische Verschiebung der Mischassoziate, Kx Misch-
~ca = cma+2cna + cab
assoziations-Konstante in 1/Mol, c ma Monomeren-
konzentration der Komponente a.
c ma läßt sich leicht berechnen, wenn die zugehö-
~cb=cmb+2cnb + cab
rige Eigenassoziations-Konstante bekannt ist.
Um dieses Verfahren anwenden zu können, müs-
sen einige Voraussetzungen erfüllt sein. Für die
Substanz im Überschuß muß gelten: gute Löslichkeit 'cmb
und ideales Verhalten sowie genaue Kenntnis der ~cab 'Cab
Parameter der Eigenassoziation. Die Substanz im
~2cn
Unterschuß muß ein H-Brücken-Protonensignal lie-
fern, das möglichst weit von Signalen ihrer Mi- J2cnb
schungspartners entfernt liegt. Die Verbindungen
vxa vna va vnb vma vxb vb vmb
sollen ferner eine geringe Eigen-, aber eine starke
Mischassoziation zeigen. chemische Verschiebung

Abb. 1. Schematisches Spektrum der H-Brücken-Protonen-

Herleitung der Auswertemehode
In den beiden Molekülen eines Mischassoziats be-
finden sich die sauren Protonen in chemisch ver-
signale für die Mischassoziation, v, vn , i>m gemessene Ver-
schiebung, Eigenassoziat-Verschiebung, Monomerenverschie-
bung, c, c n , c m Einwaage-, Eigenassoziat- und Monomeren-
Konzentration.

Sonderdruckanforderungen an Prof. Dr. H.-H. PERKAMPUS, * Jetzige Anschrift: Dr. H. BREUER, 34 Göttingen, Theodor-
Institut für Physikal. Chemie der Univ. Düsseldorf, D-4000 Heuss-Str. 18.
Düsseldorf, Fa. Henkel, Gebäude Z 10.