Chapter 5

PF{OTOCHEMISTRY

#.i,, 5. 1 I}{IRODUCTION
definition o:of photochemistry is th .As
per
tsr "The

v
.ql44r$.etc.
The simplest photochemical process is
e@bsequent emission gf pbglqLby al gas
gut pnase atom .,r.h
pbu*_ato.!o
" vI

asjdium- When the sodium atom absorbs a photon it is said to be excited. After a short
eriod of time, the excited state sodium ator4_Blsits a ph.qtof6@ nn light and falls

palir'S ur trre werl KrIOwn uame [esl jI group I ano II metal salls \Llul, I\45r, vavn, DruI2
'.,basisofthewe1lknown''flametesu.bfgroupIaffiiCl,NaBr,CaC|z,SrC]z,
etc.), or the sodium atom=l;;G electrically excited and this is the basis of energy
i,, :efficient orange som-srree[ ugnrs Ltt rgure 5,1).
P 1l

Photon Photon
589 nm 589 nm

.t
I{r: or
Thermal
I{a
t\
excitation
or
Electrical
excitation
ground state excited state ground state
sodium atom sodium atorn sodium atom
Figure 5.1: Absorption and emission of photon by sodium atom
The photochemistry is very important as life itself depends on photochemical
; :.'- c'-:S-ies like photosynthesis. Photochemistry also deterrnines the composition of Earth's
- .--- - : I itere support-q life ancl shielcls us frorn damaging W radiation. Further,
l-r'- - --l^,

;::: - rhenistryls a central branch frorn which rnany other processes fincl applicatioos, as
.-.':: -: Figure 5.2.
272 En gitl q e rin g Chenr.istr

Analytical Quantu.nr
Chemistry Theory

Spectroscopy Fhotophysics

Photobiolory Organic
Chemical Synthesis
kinetics

Figure 5.2: Applications of Photochemistry

s.2IMPORTA\Tf TERI\{S USED IN PHOTOCHEMISTRY
Following are some important terms used in photochemistry as given by Commission or,
Photochemistry (IUPAC) in 1996:
i. CHAfuGETRANSFER @D TEANSITION:An electronic transition in which a large fraction
of an electronic charge is transferred from one region of a molecular entity, called the
electron donor, to another, called the electron acceptor (intramolecular CT) or from one
molecular entity to another (intermolecular CT). Typical for donor-acceptor complexes or
multichromophoric molecular entities. In some cases the charge transfer absorption band
may be obscured by the absorption of the partners.
2. EINSTEIN: One mole of photons. Although'widely used, it is not an IUPAC sanctioned unit;
It is sometimes defined as the energy of one mole of photons. Its use is discouraged.
3. ELECTfuONIC ENERGY MIGRATION 6r Hopping)iThe movement of electronic excitatioq
energy from one molecular entity to another of the same species, or from one part of a:
molecular entity to another of the same kind (e.g. excitation migration between thej
chromophores of an aromatic polymer). The migration can happen via radiative :oi
ra di a tionle s s proce ss es .
4. EMISSION: Radiative deactivation of an excited ,qtatei transfer of energy from a mol
entity to an electromagnetic fi.eld.
5. EXCITED STATE: A state of higher energT than the ground state of a chemical
photochemistry an electronically excited stateis usually meant.
6. FAEQUENCIT(v or ol): The number of wave periods per unit time. The linear frequency,
the number of cycles per unit time. The SI unit is Hz = s-1. For the angular frequenc/;
symbol ol (= 2uv) is used, with rad s" as the SI unit.
7. GROUND STATE: The lowest energy state of a chemical entity. In photochemistry grou
electronic state is usually meant.
8. HUND RULES
(i) Of the different multiplets resulting from different con-frgurations of electrons
degenerate orbitals of an atom those with greatest multipticityhave the Iowest
(multiplicity rule).
(ii) Among muitiplets having the same multiplicity, ^(urrguiu, the lowest-energy one is that with th9
Iargest total orbital airgular momentum momentum iie) (valid tf the rctal
or:bjtal angr.;-Lar momentum is a constant of motiod. '

iiii; I:: ccii:figiraticns cor:taining ."i:ells Jess than ira.lf full of electrons. tlre terir having the
].,f,i-r,;rist, i,ot,ai a:.rEr;].a-r' n'icli:,e:-ii,',-llt:r .fiiais i.i.'t,',o"t. in en,:rg', ra,lieic,.as i:r tlicse u'itir shells mor€

.,i,.:,,,- i-:,..- i-.,,, ] l,l-,t i,rl':,.'., l::.''r.r. ,1',,. j.r-';-rr:,

-',;',1r.;g jgr'qr,'i,rs''.
'1{'.7-].13p '!j:'e sll"it,:,irt:"g nrig).
sF-

t1t i' r'i 7t

Fkolt:'-'ii I

liunci rr;ies ap.ciy if the 3C h l,r lll ir i; '; il-i: i

"Prussr:ii-Sai-;.r,ciers" r1:-r3 ''|
t
"
: t -l it ]J
l-'
-r ..t- "^. .i
-i, .r-
,-* .:
l c ill'3 t1 ill'3s iil - ii:s ;
:'ule is applieC to mclecules.
o
ulo trrYTERNAL COiYVERSION: A phoiophysical process. Isoenergebic ratiiaiionless rransirion
between two eiectronic states of the same multiplicity. When the transition results in a
vibrationally excited molecular entity in the lower electronic state, this usually undergoes
deactivation to its lowest vibrational level, provided the final state is not unstable to
dissociation.
LOWPEESSUZE MERCtnt LAMP Ard: A type of resonance lamp which contains
mercury vapour at pressures of about 0.1 Pa 0.ZS x 10-3 Torri 1 Torr = 133.3 Pa). At 25oC,
such a lamp emits radiations mainly at 253.7 and 184.9 nm. Other terms used for such a
lamp are germicidal, cold and hot cathode, Wood lamp.
MULTIPLIAW (Spin AAtipt*itil:The number of possible orientations, calculated as 2^9+
1, oJ the spin angular momentum corresponding to a giyen total spin quantum number (9,
for the same spatial electronic wavefunction. A state of iinglet muttiplicity has ,S= 0 and,25
+1=l.Adoublelstatehas,g=Il2,25+I=2,etc.Notethatwhen S>L(thetotalorbital
angular momentum quantum number) there are only 2L + I orientations of total angular.
momentum possible.
PHOTOCATALYSIS: Catalytic reaction invoiving light absorption by a catalyst or by a
substrate.
PHOTOELECTROCHEMISTEI4'A term applied to a hybrid field of chemistry employing
techniques which combine photochemical and electrochemical methods for the study of the
oxidation-reduction chemistry of the ground or excited states of. moiecules or ions. In general,
it is the chemistry resulting from the interaction of light with electrochemical systems.
QUENCHING; The deactivation of an excited molecular entity intermolecularly by an
external environmental infiuence (such as a quenchel or intramoleculariy by a substituent
through a nonradiative process. When the external environmentai influence (quencher)
interferes with the behavior of the excited state after its formation, the process is referred to
as dynamic quenching. Common mechanisms includej energy transfer, charge transfer, etc.
When the environmental influence inhibits the excited state formation the process is
referred to as static quenching.
15. SELECTIOI{ RULE: A selection rule states whether a given transition is allowerC or
forbidden, on the basis of the symrnetry or spin of the wavefunctions of the initial anC final
states.
16. SPINOHBIT COUPLING: The interaction of the electron spin magnetic moment with the
magnetic moment due to the orbital motion of the electron. One consequence of spin-orbit
coupling is the mixing of. zerc order states of different multiplicity. This effect may result in
frne structure called spirorbit splitting.
I7. SPINORBIT SPLITTINGjRemoval of state degeneracy by spirorbit coupling.
18. SPINSPIN COWLING: The interaction between the spin magnetic moments of different
electrons and/or nuclei. It causes, e.g. the multiplet pattern in nuclear magnetic resonance
spectra.
19. WBRA,TIONAL RELAXATION: The loss of vibrational excitation energy by a molecular
entity through energy transferto the environment caused by coliisions. The molecular entity
reiaxes into vibrational equilibrium with its environment.
20. WAVELENGTH (X): The distance, measured along the iine of propagation, between two
corresponding points on adjacent waves. The waveiength depends on the medium in which
the wave propagates.
 1-7 / En g in ee rirt g Clrc.nzi,str

2L. WAVENLhIBEE (o,v-): The reciprocal of the wavelength, , or the number of waves per uni
iength along the direction of propagation. The SI unit is m-1, but a commonly used unit i
cm-1.

5.3 PFTOTOCHEh4ICAL REACTION PROCESSES

A photo-excited species, [X-Y]*, can relax (react) via a variety of pathways as given belov
in Figure 5.3.
/
Dissociation
Direct Reaction
Isomettzattons

X-Y F-{- Energy Transfer

Ground sta Excited. state Luminescence

Quenching
Photoionization
-12--?' Figure 5.3: Reactions of excited species
5.3.1@ion
T tay f radicals (blgggqd or, in the case oi
nitrogendioxidetorF-ixideandoXene.ThesetypesoffiSare
.'-.v-*e%k-\
impOrtant in ry. '-

Excited state .:i

INorl* ---------------- No + o ,

Pl-Cll # Cl'+ Cl' i

Figure 5.4: Disso6iation of excited state speeies 'i:
::4

Photo-excited species may also be able to fragment. €.g., 2-pentanone can be pho
excitedtoaspecieswhicheIiminates@oneaSgivenbeIow:
o" o
Hzc:cHz
H3.Ufr,.Aci
-,/ s.g.zDirect Reaction
The photo-excited state may undergo reactions unavailable to the ground state
E.g., photo-excited ketone can undergo a lZ+Z] cycloaddition with an alkene to
"
oxetane (a cyclic ether with a four membered rin$, a Paterno-Biichi reaction.
5.$"3 Isolterization

Lr a atn+.
UU d-
+L^+ ^.il^v,s free rotaticn around t]:e alkene double brnd. This photo-excited
Lr& Ul-, ulIO. v 4
iJ

s;iecies is aliie to::eia:l-irack to i,he grc,utid staie t,., sj,te c;,s'stilbene (Figure 5,6).
 +XYZ

[R = Cyano or COOH or COOET etc.]

Figure 5.5: Direct reaction of excited state species

+Y-X

,/\
Iro
transstilbene cisstilbene
Figure 5.6: fsomerrzation of excited state species
i Attother example of isomerization reaction is photo induded Iiransto-cit
cis conversion of all-
(Figare 5.7). tt-cisretanal thermally relaxes back to the all-
^rretinal to ll-clsrretanal
srretinal configuration. Retinal is derived from retinol (vitamin,$.

11
CHO
hv

or
trans-Retinal Thermal excitation 11- cz^rRetinal

Figure 5.7: Isomerizati.on of Retinal

,@
@ I4-state-ilggies. This process is
, gt.a
used to
!o j-f oaUgg-Srnglgt_oxl€L_--
nrodrree sinslet oYvec

"rGt-;;. L@Tnrfi
b.rsui, *i[To
-tiansfer
.;;i# to triplet o#en, which
is conveiled-To Englet oxygen (Figure 5.8). Singlet oxygen has a diffe'o"T;44ffi6 speetrum
cOmpa s.

[x-Y] * +z x-y + n_l*

Excited state
lRose Bengal DyeJ* * Oz--------------- lRose Bengal Dyel + O,
triplet Singlet

Figure 5.8: Energy transfer by collsion

The energy transfer may undergo intersystem crossing and relax in an intramolecuiar
manner. e.g., Sr (excited singiet) state of naphthalene can convert into the Ti (excited
tripiet) state.
276 En g ine e rin g Ch endstrl,

tx-g +
LmL^,^--Lmt
Singlet TriPlet
Figure 5.9: Intramolecular energy transfer
5.3.5 Lumi.nescence
Excited state species can emit light itt A."p3qqess cailed luminescence. If the process is
qu-itE
qutcK,
f,ne fluoiesG*a
ds- as
irtne'ii[Cit6fsTete iB p?6aiicc
If ttre'ii[Cit6frsTete i3
phoiphoied6dnCe. to
pmduee"cEemical lig-Et":Tg. emffiy
5.3.6 Quenching
In the liquid state, the excited state species may be que of
the excited state species is conve_rte{ i_4_t_o _v_ibr.ational enr is
gg!@Uyeffeg_Lud w olvitnlJ (piiiit s,t0.

X-Y + S*
S - Solvent

Figure 5.10: Energy transfer by quenching

7 Photo- ionuzatron
5. 3.
Photo-ionization processes are of great importance high in the atmosphere where
pressures are low and short wavelength UV radiation from the sun has a high flu
e.g., photo-ionization of nitric oxide by photon of wavelength 134.3 nm (Figure 9.til.

tx-Ylt + e
134'&nrn
No + hv ixo]:k r- No* + t
Figure 5.i. 1: Photoionization

5.4 THE CHEMISTRY OF EXCITED STATES

Excited states of most importance are those in which the electrons of an atom
molecule are ilistributed in a higher energy configuration.
5.4.t Absorption of Radiation
Absorption cf li.ght usualiy occu,rs in a singie step. Consider tvyo states g and
energies Es ?-r'jcl E.. The energ5'gap betv'een the states must correspond exactly
phcrton ener"g:,-.
F=
JJt
l',,,
J-t L
 Es t" = hv'

fo=.It ! I*L.L-*"*L 6il

is the light radiation absorbed by the medium which causes
-trence -isnored in

(iii)
radiation when passed through transparent
Beer independently with a gap of about 100

whena lig.b!*rg-algwed to
_ot
therate ty ryrlh the thickness
:, of-the--medium--ip_4gg_.jll _p.rggor!-ij1r-4! to the, intensity of the incidetrl ..tight.
i M3llr-es'atically,
dL-r
--=dt KI (iv)

where-dl is the infinitesimal decrease

in intensity for medium of thickness dt
-'l t l<-
Integrating equation (iu)andputting I= Iq when t = 0, we get

Kdt Where I0 is intensity of incident lighti I, is

intensity of transmitied light; K is
In constant dependent on wavelength of light
ln' = Kt
Ir
,\ -Kt
-_.
It = Io'
(v)

\lodifnng equation ft),we get:

-- Kr where lrlIo = transmittance (T') (w)

278 En gi,rreerirc g Chenr.i.str1,

5.4.3 Beels Law

According to this law, When q mqngchromatic light is passed through a solutiorr the rate of
decrease in intensity with the thickness of the solution is directly proportional to the intenJfi'
of tLe_ incident lig_lt qq_gSJblk 9on_9*94t-ratiqt qf the solutigJr. Mathematically,

where-dl is the infinitesimal decrease

dI in intensity for solution of thickness dt (vii)
- = K'IC
dt and C is conc. of solution in mol/lit
integrating equation (vii) between I = Ioandt=0
Whbre I0 is intensity of incident tight; It is
It = Ioe -K'Ct intensity of transmitted light; K' is (viii)
constant dependent on wavelength of light

From equation ftil (LamAert's law) and (viii) (Beer's law), we get the following equations
which ultimately give equation (ix,).

It = Ioe ect
rt
T

- ect
Iov=o
i - -I.
*..--
\ -----.
':.
-

- -'----
!

,^ =-ect'-'-:&r
(ix)
-,____ \1og
i - ro

The expression i+_ ggUglr--on- hx)*is..termed..-as mathema.t1sa]-statement for Beet'

trapsmiitanc-e-(T) and molayapporpJiollg,oq{S-cnpp-tk): --\

't
tqs g'/l'F 4 ::c t:tgg*gf ): -_L'gJ
5.4.4 Emission of Radiation
Radiations can be emitted in two ways as des
5.4.4.1 Stimulated emission Stimulated emi
excited species interacts with the oscillating
incident radiation (Figure 5.19. When an a
frequency yig i-rlgident upon it, then thb ato
to the lower energy state E* by emitting an a
two photons of same frequency are produc
emission. Stimulated emission is an essential
E" E"
hv G
2hv
G
i-
t- (i

r::iu J:i i s d
'St: