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I4 COMPLEX MOLECULES
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CHARACTERIZATION OF ELECTRONIC TRAN-

SITIONS IN COMPLEX MOLECULES

BY MICHAELKASHA*p
Received 3rd July, I950
A summary is given of the types of conclusions which may be drawn from
a study of the emission properties of complex molecules under optical excitation
in suitable systems. The types of radiationless transitions in complex mole-
cules are discussed, and a resultant spectroscopic criterion stated : T h e emitting
level of a given multiplicity is the lowest excited level of that multiplicity. Inter-
combinations in complex molecules are described, and their importance is shown
t o arise from the high probability of the excitation of triplet states-a con-
clusion which runs counter t o the trend of spectroscopic thought of a few years
ago. An atomic number criterion is stated (after McClure) which permits the
identification of intercombinations by a study of intensity of the transition with
heavy atom substitutions in a complex molecule. Finally, a listing of empirical
criteria is made which permits a distinction between pure n-electron transitions
(T -+ n-*) and transitions involving excitation of non-bonding N, 0, and S atom
electrons t o anti-bonding T molecular orbitals (n 3 n*). The most definitive
of these criteria is the disappearance of n -+ n* transitions i n acid media. An
unusual enhancement of the spin-orbit coupling process for n --f n* transitions
is reported and a possible interpretation is given.

Much useful information concerning the electronic states of complex

molecules can be gained from a study of the emission properties of such
molecules under optical excitation. In particular cases it may be
necessary t o study the molecule in rigid glass solutions at the temperature
of liquid nitrogen in order to observe its light emission properties. How-
ever, since there is hardly a case in which light emission can not be ob-
served with a moderate quantum efficiency, the method of emission
spectroscopy can be applied almost universally. The information derived
from such studies forms an essential supplement to that obtained from
absorption spectra in the vacuum ultra-violet, high resolution spectra of
vapours, and absorption spectra of solutions. In a series of forthcoming
publications by the writer a detailed study of emission spectroscopy of
complex molecules is reported .1 The present paper summarizes the
type of information revealed by such investigations.
Radiationless Transitions in Complex Molecules .-Two basic types
of radiationless transitions are observed in most complex molecules.
These axe merely defined here, a full discussion and references being given
e1sewhere.W 1~
* U.S. Atomic Energy Commission Research Fellow.
t Present address : Department of Chemistry, The University, Manchester,
England.
Emission Spectroscopy of Complex Molecules, M. Kasha, t o be published soon.
( a ) Relations between Lifetime and Quantum Yield.
(b) Internal Conversion of Electronic Energy.
(c) Intersystem Crossing of Potential Surfaces,
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MICHAEL KASHA I5
INTERNAL CONVERSION may be defined as the rapid radiationless
combination of excited electronic states of like multiplicity (combination
in the spectroscopic sense of undergoing transition between). I n general,
internal conversion to the ground state does not occur with a high proba-
bility, although in certain types of molecules the latter process is sig-
nificant and diminishes the total intrinsic quantum yield of luminescence.1'
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The phenomenon of internal conversion is manifested by the appearance

of a unique luminescence, regardless of which state of a given multiplicity
is excited. It yields a most useful spectroscopic criterion : T h e emitting
electronic level of a given multiplicity i s the lowest excited level of that
multiplicity.
An important recent application of this criterion is the re-assignment
by Shull a of Sklar's lowest calculated triplet level of benzene t o the
emitting triplet level ; Sklar arbitrarily has assigned the observed triplet
level t o one of the higher calculated levels.
INTERSYSTEM CROSSINGis the spin-orbit-coupling-dependent internal
conversion. In most cases this is the radiationless transition from the
lowest excited singlet level to the lowest triplet level of the molecule.
Analogous t o radiative transitions involving n-electrons (e.g. in aromatic
hydrocarbon molecules), a prohibition factor of about 106 distinguishes
inter-system crossing from internal conversion. Moreover, since spin-
orbit coupling forces are involved, the introduction of heavy 1 0 (i.e. high
atomic number) and paramagnetic a atoms into the molecule will strongly
increase the probability of the transition, as will strong external electric
and magnetic fields. Despite the large prohibition factor, however, inter-
system crossing is a rather probable process in most molecules. I n fact,
although usually observed only very weakly as a direct absorption from
the ground (assumed singlet) state, the lowest triplet state is readily excited
t o emission (under conditions of low quenching, viz.,rigid glass solutions).
Thus, the lowest triplet state has been located in several hundred complex
molecules through a study of their phosphorescence s p e ~ t r a . ~ ~
The facile excitation of the lowest triplet state (by light absorption
to the lowest excited singlet state) is really a consequence of the very
high rate of internal conversion (e.g. between singlet states). The follow-
ing analysis of the rates involved may help t o make this clear.
A molecule is excited optically t o its nth excited singlet state, 3.
Under steady excitation a spectrum is photographed in search for the
spontaneous S" -t- emission (this has not been observed thus far in the
cases studied). The ratio of the rate constant (reciprocal lifetime ")
"

for the spontaneous Sfi +- luminescence to the rate constant for the
radiationless Sfi -t S' internal conversion is given by the intensity ratio

since the intensity of the fluorescence S' 4S indicates the number of

internal conversions. Numerous observations of this sort have placed
the upper limit at the value indicated.
Thus, the internal conversion process takes place at least 104 times
as fast as the spontaneous Sn +- emission. The intrinsic lifetime of
the latter can be calculated from the integrated absorption of the band
corresponding t o the S a c S absorption: we shall assume this to be

(d) T- and %-electron Transitions in N-heterocyclics (with C. Reid).

(e) %-Electron Transitions in Molecules Containing - Y = X : Groups.
If) Internal Conversion t o the Ground State.
(g) Summation of the Quantum Yield.
ZShull, J . Chem. Physics, 1949,17,295.
Yuster and Weissman, ibid., 1949,17, 1182.
Lewis and Kasha, J . Amer. Chem. SOC.,1944,66, 2100.
6 Nauman, Thesis (University of Califorpia, Berkeley, 1947).
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16 COMPLEX MOLECULES
I O - ~ sec., a value commonly found for intense u.-v. absorptions. Then
the reciprocal rate of the internal conversion process is
l / R l c Q IO-" x / k , 6 1 0 - l ~sec.
The natural limit on the rate of internal conversion may well be the time
of a vibrational period; shorter estimates are actually obtained from
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spectroscopic data in some cases. As a consequence of the very high rate

it is t o be expected that internally converting levels will be somewhat
" "

broadened in a band width relative t o the band width of the fluorescing

"

level with a natural lifetime of 10-7 to 10-9 sec. In other words, the
"

lowest absorption band of a given multiplicity manifold will be better

vibrationally resolved than the higher energy bands of the same manifold
(e.g. singlet-singlet transit ions).
For intersystem crossing we apply an arbitrary prohibition factor of
I 06, giving an intersystem crossing reciprocal rate

.
I/k, < 108 I/kIc < 10-7sec.
The probability of intersystem crossing in a molecule is measured by
the intersystem crossing ratio x, which is defined as the ratio of quantum
yields of phosphorescence to fluorescence under steady simultaneous
excitation 1 c

A fluorescence lifetime of 10-8 sec. is arbitrarily assumed here for

illustration. The actual observed values of x are of the order of magnitude
of I for molecules with a-electron energy levels,lc indicating that the
general assumptions made in the rate analyses are approximately correct.
Intercombinations in Complex Molecules .-Having observed the
long-lived luminescence corresponding t o the triplet-singlet emission of
the molecule, we can locate the converse singlet-triplet absorption band
with confidence. (If there are two luminescences, the long-lived one
is naturally identifiable as the intercombination process. However, if
only a single luminescence is observed, even under conditions of minimum
quenching, the criteria t o be described below must be applied.)
The intensity (integrated absorption) of the converse absorption band
mag be calculated from the measured lifetime of the luminescence by the
well-known expression 6 , 7

From the integrated absorption and an assumed band width for the type
of transition in question, the peak molar absorption coefficient can be
estimated. Using the latter and the frequency of the 0, o-band of the
phosphorescence emission spectrum, the singlet-triplet absorption can be
found.7 Since this is usually about I O ~times weaker than the normal
singlet-singlet transitions, rather long optical paths must be used, or
else concentrated solutions or even the pure liquid (or solid) substance
must be studied. Under these conditions absorption of light by an impurity
easily could be misinterpreted as a forbidden electronic transition, were
it not for the double check of correspondence with the 0, o-band of the
emission spectrum, and with the integrated absorption intensity calculated
from the mean lifetime of the emission process.
To identify spectroscopically the long-lived luminescence and converse
absorption bands as intercombinations, use is made of the character-
istics of the spin-orbit coupling process. As is known from the theory of
'Ladenburg, Veyh. dtsh. physik. Ges., 1914,16, 769; 2. Physik, 1921, 4,
451. Tolman, Physic. Rev., 1924,23, 693. Perrin, J . Physique Rad., 1926, 7 ,
go ; Ann. physique, 1929, 12,169.
Cf. Lewis and Kasha, J . Amer. Chem. SOC.,1945,67, 994.
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MICHAEL KASHA 17
atomic spectra, the probability of spin-orbit coupling increases rapidly
with increasing atomic number of the atom. This principle has not been
applied generally in molecular spectroscopy, although it is well known
that, e.g. in the halogen series of molecules, the probability of the singlet-
triplet transition in the visible region increases greatly in intensity in
the order Cl,, Br,, I,.
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McClure 8 made the valuable extension of this principle to heavy-atom

substituted . complex molecules, showing that like the (radiationless)
intersystem crossing process,1c the radiative intercombination process
likewise increases rapidly in probability with increasing atomic number
of the substituent. Thus, the rate constant for phosphorescence k , = I / T ,
as well as the oscillator strength f (or the integrated absorption, Jedv)
increase rapidly with increasing atomic number. This is shown clearly
in Fig. I, which is a plot of McClure’s data for the monohalo-benzenes

FIG. th the effect of atomic number on intercombinations in the spectra of

substituted complex molecules.

and naphthalenes. The solid line indicates the probability of the

triplet-singlet emission process measured as the phosphorescence lifetime.
The dotted lines show how one of the singlet-singlet transitions behaves
for the same series of halo-derivatives. (The increase in f for bromo-
benzene and especially iodobenzene is probably due t o the approach of
the non-bonding halogen transition to the benzene 2600 A absorption ;
the dotted line is arbitrarily drawn downward to suggest the correction
required.) Obviously the atomic number is the wrong parameter against
which to plot the probability of singlet-singlet transitions : some other
property of the halogen substituent would give a more rational dependence.@
The atomic number effect is particularly valuable for the identification
of intercombinations because the frequency of the transition changes only
8 McClure, J . Chem. Physics, 1949.17,905.
S Matsen (Symposium on Molecular Structure and Sfiectroscopy, Ohio State
University, Columbus, Ohio, I 3th June, 1950)has presented a molecular orbital
treatment of the problem which explains the anomalous f-values of the 2600 A
transition of the halo-benzenes in terms of an inductive effect.
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18 COMPLEX MOLECULES
slightly while the intensity changes by a large factor (e.g. the factor is
1000 for the lowest singlet-triplet of the mono-iodonaphthalenes com-
pared with naphthalene).
Armed with this increased knowledge on the nature of intercombin-
ations in complex molecules, great progress in this branch of molecular
spectroscopy may be anticipated.
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n +- n* and n +- ‘ZF* Transitions.-A study of the emission spectral

properties of the N-heterocyclics, which the writer has carried out to-
gether with Dr. C. Reid,ld has indicated the optical similarities of some of
these molecules to such molecules as carbonyl, nitro, and nitroso com-
pounds. In, e.g., the carbonyl compounds, the lowest singlet-singlet
transition has been characterized tentatively as a transition corresponding
to the excitation of a (nearly) non-bonding (oxygen) electron to an anti-
bonding 7~ molecular orbital.10 We have obtained definite physical
evidence for this interpretation and have found analogous transitions
(involving the non-bonding nitrogen electrons) in various N-heterocyclics
(e.g. pyridine, pyrazine, phenazine). For convenience we designate non-
bonding electrons as n-electrons, and the corresponding transitions as
n + T* transitions. These transitions are characterized by remarkably
different properties in comparison with -.rr 3 T* transitions as shown,
e+., by the spectra of the aromatic hydrocarbons. A summary of dis-
tinguishing empirical criteria is offered.
VIBRATIONALBANDWIDTH (VAPOURSPECTRUM) .--.rr -+ m* transi-
tions : moderately broad, owing t o unresolved rotational structure.
n + T* transitions : “ atomic ” in sharpness, a fact commented upon
by numerous observers. This seems t o be due t o the weakness of the
P and I? rotational branches, the strong Q branch predominating.
VIBRATIONAL BAND WIDTH (SOLUTIONS).--.~~ +- T* transitions : vibra-
tional fine structure preserved (e.g. the 2600 band of benzene). n +- -P*
transitions : very‘ blurred, usually only slight vibrational structure re-
mains, even in hydrocarbon solvents. This is all the more striking in
view of the sharpness of the vapour absorption lines. Probably it is a
characteristic of the non-bonding orbitals which leads to an unusual
perturbation in solutions. I n hydroxylic and other solvents, vibrational
structure is completely blurred. Complex formation, probably involving
hydrogen bonding in most cases, occurs and changes the non-bonding
character of the orbitals.
ACIDIC SOLVENTS.--P +- -P*transitions : the transition is preserved,
although some blurring of fine structure occurs ; usually there is little
change in intensity. n +- -P* transitions : the transition “ disappears ”
(moves t o very high energies). Addition of a proton t o the non-bonding
pair of the hetero-atom greatly increases the binding energy of the “ lone
pair ”. This behaviour offers the clearest proof of the excitation of non-
bonding electrons in such molecules.
VIBRATIONALENVELOPE.--^ + -P* transitions : complex vibrational
envelope, many normal vibrations excited. n --f -P*transitions : usually
a unique vvib excited ; this can probably be explained in terms of the
localized character of the non-bonding electron orbital.
RATIO OF TRANSITION PROBABILITIES, P11/P31 (singlet-singlet against
singlet-triplet).-v --f T* transitions : the oscillator strength ratio
f i l / f s l ~ roS for the radiative process. For the radiationless process
oP/QF H I, which implies an equal probability of transition t o the lowest
triplet (and consequent triplet-singlet emission) and of spontanteous
singlet-singlet emission.
For N --+ T* t-ransitions f l r l f s l104,
~ and > 1000. Here is
evidence for a striking increase in the probability of the spin-orbit coupling
process in such transitions. The increase by a factor IOO to 1000 is much

IOMulliken, J . Chem. Physics, 1935, 3, 564. McMurry and Mulliken, Prac.

Nat. Acad. Sci., 1g40,26,312. McMurry, J.Chem. Physics, 1g41,9, 231 and 241.
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MICHAEL KASHA 19
more than can be accounted for by an increase in atomic number in going
from C to N to 0. It is t o be noted that the djP/Opproperty here means
that fluorescence is scarcely to be observed in these molecules (some
N-heterocyclics, all carbonyl, thiocarbonyl, nitro, nitroso, azo compounds) :
the forbidden conversion t o the triplet state is essentially complete.
" "

A possible interpretation of the greatly enhanced spin-orbit coupling

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for n --f T* transitions is that sp-hybridization which is present or can

be plausibly introduced into non-bonding orbitals brings the optical
electron much closer t o the nucleus than in the case of an electron in a
Ir-orbital ; the spin-orbit coupling process occurs near the electric field
of the nucleus of an atom. There are difficulties in this interpretation,ld
which, however, must be resolved by theoretical computations.

Department of Physics,
University of Chicago.