Introduction to photochemistry

J. C. Scaiano (Ottawa)
Basic principles of photochemistry including some selection rules, energy
transfer processes and the properties of excited state reactions.
1st NANOBIOPHOTONICS SUMMER SCHOOL
UNIVERSITY OF OTTAWA
April 30-May 4, 2012
Co-organizers Hanan Anis (Engineering)- Tito Scaiano (Science)
Much of the material in these classes is based on the books:
Turro, N. J.; Ramamurthy, V.; Scaiano, J. C. Principles of Molecular Photochemistry: An
Introduction; University Science Publishers: New York, N.Y., 2008.
Turro, N. J.; Ramamurthy, V.; Scaiano, J. C. Modern Molecular Photochemistry of
Organic Molecules; University Science Publishers: New York, N.Y., 2010.

http://photo.chem.uottawa.ca

and follow teaching

1

What Is Molecular Organic

Photochemistry?
The field of molecular organic photochemistry can be
conveniently classified in terms of:
the photophysics of organic compounds (the interactions of
light and organic molecules resulting in net physical changes)
and,
the photochemistry of organic compounds (the interactions of
light and organic molecules resulting in net chemical changes)

Ground state
reactants

Ground state
products

The overall reaction

h

Ground state
reactants

Ground state
products

The next level of detail

Ground state
reactants

Excited state
reactants

Reaction
Intermediates

Ground state
products

The chemistry of
excited states

A global paradigm
More than one type of
*R excited state can be
involved in a reaction

F for funnel, when a

real intermediate is not
involved, will not be
covered in any detail

Simplification for a
short course

When intermediates in
the reaction are formed
in an excited state,
termed adiabatic

Reactive intermediate (I) that can typically be described as having the

characteristics of a radical pair (RP), a biradical (BR), or a zwitterion (Z).

Wavelength and color

UV

Visible region

More energy, bonds break

NIR & IR

Less energy, bonds vibrate

Light absorption
The absorption of light is a pre-requisite
for it to be able to cause chemical
change.

LUMO

This can be viewed as another

expression of the laws of energy
conservation.
Most molecules have all their electrons
paired in their ground states, and the
simplest (but not the only) effect of light
absorption is the promotion of an electron
from the HOMO to the LUMO.
Molecular oxygen and stable (or
persistent) free radicals are exceptions of
molecules that have unpaired electrons in
their ground states.

Light
absorption

HOMO

S0

S1

A standard abbreviation:
Light absorption = h

An Everyday Working Paradigm

Study questions
1. What are the electronic characteristics of the HO and LU involved in
the R + h R process?
2. What is the electronic configuration of R (i.e, the orbital occupancy of
the HO and LU)?
3. What are the plausible primary photochemical and photophysical
processes typical of R based on its electron configuration
(HO)1(LU)1?
4. What are the electronic natures of the NB orbitals of I?
5. What are the plausible secondary thermal reactions of I leading to P?

How much energy do photons carry?

The energy of light depends on its wavelength, the shorter the wavelength,
the higher the energy.

When we count molecules we use Avogadros number.

When we deal with

light we measure photons in einsteins, which correspond to one mole of
photons or 6.02 x 1023 photons. The energy associated with one einstein
depends on the wavelength (or frequency) of light.

When all the conversions are done its worth remembering a simple equation:

Relating the photon energy to the energetic requirements of the chemistry we want to initiate is
essential to determine if the process is plausible.

Ground state
reactants

Singlet
States
Sn

....
S

Excited state
reactants

Reaction
Intermediates

Light absorption normally

occurs with spin
conservation.

Triplet
States

Tn

....
1

Ground state
products

For the vast majority of

molecules this means the
initially formed excited state
is a singlet, not always the
lowest one (S1).

10

Can shorter wavelengths cleave a photostable molecule?

electron spins"
absorption"
emission"
non-radiative"

LUMO+2
LUMO+1
LUMO

h!

relax

fast

HOMO

S0

S2

S1

In most cases upper excited

states (higher than S1, such as S2,
S3, ... Sn) relax rapidly to the
lowest excited electronic state, S1
from which most photochemistry
and photophysics (such as
fluorescence) take place. This is
known as
s rule and is true for most
molecules in solution.

A consequence of Kashas rule is that most molecules show wavelength-independent behavior. Sometimes
molecules show wavelength dependence simply because different isomers or conformers can be excited at
different wavelengths; this can be seen as a trivial case: different species showing different behavior.

11

Ground state
reactants

Excited state
reactants

Reaction
Intermediates

Ground state
products

Light absorption normally

occurs with spin conservation.
Singlet
States

Triplet
States

For the vast majority of

molecules this means the
initially formed excited state is
a singlet, not always the lowest
one (S1).

Kasha's
Rule
S

Note that upper states (S2

Sn, T2 Tn) are absent; this is
because their lifetimes are
usually very short and they
relax to S1 or T1, which in most
cases are the states that are
responsible for chemical and
spectroscopic properties.
12

Azulene and violation of Kashas rule

Kashas rule (a reminder from Wikipedia)

Kasha's rule is a principle in the chemistry of electronically excited molecules. The rule states that
photon emission (fluorescence or phosphorescence) occurs only from the lowest-energy excited
electronic state of a molecule.
13

Ground state
reactants

Singlet
States

Excited state
reactants

i sc

Intersystem crossing from the first

excited singlet state to the lowest
triplet state

Reaction
Intermediates

Ground state
products

Triplet
States

Triplet states play a very

important role in
photochemistry, but they are
usually derived from the initially
formed singlet state.

The importance of spin

14

Let the electron spin change

In the first few slides we assumed that electron spin is conserved in all cases. This is
not always the case, and quite frequently one of the fates of S1 is for one of the
electron spins to change to produce a lower energy state called a triplet state, T1.

A different representation,
the Jablonski diagram

Note electron spin change

S1
T1

The T1 state is at
lower energy
(think Hunds rule)

S1

T1

S0

Changing electron spins is of course a forbidden process. For the moment we just need to know that processes
are slowed down for this reason, and that there are mechanisms by which the total angular momentum can (and
must) be conserved. The change from S1 to T1 is called intersystem crossing (ISC).!

15

Ground state
reactants

Excited state
reactants

small
S

Reaction
Intermediates

S
T

n,*

big

Ground state
products

,*

The singlet-triplet gap, EST, is an important property of a

molecule, small gaps are encountered for n,* states and
large ones for ,* states.
16

The state energy diagram is a fundamental paradigm of

modern molecular photochemistry

Jablonski diagram
17

18

The Jablonski diagram-everyday version

S1

IC

T1

A remarkably useful tool, the Jablonski

diagram lets us see the energetic, multiplicity
and dynamic connections between electronic
states of a molecule. Solid lines are always
radiative processes color coded here as:

Absorption
Fluorescence
Phosphorescence
Wavy lines always show radiationless
processes, such as intersystem crossing and
internal conversion (IC).

S0
Multiplicity axis

The horizontal axis is used to show

multiplicity. Only states of the same
multiplicity are shown vertically aligned.

The simplicity of the Jablonski disgram is mostly due to Kashas rule that most of the time lets us ignore all
those upper electronic states. Sometimes we may find that even if a molecule obeys Kashas rule the upper
states do play an important role. Benzophenone and anthracene will be such examples.

19

EXAMPLE: Butyrophenone: putting a face to R, I and P

Ground state
reactants

Excited state
reactants

Reaction
Intermediates

Ground state
products

H-atom transfered

CH3
O

Butyrophenone

CH3
O*

CH2
k r xn

OH

Biradical
generated
in the triplet
state

20

EXAMPLE: Butyrophenone: Norrish Type II reaction

Ground state
reactants

Excited state
reactants

CH3

CH3

O*

k r xn

Reaction
Intermediates

CH2
OH

Triplet
biradical

Ground state
products

CH2
OH

Singlet
biradical

CH2 CH2
OH

Enol

21

EXAMPLE: Butyrophenone: the complete reaction

Ground state
reactants

Excited state
reactants

Reaction
Intermediates

Ground state
products

Final
product

OH

CH2 CH2
CH3
O

CH3
O*

k r xn

CH2
OH

CH 3
O

Product forming
reactions

OH
Ph

22

EXAMPLE

Back reaction reduces the quantum yield

Ground state
reactants

Excited state
reactants

Reaction
Intermediates

Ground state
products

Final
product

OH

CH2 CH2
CH3
O

CH3
O*

k r xn

CH2
OH

CH 3
O

Product forming
reactions

OH
Ph

23

Quantum yield
The number of molecules of I or P produced per photon
absorbed is called the quantum yield () of the formation of a
reactive intermediate (I) or a product (P).

Note the use of capital for quantum yields

24

Quantum yields
From standard
analytical
techniques

Rate at which a process occurs of

rate of formation of a product, or
of disappearance of a reactant
Intensity of light, i.e. rate of light
absorption

Note that the denominator refers to

absorbed photons, not incident
photons

Chemical systems or physical devices

called actinometers allow the
determination of the number of
photons in an excitation beam
25

Norrish I vs. II. Which one when?

Norrish II, hydrogens are essential

Norrish I, weak C-C essential

Substitution at the and position

can determine competitive processes

26

Ground and excited states are different

Different geometries and
different vibrational
properties make them
spectroscopically different

IR frequency is
1665 cm-1 in the ground state
O
1222 cm-1 in the triplet state

27

Excited state energies

The energy required to produce an electronically excited state
(R + h *R)
is obtained by inspecting the absorption or the emission spectrum of the
molecule in question, as well as applying Einsteins resonance condition
for the absorption of light.

LUMO
h is Plancks constant (1.58 1034 cal s = 1.58
1037 kcal s), is the frequency
(commonly given in units of s1 = Hz), is the
wavelength at which absorption occurs
(commonly given in units of nanometers, nm), c
is the speed of light (3 108 cm s1)

Light
absorption

HOMO

S0

S1
28

Einstein as a unit
Einstein = energy of a mole of photons

N0 = Avogadros number

Worth remembering!
28600
E =
= energy in kcal /mol
(in nm)
28600
e.g.
= 71.5 kcal /mol
400 nm
29

Relationship among energy, wavelength & frequency

Visible region = 400 to 700 nm

30

Energies, energies, energies

31

Time scales
short

long
33

Born-Oppenheimer approximation
The BO approximation states that the motions of electrons in orbitals are much
more rapid than nuclear vibrational motions. This approximation assumes that
the light mass, rapidly moving electrons can immediately adjust their distribution
to the positive potential of slowly moving, heavy massive nuclei.
The important consequence of this approximation is that it allows electronic and
nuclear motions to be treated independently mathematically and makes it
possible to compute a good first guess of, the true molecular wave functions of
a molecule

0 S
Electrons

Nuclei

Spin

This approximation breaks down whenever there is a significant interaction

between the electrons and the vibrations (called vibronic coupling) or between
the spins and the orbiting electrons (called spinorbit coupling).

34

Transitions in formaldehyde"

Transitions at relatively low (UV/Vis) energies involve:!

CO

) ( n ) ( * )
O

CO

*!
n!
!
ground!
state!

n,*!

,*!
standard abbreviations

35

Excited state properties determined by type of

excitation
The other labeling
S2 (,*)

*
n

S1 (n,*)

n,*

,*
S0

Half-filled orbital
localized on oxygen:
species resembles
an alkoxy radical

Transitions involve
only the system, no
free radical properties
expected. In aromatic
ketones the aryl system
is usually involved

36

Formaldehyde orbital occupancy

Recognizing standard state labels

37

Energies of the excited state of formaldehyde

Coulombic term
(classical)

Electron exchange
(Pauli)

38

Comparing acetone and benzophenone

39

Ground state
reactants

Excited state
reactants

small
S

Reaction
Intermediates

n,*

big

Ground state
products

,*

40

Ground state
reactants

Excited state
reactants

Type
C H 2= C H2

C H 2C=O
P h2C=O

,*

Reaction
Intermediates

E(S-T)

,*

70

40

,*

35

n,*
n,*

10
7

Ground state
products

Each electronic state can be

described in terms of a
characteristic electronic
configuration which in turn
can be described in terms
of HOMO and LUMO and in
terms of a specific spin
configuration, either a
singlet or a triplet state.

kcal/mol

41

Electronic Energy Difference between

Molecular Singlet and Triplet States of R
Hunds rule

For organic photochemistry, Hunds rule can be rephrased for MOs as follows:
For molecules possessing two half-filled orbitals, one a HO and the other a LU, the
triplet state () is always of lower energy than the energy of the corresponding
singlet state () derived from the same electronic (HO)1(LU)1 configuration

42

Exchange interaction, J

CH2O
TRIPLET STATE: the average repulsion energy will be less than the repulsion computed
from the classical model because of the tendency of electrons with parallel spins to avoid
each other, and thus reduce electronelectron repulsions
43

Singlet triplet gap

n,* for formaldehyde

The energy gap between a singlet and a triplet state of the same electronic
configuration of half-filled orbitals (i.e., the same orbital occupancy) is purely the
result of electron exchange and is responsible for the observation that the energy
of a triplet state is generally lower than that of a singlet state of the same
electronic configuration (the same orbital occupancy) for organic molecules.

44

Singlet-triplet splittings

45

Basics of carbonyl photochemistry!

T1 state!
S1

,*

Benzophenone: n,*

p-MeO-ketones: ,*

T2

n,*

T1

Benzophenone!
phosphorescence!
O

77 K glass

So

380

420
460
Wavelength,

500
nm

540

46

More on benzophenone
77 K
S2 (,*)

100 kcal
12 - 1

~10 s
S1 (n,*)
74 kcal

T2 (,*)

1011 s- 1

100%
T1 (n,*)
69 kcal
380

<107

6 -1

10 s

420
460
Wavelength,

500
nm

540

2 -1
1.8 x 10
s (90%)

S0

Jablonski diagram at 77 K

47

vertical

Franck-Condon (FC) principle

The FC principle states that because nuclei are much
more massive than electrons (the mass of a proton is
1000 times the mass of an electron), an electronic
transition from one orbital to another takes place while the
massive, higher-inertia nuclei are essentially stationary.
Expressed in quantum mechanical terms, the FC
principle states that the most probable transitions
between electronic states occur when the wave
function of the initial vibrational state (1) most
closely resembles the wave function of the final
vibrational state (2).

48

When the ground and excited state

geometries differ extensively, the
original nuclear geometry of the ground
state is a turning point of the new
vibrational motion in the excited state,
and that vibrational energy is stored by
the molecule in the excited state. This
vibrational energy is released as the
excited states relaxes to a lower
vibrational state.

Again, vertical

Vibrational energy storage in FC transitions

49

Colored objects
A green object, such as a leaf, reflects only those wavelengths that create the
visual effect of green. Other colors in the incident light are absorbed by the leaf.
Red light is absorbed by the chlorophylls, blue light is absorbed by carotenoids.

Source: CHM220 notes, Univ. of Toronto

A chromophore (color bearer) is

defined as an atom or group of
atoms that behave as a unit in light
absorption. A lumophore (light
bearer) is an atom or group of
atoms that behave as a unit in light
emission (fluorescence or
phosphorescence). Typical organic
chromophores and lumophores are
the common organic functional
groups, such as ketones (C O),
olefins (C C), conjugated polyenes
(C C C C), conjugated enones (C C C
O), and aromatic compounds
(benzene ring and condensed
benzene rings).
50

Oscillator strength
The oscillator strength f is defined as a measure of the intensity
or probability of an electronic transition that is induced by light.

Bottom line: big extinction coefficient short radiative

lifetime, possibly high fluorescence quantum yield
51

Electronic spectra

Examples
Atoms

Molecules
Gas phase

Molecules
solution

52

S0 S1 transitions

The real lifetime is frequently

much shorter, as a result of
radiationless transitions that
contribute to excited singlet decay.
53

More on Franck-Condon principle

54

The anthracene case

S1
Fluorescence
IC

Absorbance

T2
T1

S0

Wavelength, nm

Vibrational states play an

important role in absorbance
and in emission

The absorption and emission spectra of anthracene reveal features beyond the one line state Jablonski
diagram; these are due to the vibrational states of anthracene (the same ones we see in an IR spectrum).
Anthracene is unusual in thet the 0,0 bands for absorption and emission coincide almost exactly.

55

Fluorescence
Cyclohexane with (right) and
without (left) anthracene

How does
fluorescence look?

Visible light

UVA light

Fluorescence is light emitted when an electronically excited state relaxes to a lower state (usually the
ground state) of the same multiplicity.

56

Mirror image rule

Emission spectrum is typically a mirror image of the absorption spectrum
of the S0-S1 transition, but shift to longer wavelengths

Same electronic transition being involved in both absorption and emission

and the similarities of the vibrational energy levels of S0and S1
In many molecules vibrational energy levels are not significantly altered by
the different electronic distributions of S0 and S1
Source: Ajayaghosh web notes

57

Stokes shift
Owing to a change in dipole moment of the
molecule in its excited state compared to that of the
ground state, the energy difference between S0 and
S1 is lowered prior to fluorescence emission (in
about 0.1 to 100 ps). This is the Stokes shift.
Excited singlet
relaxation
G.G. Stokes (1819-1903)

Not a Jablonski diagram

Source: CHM220 notes, Univ. of Toronto

58

Stokes shift: example

When electrons go from the

excited state to the ground
state there is a loss of
vibrational energy.
Source: CHM220 notes, Univ. of Toronto

59

The example of terphenyl

The absorption spectrum of p-terphenyl is devoid of structure, but the emission
spectrum shows vibrational structure The deviation from the mirror image rule
usually indicates a different geometric arrangement of nuclei in the excited state
and the ground state

In the case of p-terphenyl, the individual rings become more coplanar in the excited
state. As a result, the emission spectrum is more highly structured than the
absorption spectrum. This is unusual, the opposite is generally observed.

Source: Ajayaghosh notes on web

60

Chromophore and substituent: whos who?

61

Absorption and emission

62

Extinction coefficient measuring how allowed a transition is

63

Excitation
spectra

The wavelength at which

emission is monitored
should always be reported
with excitation spectra

64

Excited state character

65

Vibrational structure

It is rare to observe this level of detail at room temperature

66

Energy gap law

The decay rate of excited electronic states in a large molecule or of
an impurity in a solid is calculated for a model of a large number of
displaced harmonic oscillators. The rate depends exponentially on
the energy difference (gap) between the initial and final electronic
states.
Englman R & Jortner J. The energy gap law for radiationless transitions in large
molecules. Mol. Phys. 18:145-64, 1970.

In the absence of a Zero Order surface crossing between S1 and S0, an S1 S0

internal conversion must occur via a "Franck-Condon forbidden mechanism, i.e., the
nuclei in one state must undergo a rather drastic change in position and momentum as
a result of the transition, since the net overlap of vibrational wave functions in both
states is small. For such situations, the S1 S0 internal conversion is generally ratelimited by the Franck-Condon factor, < |>2 = f.

67

Energy gap law

applies to radiationless transitions"

k
Singlet
States

13

ic

= 10

- E

(s ec

-1

ISC
Triplet
States

Frank Condon factor:

"

Proportional to the overlap"

of the wavefunctions for"
the initial and final states"

f v ex p(- E)
Ground
Singlet
State

68

Energy Transfer

Fig. 7.1: Energetically favorable

conditions for the energy-transfer
process;

R +MR + M

The darker lines indicate the lowest
vibrational level for each electronic
state, and the lighter lines indicate the
excited vibrational levels for each
electronic state. Some vibrations

Of M are excited in order to conserve
energy during the energy-transfer step.

69

Energy transfer schematically

This example involves electron exchange

70

Trivial energy transfer

also known as radiative energy transfer

D*
*D

D + h

A + h

A*

no electronic interaction between D*

and A
*D

D* emits a quantum of light which is

absorbed by A

A physical encounter between A and D* is not required, the photon must only be
emitted in an appropriate direction and the medium must be transparent in order to
allow transmission.

71

Exchange energy transfer

also known as orbital overlap, collisional, and
Dexter energy transfer

donor*!

acceptor!

donor!

acceptor*!

electron clouds of D* and A overlap in space and

electron exchange occurs in the region of overlap
72

Electron exchange processes

Energy transfer
the only mechanism in some cases

Triplet-triplet annihilation
Charge transfer
Charge translocation
A theory of energy transfer by electron exchange was worked out by Dexter:

kET (exchange) = KJe

# 2rDA &
%
(
$ L '

K is related to specific orbital interactions like overlap dependence on specific orientations

of D* and A
J is the normalized spectral overlap integral, where normalized means that both the
emission intensity (ID) and extinction coefficient (A) have been normalized to unit area on
the wavenumber scale

J, by being normalized does not depend on the actual magnitude of A

rDA is the donor-acceptor separation relative to their van der Waals radii, L
By being defined in this manner rDA corresponds to the edge-to-edge separation

73

Coulombic energy transfer

also known as dipole-dipole, resonance, and Frster energy transfer

donor*!

acceptor!

donor!

acceptor*!

A transmitter-antenna mechanism for

energy transfer
74

Coulombic energy transfer

The dipole-dipole interaction represents a classical Coulombic interaction so we can make a classical analogy
the electric field
around an excited
molecule D* behaves
like a field generated
by a classical
oscillating dipole

D*

Coulombic interaction

the electrons in the

ground state of A are
assumed not to be
oscillating at all

the oscillating field of D* causes the excitation of nearby electronic systems

(provided certain resonance conditions are met)
this is analogous to absorption of a photon by A to generate A* as a result of
coupling between Ae- and and the oscillating electric field of the light wave

This mechanism will be most plausible for S-S energy transfer because
multiplicity conserving transitions have large transition dipoles

75

Coulombic or Frster mechanism

electrostatic interaction energy (E) between 2 dipoles is directly related to their magnitude
and the distance between them...

D A
E(dipole dipole) 3
RDA

* in this case we use

the center-to-center
distance, RDA

Frster related the dipole moments to the oscillator strengths of the transitions:

quantification of E in terms of measured oscillator strengths,

is a measured
property of a real system (electronic, vibrational, and spin factors) and is
related to the inherent radiative lifetime and the extinction coefficient

rate of energy transfer is related to the interaction energy according to:

2

% D A ( D2 A2
2
kET ( dipole dipole) E ' 3 * = 6
RDA
& RDA )
76

Coulombic or Frster mechanism

The rate constant and efficiency of ET can be easily related to the separation distance if we first define RDA0 as
the critical distance where the rate of ET is equal to the inherent rate of deactivation...

k ET [ A] = k D

at RDA = RDA

RDA0 = 6.5[A]1/3

taking into account geometry

and assuming D* and A are
spherical

Rate constant for any separation

6

# RDA0 &
1 # RDA0 &
kET kD %
( = %
(
$ RDA ' D $ RDA '

Efficiency for any separation

6

$ RDA0 '
ET & )
% RDA (

77

The diffusion limit

Debyes equation provides an easy approximation

A typical value for kdif in a

fluid solvent at room
temperature is around

1010 M-1s-1

An upper limit for kET

The units of kET are usually M-1s-1

78

A few useful numbers,

not a lot to say

Based on Debyes
equation

79

Light in biology

Wavelength ranges are labeled in photobiology

as UVA, UVB and UVC
UVA : 315 to 400 nm
UVB : 280 to 315 nm
UVC : below 280 nm.
In some cases the boundary between UVA and
UVB is placed at 320 nm.

80

Redox properties of excited states

Reduction

Oxidation

"vacuum"

EA

IP

LU
E*
HO
ground
state

Excited
state

ground
state

Excited
state
81

Redox properties of excited states

Important take home message
Excited states of diamagnetic molecules with
closed shell ground states are always better
oxidizing and reducing agents than their
corresponding ground states

This is not necessarily true of

species with open shell ground
states such as radicals

82