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Orbital Interaction Theory of Organic Chemistry, Second Edition.

Arvi Rauk
Copyright ( 2001 John Wiley & Sons, Inc.
ISBNs: 0-471-35833-9 (Hardback); 0-471-22041-8 (Electronic)

CHAPTER 15

PHOTOCHEMISTRY

The ground state of a molecule represents only one of, in principle, an innite number of
electronic states. Because the electron distribution is dierent for each state, the bonding,
structure, and reactivity will be dierent from the ground state. Each electronic state is
de facto a separate chemical species, with its own set of chemical and physical properties.
Excited electronic states are higher in energy than the ground state so energy must be
introduced in some manner to excite the molecule. In photochemistry the energy is
introduced to the molecule by the absorption of a photon of light hn which falls in the
UV/visible spectral region.
PHOTOEXCITATION
The geometry of a molecule in its ground state represents but one point on a 3N 6dimensional potential hypersurface (3N 5 in the case of linear molecules). It is a stationary point (all forces acting on the nuclei are zero) corresponding to a local minimum
(all displacements of nuclei from their equilibrium positions lead to a rise in the potential
energy). Other stationary points on the ground-state potential energy hypersurface may
represent dierent conformations of the same molecule or dierent molecules (including
dissociation fragments). Each excited state has a similar potential hypersurface associated with it. Stationary points on excited-state surfaces will not in general coincide with
those on the ground-state surface. Figure 15.1 shows a one-dimensional cross section of
the ground state, S0 , and two excited-state potential surfaces, one of which is bound like
the ground state, S1 , and the other of which is unbound, S2 . In fact, Figure 15.1 may depict a state correlation diagram of the kind discussed in Chapter 14. On bound surfaces,
the vibrational motion is also quantized. The spacing of the vibrational energy levels
(4004000 cm1 or 440 kJ/mol) is such that at room temperature most of the molecules
are in the lowest vibrational state. In addition, rotational motion of the molecule about
its center of mass is also quantized. The spacing of the rotational energy levels depends
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Figure 15.1. Potential energy surfaces for bound states, S0 and S1 , and a dissociative state, S2 .

inversely on the moment of inertia. For large molecules (more than a few rst- or higher
row atoms) or in solution, the rotational structure is not resolved, although at room
temperature, a number of rotational levels will be populated. The range of structures in
the ground vibrational state is given by the vibrational wave function shown for the
lowest vibrational level of S0 in Figure 15.1. The time required to excite the electron
(1015 s) is very short compared to vibrational periods (>1013 s). The shaded area in
Figure 15.1 represents the range of structures from which vertical excitation may take
place if the energy of the photon corresponds to the approximate energy dierence between the ground-state lowest vibrational level and some vibrational level of an excitedstate potential energy surface. In general, the excited state reached by vertical excitation
from the ground state will be hot (vibrationally excited) and may dissociate if the vibrational mode of the excited state corresponds to bond stretching. A more detailed representation of the sequence of events after photoexcitation is given by a Jablonski diagram.
JABLONSKI DIAGRAM
A generic Jablonski diagram for a molecular system is shown in Figure 15.2. Singlet
states and triplet states are shown as separate stacks. Associated with each electronic
state is a vibrational/rotational manifold. The vibrational/rotational manifolds of dif-

FATE OF EXCITED MOLECULE IN SOLUTION

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Figure 15.2. Modied Jablonski diagram: A absorption; F ourescence; P phosphorescence;


IC internal conversion; ISC intersystem crossing; VC vibrational cascade.

ferent electronic states will in general overlap each other. Straight lines represent photon
absorption (A) or emission, the latter as uorescence (F) or phosphorescence (P). Wavy
lines correspond to radiationless transitions which involve vibrational relaxation via a
vibrational cascade (VC) to the zero vibrational level of the same electronic state. Energy
is carried away through collisions with solvent. If vibrational/rotational levels of two
electronic states overlap, then it is possible to move from one state to the other (lower)
without a change in energy. If a change in spin multiplicity is not involved (S ! S or
T ! T), the process is called internal conversion (IC); if a change in spin multiplicity is
involved (S ! T or T ! S), the process is called intersystem crossing (ISC). Both IC and
ISC are immediately followed by VC.
FATE OF EXCITED MOLECULE IN SOLUTION
The fate of an excited molecule depends on the rates (time scales) of competing processes. As already mentioned above, the time scale for photon absorption (A) is very

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fast, 1015 s. For molecules containing elements with atomic number less than about 50,
electron spin is strongly conserved. As a result, only singlet states are accessible in the
primary excitation process. The time scale for the vibrational cascade and for internal
conversion between higher excited states is governed by vibrational motions or collision
frequencies in dense medium. Both are about 1012 1013 s. Internal conversion between
S1 and S0 may be substantially slower, 106 1012 s, of the same magnitude approximately as uorescence, 105 109 s. Ultimately, useful photochemistry is limited by the
uorescence lifetime, tF , which for absorptions in the near UV may be estimated from
the molar extinction coecient as [314]
tF s A

104
emax

A photochemical transformation can be accomplished only if the photoexcited molecule


has a chance to do something before it uoresces. Intersystem crossing time scales may
vary considerably, 101011 s. Return to the ground state by means of phosphorescence
is comparatively slow, 10 2 104 s. The rates of chemical processes depend on the magnitudes of barriers hindering the change. Intermolecular processes depend additionally
on collision frequency between reactant (the photoexcited molecule) and substrate as
well as possible orientational (stereoelectronic) criteria. Eective barriers hindering
reaction tend to be lower in photochemical processes, partly because bonding in the
excited molecule is weaker and partly because the excited molecule may be vibrationally
excited (hot). The collision frequency for intermolecular reactions may be maximized if
the substrate can function as the solvent or if the reaction is intramolecular.
DAUBENSALEMTURRO ANALYSIS
The following very useful approach for the analysis of photochemical reactions is due to
Dauben, Salem, and Turro [13]. A bond, ab, made from fragment orbitals fa and fb
of molecular fragments, a and b, is broken in the process under consideration. The relationship to the orbital interaction diagram is transparent (see Figure 15.3). The orbitals
fa and fb are the left- and right-hand sides of the interaction diagram, while the assembly ab is the middle. The ``middle'' constitutes the reactant. The noninteracting rightand left-hand sides constitute the products. Assume that the orbital fb is lower in energy
than fa . The two electrons originally in the bonding orbital may be distributed in
four distinct ways between the two fragment orbitals, fa and fb , yielding four states,
Z1 . . .fb 2 fa 0 , Z2 . . .fb 0 fa 2 , 1 D . . .fb 1 fa 1 , and 3 D . . .fb 1 fa 1 .
The rst two states are zwitterionic, since the bond dissociates heterolytically. Also, since
both electrons occupy the same orbital, both zwitterionic states are singlet states and
will be totally symmetric with respect to any symmetry operation which may be preserved in the dissociation. By our assumption that Efb < Efa , it is expected that
EZ1 < EZ2 . The remaining two states arise from homolytic dissociation of the bond
and therefore are diradical in character. Both singlet and triplet states arise. If any residual interaction persists (i.e., if the bond broken was a p bond or the products are
held together in a solvent cage), then the triplet diradical state is lower than the singlet
diradical state. Otherwise the two have the same energy. Since the electrons end up in
dierent orbitals, the spatial symmetry of the diradical states is determined by the symmetry properties of fa and fb . The diradical is symmetric (S) if fa and fb are both

NORRISH TYPE II REACTION OF CARBONYL COMPOUNDS

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Figure 15.3. (a) Orbital interaction diagram for the formation of a bond between molecule fragments a and b. (b) Orbitals for DaubenSalemTurro analysis of the rupture of the ab bond: lefthand side, orbitals of the bond with other occupied and unoccupied MOs of the reactant (molecule
ab); right-hand side, congurations which arise from the orbitals which made up the bond (other
orbitals of fragments a and b not shown).

symmetric (S) or both antisymmetric (A) with respect to a preserved symmetry operation. If fa and fb have dierent symmetry properties, one S and the other A, then the
spatial symmetry of the diradical states is A. Notice that the latter case could not arise
if fa and fb are the orbitals involved in the original bond, since they could not have
interacted to form the bond if they were of dierent symmetry. It will generally happen
that one or more of the orbitals of the fragments a and b will be comparable in energy
to fa and fb so that other diradical and zwitterionic states must be considered and the
situation of dierent symmetries may occur among these. The same holds true for the
reactant excited states.
As mentioned earlier, heterolytic cleavage of a bond to form charged species is never
observed in the gas phase and is very unlikely in nonpolar solvent. Thus the expected
overall order of the energies of the product states arising from the bond rupture is
E 3 D U E 1 D < EZ1 < EZ2 . If the energy separation of fa and fb is large, or if fa
and/or fb are diuse, that is, the Coulomb repulsion of two electrons in the same MO
(neglected in Huckel theory) is not large, the energy separation of the diradical states
from Z1 may not be very large and may indeed be reversed if the dissociation is carried
out in a highly polar solvent like water. Examination of several reactions of carbonyl
compounds will serve to exemplify the principles of DaubenSalemTurro analysis.
NORRISH TYPE II REACTION OF CARBONYL COMPOUNDS
A common photochemical reaction of carbonyl compounds is the transfer of a hydrogen
atom to the carbonyl oxygen atom:

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Figure 15.4. (a) Frontier orbitals of the fragments; (b) electronic congurations with two electrons;
(c) order of the energies of the electronic states.

The lower electronic states of the reactants (left-hand side) are those of the carbonyl

group shown in Figure 14.8c, since the sCH and sCH
orbitals are too far apart to participate in the lower electronic states. In other words, the light will be absorbed by the
carbonyl compound. The local group orbitals of the product fragments and the states
which arise from them are shown in Figure 15.4. The reaction is considered to take place
in the plane of the carbonyl group, and the orbitals are symmetry typed according to
their behavior with respect to reection in this plane.
A DaubenSalemTurro state correlation diagram for the photochemical step of the
Norrish Type II hydrogen abstraction reaction is shown in Figure 15.5. The reactant
(carbonyl) states are classied in point group Cs and also as S or A. The placement of the
reactant and product states on the same energy diagram need only be approximate. The
singlet and triplet np  states are located by virtue of the observed lowest electronic transition in the UV spectra of carbonyls, about 250 nm or 5 eV relative to the ground state.
The pp  states are higher, with a larger singlettriplet gap. Assuming the ground states
of reactants and products to be of similar energy, the diradical states may be placed at
about the energy required to dissociate a CC or CH bond, about 360 kJ/mol or 4 eV.
The state correlation diagram indicates that the reaction should proceed via the np 
states which correlate directly with the product states of the respective multiplicity. The
pp  states of the carbonyl group correlate with higher electronic states of the products.
The carbonyl ground state correlates with the Z1 state of products. Both singlet and
triplet np  states cross with the ascending ground state at the regions marked by shaded
circles. At the crossing of singlet states, IC may allow a substantial fraction of the reaction to revert to the reactants. Intersystem crossing is usually much less ecient, and
therefore a higher quantum yield would result if the reaction were carried out on the
triplet potential energy surface.
The eciency of photon capture to form the 1 np  state is very low since the excitation is electric dipole forbidden in the local C2v point group of the carbonyl. Direct

NORRISH TYPE I CLEAVAGE REACTION OF CARBONYL COMPOUNDS

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Figure 15.5. DaubenSalemTurro analysis of the photochemical step of the Norrish Type II
reaction. The reaction is ecient on the 3 np  surface to yield triplet diradical products. It is less
ecient on the 1 np  surface since IC is relatively ecient.

excitation to the 3 np  state is both space and spin forbidden. The triplet state, 3 np  ,
may be reached via sensitization using compounds which undergo ISC very eciently
and whose lowest triplet states are above the 3 np  state of the carbonyl. Conversely,
the presence of compounds whose triplet states are below the 3 np  state of the carbonyl will result in quenching of the reaction.
NORRISH TYPE I CLEAVAGE REACTION OF CARBONYL COMPOUNDS
A second common photochemical reaction of carbonyl compounds is the cleavage of the
bond adjacent to the carbonyl group:

As with the Norrish Type II reaction, the lower electronic states of the reactants
(left-hand side) are those of the carbonyl group shown in Figure 14.8c. The local group

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PHOTOCHEMISTRY

Figure 15.6. (a) Frontier orbitals of the fragments of a Norrish Type I cleavage; (b) electronic
congurations with two electrons; (c) order of the energies of the electronic states.

Figure 15.7. DaubenSalemTurro analysis of the photochemical step of the Norrish Type I reaction for (a) saturated carbonyls and (b) conjugated carbonyls. The reaction is most ecient on the
3
pp  surface to yield triplet diradical products. It is also ecient on the 3 np  surface since IC
permits formation of products in their ground state.

NORRISH TYPE I CLEAVAGE REACTION OF CARBONYL COMPOUNDS

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orbitals of the product fragments and the states which arise from them are shown in
Figure 15.6. The reaction is again considered to take place in the plane of the carbonyl
group and the orbitals are symmetry typed according to their behavior with respect to
reection in this plane.
A DaubenSalemTurro state correlation diagram for the photochemical step of the
Norrish Type I a cleavage reaction is shown in Figure 15.7. The reactant (carbonyl)
states are classied in point group Cs and also as S or A. The state correlation diagram
indicates that the reaction should proceed most eciently via the triplet pp  state which
correlates directly with the ground state of the products. The 3 np  state of the carbonyl
group also cleaves relatively eciently via internal conversion at the crossing of the
triplet surfaces. Reaction via 1 np  also occurs since the 1 np  state correlates with a
higher singlet electronic state of the products and can then undergo internal conversion
and vibrational cascade to the lowest singlet state of products. However, in this case,
recombination of the radical pair is very fast if the radicals have been held together in a
solvent cage or within the same fragment, as in the case of a-cleavage of cyclic ketones.
The carbonyl ground state correlates with the 1 D1 state of products. This reaction corresponds to thermal cleavage of the a CC bond.