Zeitschrift fr Physikalische Chemie Neue Folge, Bd. 101, S.

197208 (1976)
by Akademische Verlagsgesellschaft, Wiesbaden 1976

The Frster Cycle Reconsidered

By
Zbigniew R. Grabowski and Anna Grabowska
Institute of Physical Chemistry, Polish Academy of Sciences, 44 Kasprzaka,
01-224 Warsaw, Poland

With 5 figures
(Received November 10, 1975)

The Frster cycle is reconsidered, with emphasis on the thermodynamic

approximations and on the necessary experimental precautions. Some examples
of acid-base equilibria in excited states are discussed along with new possible
applications of the cycle.
Der Frster-Zyklus wird neu diskutiert unter Bercksichtigung thormodyna-
mischer Nherungen und mglicher Mefehler. Einige Beispiele von Sure-Base
Gleichgewichten in angeregten Zustnden und neue mgliche Anwendungen des
Zyklus werden diskutiert.
Just after the discovery of protolytic reactions occuring within
the lifetime of electronically excited states [1], Theodor Frster
proposed a term scheme to interpret the observed effects which since
that time is known in the literature as the "Frster cycle" [2] (Fig. 1).

-B* H*
+

"T
hcvn.
hcvn.

+H*
Jri.

(A) (b)

Fig. 1. The Frster cycle for a reaction A ^ + H+; AHostandard heat of

reaction

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IOS Zbigniew R. Grabowski and Anna Grabowska

The cycle combines thermodynamic and spectroscopic data and allows

one to predict the chemical equilibrium constants in the excited
states :

pK* pKG -
(i& j&) -
(1)

where the asterisk and 67 refer to the excited and ground states
respectively; for an acid-base reaction
A ^B + H+ (2)
[fJ+l I 7? "I
the equilibrium constant =

.
, and pK =

logio K;
v~Q and i-QQ the wavenumbers of the pure electronic transitions in
are
the conjugate acid and base, correspondingly.
hi numerous cases quantitative studies using independent methods
have demonstrated the high degree of its reliability [3,4]. As will be
shown, the cycle can be applied to many equilibria involving electroni-
cally excited species. One of the most important features of the cycle
is the possibility to use it even in cases in which the equilibrium cannot
be physically established within the lifetime of the excited species.
The reliability of the Frster cycle has been questioned occasionally
in the literature which stimulated us to review critically the subject,
a quarter century after the publication of Frster's classical paper.

Thermodynamics of the cycle

At first, the question arises, whether the use of thermodynamics
is allowed on the level of electronically excited states. The electronic
relaxation times are usually several orders of magnitude longer than
the time for thermal equilibration in all other degrees of freedom of
a polyatomic molecule in a liquid surrounding. The analyses based
on Stbpanov's general relationship between absorption and lumines-
cence spectra [5] provide good evidence for the Boltzmann distribution
of vibrational degrees of freedom within the lifetime of excited
states [6]. This justifies the separation of the electronic degrees of
freedom from all other ones, which is equivalent to the treatment of
the excited species as new chemical entities. Hence, the equilibria
between excited molecules can be defined in terms of partition func-
t ions with the exclusion of electronic degrees of freedom. The proliiin
is simplified by the fact that the cycle in Fig. 1 involves only the
differences in energies, whereby the ground state process serves as

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 The Frster Cycle Reconsidered 199

a reference for the excited level. In fact, we consider two closely analo-
gous systems. The differences arise from the change of the electronic
wavefunction on excitation, which leads to changes, e.g., in dipole
moments, force constants etc.
The shift of chemical equilibria in the ground and in the excited
states is given by:
-
RT In K*/K<* =
(ziGo) =
0*- 0 - ( 80* -
AS0G). (3)
The most frequently used form of the Frster cycle, Eq. (1), results
from an approximation:
80* ^ ASoG (4)
which will be discussed later on. Assuming the validity of (4), we

obtain :
*

% -
Nhc [vi i&),-
(5)
and in this sense Fig. 1 is understood by most workers in the field.
In the exact derivation of the Frster cycle we must take into
account that the idendity 00 0*0 ^0 refers to zeroth vibrational
=

levels, and thus to 0 temperature

at 0: =

-
Nhc [vi &) ~ zlF0*(0) zlFoG(0).
-
-
(6)
We substitute (
can ) for zl(z)Fo), neglecting PzJF0. (H0 E0 =

+ FFo; in condensed systems at 1 atm FFo amounts only to a few

cal mole-1 ;

Fo, being still much less, is negligible in comparison
with all other effects.) For temperatures above 0 K, we can apply
statistical thermodynamics. The equilibrium constant for the reaction
(2) is:
im\ ZB{T)ZH(T) n -/iH0(o)!itT /7\
' 7 ' e ' [l>
_
~ ZA(T)

0( ) = RT2 dndKJT) 0(0) + RT2 In

Za(T^T)
(8)

The difference we look for, is :

0*( ) -
( )
=
0*(0) -
d/7oG(0) + RT2 In ggjfg^
(9)
Translational and rotational partition functions cancel out for both
electronic states. Internal rotation degrees of freedom may contribute
only in very exceptional cases : on excitation the number of vibrational

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200 Zbigniew . Grabowski and Anna Grabowska

degrees of freedom does not change. The majority of the vibrational

frequencies remain practically unchanged in polyatomic molecules.
Since A and differ by one proton only their structures are usually
very similar; those vibrational modes which change their frequencies
on excitation, do it the same way in both species, unless A* and B*
are of different orbital origin. For this reason the corresponding
factors cancel each other. Moreover, changes of vibrations with
wavenumbers > 1000 cm-1 do practically not influence the partition
functions because the population of these modes above the zeroth level
is negligible at 300 K.
For the few vibrational modes which may influence the right hand
side of Eq. (9) we carry out a numerical estimate for a highly
contributing very low-frequency vibration, say 50 cm-1, in order
=

to test its influence. Let the change in this frequency in the excited
state be 10/0 in only one of the species, A or B. At 300 we =

obtain from (9) in this case

[AH0*(T) -
AB~oG(T)] -
[AH0*{0) -
AH0G(0)] 0.6 cal
=
mole-1.
Such an error in the estimation of ( ) corresponds to an uncer-

tainty in determination of pK: =

*)^m^Q
4 ^ 10^4 which
is negligible. Thus, 0*{ ) 0 ( ) sa 0*(0) AH0G(0), which
of change referring to for
-

justifies the use the enthalpy 0 =

evaluation of the equilibria, e.g., at room temperature.

Entropy terms
In the entropy change of reactions in polar solvents several
contrubutions may be discriminated, namely those due to:
(i) change of the number of molecules,
(ii) change of the number of charges and of the corresponding
solvation,
(iii) changes of the dipole moments and the corresponding minor
solvation effects,
(iv) changes of the internal degrees of freedom.
Comparing the entropy change of a reaction in ground state
the
with the one in the excited state must take into
we account that the
contributions (i) and (ii) are the same; these are the most important
contributions to So. With respect to (iii), the changes in dipole
moments between A* and A, and between B* and B, are most fre-

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 The Frster Cycle Reconsidered 201

quently parallel and therefore largely compensate each other. As to

the contribution (iv), one can refer to the preceding discussion of the
partition functions for reaction (2) :
ASo= -^p- Bn^- + BT^Trn^L
=
(10)
ASo* -
AS0G R\n
=
+ RT ^ In .
(11)
For the same test case of the low frequency vibration, 50 cm-1,=

we obtain ASo* ASoG 0.19 cal mole"1 K1, which contributes

=

j^^Q

to pK* by an amount pK* = 0.04. This is well within

=

the limit of error for experiments dealing with the Frster cycle.
Based on the above arguments we conclude that the assumption
ASoG ASo* is reasonable in most cases. Important exceptions will
~

be discussed below.

Spectroscopy o the Frster cycle : (0,0) transitions

The choice of the (0,0) transition energy as the spectroscopic
parameter is not the only one which is possible, but it is the most
reasonable one. It is relatively easy to determine experimentally and
to interpret it unambigously from the thermodynamic point of view.
To start the discussion of methods for the spectroscopic determina-
tion of (0,0) transitions of a single reaction partner, A or B, we con-
sider thecase of a spectrum with well resolved vibrational structure.
The (0,0) transition can be measured in absorption and in lumines-
cence. In absence of intermolecular interactions they coincide. In
solutions, the intermolecular interactions modify the electronic energy
levels differently in the ground and in the excited state. The none-
in
quilibrium ("Franck-Condon") state reached the transition under-
goes relaxation which involves the reorientation of the surroundings.
Thus, the thermodynamically meaningful (0,0) transition energy in
condensed phases should be defined as the energy difference between
the equilibrated excited state and the equilibrated ground state
(Fig.2). In fluid solvents the (0,0) transitions in absorption and in
emission do not coincide [7]. From the theory of the spectroscopic
solvent shifts [8] one can infer that the relaxation energies involved
in the excited and in the ground state (Fig. 2) are nearly equal, with
the exception of a minor correction due to differences in polarisabilities
in both states. Hence, the average of both observed transitions,
I (iooS + ^oo)> corresponds most closely to the energy difference

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202 Zbigniew . Grabowski and Anna Grabowska

Fig. 2. Solvent equilibrated and solvent non-relaxed ("Franck-Condon") states,

voo between the equilibrated states is represented most closely by the average
from values measured in absorption and in fluorescence

J
Fig. 3. A difference of vibrational spacing in absorption and in luminescence
(strongly overemphasized in the figure) results in an error of estimate of the
(0,0) transition from an average of "half-height"-wavenumbers, and especially
from an average of absorption and luminescence maxima. The intersection
point is the best approximation to the (0,0) transition in absence of vibrational
structure

between the solvent-equilibrated zero-vibrational levels of both

electronic states involved. We will call it simply the v0Q transition in
solution.
In most cases the vibrational structure of the spectra is, however,
blurred out to an envelope. In such cases an approximation method
has to be applied to estimate the (0,0) transition (cf. Fig. 3). The most
exact approximation is to use the intersection point of the mutually
normalized absorption and emission spectra, as it was the practise
in Frster's laboratory [9,10]. In the case of large Stokes shifts, when
no intersection point can be measured, the average of the "half-

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 The Frster Oyele Reconsidered 203

height" energies of the absorption and emission bands is generally

a better approximation to the (0,0) transition than the average of
the corresponding absorption and luminescence maxima (Fig. 3).

Controversial cases

a) Normalisation procedure
The location of the intersection point of the absorption and lumines-
cence spectra depends strongly on the proper normalisation of the

spectra. Sometimes when two absorption bands overlap, it is not

lg e(v)
lg f (v)

Fig. 4. Normalisation of the luminescence spectrum to the corresponding absorp-

tion maximum is often arbitrary. (1) and (2): intersection points assumed to be
(0,0) transition dependent on alternative normalisation

clear where to locate the maximum of the absorption band corre-

sponding to the same electronic transitions as the luminescence (Fig. 4).
A good example for such a case has been shown by Weller in his
paper on the protolytic equilibrium in excited acridine [9]. In such
cases common spectroscopic means should be applied to identify the

proper maximum, e.g., excitation anisotropy spectra, comparative

solvent or substituent shifts, etc. An error of 1 nm in the estimation
of the (0,0) transition at 31000 cm"1 corresponds to an error of 0.2
units in determination of the pK* value.

b) Inversion of states
In certain molecules the electronic levels invert during the lifetime
of the excited state, usually in a solvent assisted relaxation process [11].
In such cases the fluorescent state is different from that represented

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204 Zbioniew . Grabowski and Anna Grabowska

by the first absorption band. Inversion of states makes the experi-

mental determination of the (0,0) transition rather difficult. The
methods described above should be applied to the second absorption
band, this being possible, however, only in exceptionally favourable
cases.

c) Change of orbital origin between substrate and product

In numerous systems A* and B* are of different orbital origin,
e.g., the lowest excited singlet state of quinoxaline is an 1( , *) state,
while the conjugate acid, quinoxalinium ion, is a 1( , *) state [12].
The validity of applying the Frster cycle to such systems has some-
times been criticized. Japf and Jones [13] suggested that the
approximation (4) may fail if A* and B* are of different orbital origin
(electronic configuration or state symmetry). In view of the preceding
discussion it is clear that in principle the cycle can be applied to any
system of excited states, provided the conditions of approximations
are fulfilled. This seems to be true, e.g., for moderately polar azaaro-
matic systems.
This does not hold for aromatic amines. These bases considerably
change their dipole moments on excitation, whereas this change
should be negligible in their conjugate acids, the arylammonium ions.
Estimates of the correctional entropy terms were published, for
aminoanthracenes [14] and for 2-aminonaphthalene [15]. The first
estimation was erroneous, the second treated numerically only a minor
contribution, irrelevant to the case; both underestimated the effect
by one order of magnitude. The entropy term can be calculated for the
change of the dipole moment in a polar medium. Substituting into
eq. (8) of ref. [8] the values for 9-aminoanthracene [14] we obtain
^$foiv hSfoiv ^ 14 cal -1 mole-1. This corresponds to a cor-

rection for pKs, as calculated from the cycle (1), of about -f- 3.

In of this classical papers [16] Th. Frster described the

one

change of the fluorescence spectrum of 2-aminonaphthalene, estimating

pKs ta 2.
Application of his cycle resulted in a widely differing
value, pKs ss 5.5 [14]. Although the processes occuring in excited
naphthylammonium ions are complex and not yet clear [17,18],
Frster's results [16,18] strongly suggest that the equilibrium
should correspond indeed to pKs ta 2. The discrepancy seems now
to be due to the entropy terms, which can neither be neglected nor

properly accounted for.

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 The Frster Cycle Reconsidered 205

Applications to acid-base equilibria

Numerous examples of the proton transfer processes in excited
states have been critically reported in several excellent reviews [4,13,
1922]. To exemplify the conclusions which can be drawn from the
application of the Frster cycle on the reactivity of excited species,
some less known systems will be quoted.
C-acids constitute a group of compounds particularly interesting
from the point of view of chemical reactivity. The Frster cycle in-
dicates in fluorene and in its derivatives an enormous rise of the
acidity of the proton in position 9. On excitation the * values
( * pK* pKG)
=
reach about 15 for the triplet, and 30
for the singlet state [23]. These results are a challenge for a further

photochemical research.
In the large group of aromatic diazines two acid-base equilibria
were determined for three electronic states 67, and 8\ :

BH2++^BH+ + H+ (K1) (12)

BH+^B + H+ (if"). (13)
The experimental treatment of acid-base equilibria in the triplet state
needs a comment. The measurement of spectra is not straight forward
since the corresponding transitions are strongly forbidden. Phosphores-
cence, as a rule, is observed in rigid media, which excludes the solvent
equilibration in the excited state ; the spectra show usually the vibra-
tional structure making it possible to find the (0,0) transitions. For
quinoline and quinolinium ion these were confirmed by the T <- So
transition induced by oxygen under high pressure [24]. In order to
check the reliability of these data used in the cycle for the calculation
of pKT values the independent method of flash spectroscopy was
applied. Tn <- absorption spectra have been measured that way
in buffered solutions after the equilibrium had been established [2528,
12]. It is remarkable that both sets of results usually agree within
several tenth of pH.
In most diazines the following changes are observed which we
consider to be typical (cf. the upper part of Fig. 5):

< 0 and ^>0.

These observations may be qualitatively explained by the increased
polarisability in the excited state [29].

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 206 Zbigniew 11. Grabowski and Anna Grabowska

Hn pH
Fig. 5. Examples of acid-base equilibria (12) and (13) in several diazines in three
electronic states. Vertical segments mark pKG values. Changes of pK are
indicated by solid lines for the lowest excited singlet state, by dotted lines for
the triplet state. Interrogationthe value could not bo determined experi-
mentally

Polynuclear diazines containing the pyrazine ring exhibit par-

ticular properties : unusually high basicity in the triplet state, and the
lack of room temperature fluorescence of the protonated forms [12,
27,28]. As it can be judged from low temperature fluorescence spectra,
both, ApKf and ApKfIt are positive (see the lower part of Fig. 5).
It seems that the unusual behaviour of 1,4-diazines and their cations
is caused by substantial changes of molecular geometry in the excited
state [12].
Several free radicals derived from diazines by one-electron reduc-
tion provide examples of the doublet-doublet fluorescence observed
for both basic and acidic species ; the Frster cycle could be used here
for the determination of pKD in the first excited doublet state of
these free radicals [30].

Unexploited applications of the Frster cycle

The scope of possible applications is broader than the protolytic
equilibria discussed so far.

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 The Frster Cycle Reconsidered 207

The processes of chemical relaxation, leading from one to another

excited species, can be roughly divided into two groups:
(i) those involving reactants well defined in both ground and
excited state as chemical entities. The reactions are here the same in
excited as in the ground state, only quantitatively modified;
(ii) those involving one reactant which does not exist in the
ground state as a chemical entity. The processes are in this group
specific for the excited states, e.g., excimer formation or excitation
energy transfer.
Because of its very nature, the Frster cycle may be applied to
the first group of processes only.
The equilibria between the hydrogen-bonded complexes and their
components can be successfully treated in this way [4,31]. The in-
vestigation of complex formation between ligands (L) and metal
ions (M) seems to be promissing; keeping in mind the necessary pre-
cautions, one can predict by means of the Frster cycle the equilibria
between M and L* or between M* and L. Another field of application
of the cycle appears in the isomerisation processes occuring on the
level of electronically excited molecules, as, e.g., in the naphthalene-
naphthalene system [32].
Finally, still remote but prospective seems the use of the Frster
cycle to predict the reactions in higher excited states. The already
known equilibria, e.g., in the lowest triplet state may appear useful
as a reference for the second excited state of the same manifold.

References
1. Th. Frster, Naturwissenschaften 36 (1949) 186.
2. Th. Frster, . Elektrochem., Ber. Bunsenges. physik. Chem. 54 (1950) 42.
3. . Weller, . Elektrochem., Ber. Bunsenges. physik. Chem. 56 (1952) 662.
4. A. Weller, in: Progress in Reaction Kinetics, Vol. 1, ed. G. Porter. Perga-
mon Press, Oxford 1961, p. 189.
5. B. 1. Stepanov, Doklady AN SSSR 112 (1957) 838.
6. A. Kawski and J. Kukielski, Z. Naturforsch. 25a (1970) 653; A. Kawski,
Acta physica polon. A 37 (1970) 651 ; Chimia 28 (1974) 12.
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8. W. Liptay, Z. Naturforsch. 20a (1965) 1441.
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and H. Boos, in: Advances in Molecular Spectroscopy, ed. . Mangini.

Pergamon Press, Oxford 1962, p. 443.

12. A. Grabowska, J. Herbich, E. Kirkor-Kaminska and B. Pakula, J. Lu-
minescence 11 (1976) 403.

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208 Zbigniew . Grabowski and Anna Grabowska

13. H. H. Jait and H. Lloyd Jones, J. org. Chemistry 30 (1965) 964.

14. K. Rotkiewicz and Z. R. Grabowski, Trans. Faraday Soc. 65 (1969) 3263.
15. S. G. Schulman and A. C. Capomacchia, Spectrochim. Acta 28A (1972) 1.
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19. E.L. Wehry and L.B.Rogers, J. Amer. chem. Soc. 87 (1965) 4235;
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20. E. Vander Donckt, in: Progress in Reaction Kinetics, Vol. 5, ed. G. Por-
ter. Pergamon Press, Oxford 1970, p. 273; in: lments de Photochimie

Avance, ed. P. Courtot. Hermann, Paris 1972, p. 80.

21. S. G. Schulman, in: Physical Methods in Heterocyclic Chemistry, Vol. 6, ed.
A. R. Katritzky. Academic Press, New York 1974, p. 147.
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23. E. Vander Donckt, J. Nasielski and P. Thiry, Chem. Comm. (1969) 1249.
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on Luminescence 1966, ed. G. Szigeti. Akadmiai Kiad, Budapest 1968,

p. 368.
25. G. Jackson and G. Porter, Proc. Roy. Soc. [London], Ser. A 260 (1961) 13.
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-

32. . J. Turro and P. Lechtken, Pure Appi. Chem. 33 (1973) 363.

33. A. Grabowska, . Pakuia and J. Pancir, Photochem. Photobiol. 10
(1969) 415.

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