adienon by t h mole

ConsRg uenee of ahsoprm gf

i m ww Efecl
phots cheui tol poocR s o
Sn he fint slep of the moleonle f r n
outrm OY photon occ by
Vndi is 1 M E L pemam
h y
w amd usible S0gicn. Ihe PpL PiAy ProRs Ca
chenusl
poocess n photo ecolo
hesolo
Jotlording
be dis uised hy the
The elechonic exilation transi tion ofmalkuule 7hi
oy
includeo vbsqtononl and rotatonal tramsi teon alo

wolewle mey OCc

Disoticdin huolannki nmay 0Cc.
Lonisedtzm olude oecwt by eecttom d es
Stcondny Frouss
he se tinu of the mokine in erula Slak is
shorkabeut 1o 8 lo 15 See 4 ionisakon or
disotictin df he uoleunle dlogg oOCan than p
wu LAte p t a numben pxoan y Whieh tho
Con Sulkae absovbed puary is K n
sund arvy pORK These a n e .
6) Phophores um
PholoAynthesisad yon
Delaye Pholochemial Ckoin,
Rising p
i s u%im of pri many proes
hClectDnic ExiLaton
absorpteen df phe ton foom Uw-visible Jugicm
y (excald) fovm
woulkspxo huole
fhein o uppex eleutonic stalifmollull
nuhonic stculi (giund). Ihig txemsitm
Lnaa
rodliotrtn i Callhd elueforuc tans tion
by thenbsopkcm 0f
Apectxa nppLA for thiy taconsi fëcn Kmawn
The
elkosonic Ape diuaa
iv elkchonie
Sintl FeleeEvib> Erot ^o, an
Sinte,
vibaortonal amd rstatonai
mo.
enusm wel Cotun
emrs exutatiom dfnoleunle mus
cuel ie dwung elubic
ezütatunal so.
9statonal
and
vibrutonol
execuli
Can be xepASEded -
Stali
ElecTYomC e n e r
V 3
(T)
elui g )
v
Stall ()
=V#0

v3
Guund (J)
elwhmic y4 2
enLTy(") P(J')
Strli

As
As igkuw eleronic Stali olco maans iqkr pataia
eluuhomie level Cam be JRprASAmted"ley
eneaoymKo
Mo polerut al Cnwe,
Stali (4)
Jhe frgwe represeml 9roumd eluhrouc
amd umslable
SHable eitad elehornic Stali (B)
ited Stoli ()
 U%ta6e exiid Stalk
C)
dstakle erü le
etuchomi Stali (E)
E
dies
GrUumd elhnd
stala ()
CAus
mleynaclean ditomu
ssi
i s ums the eleuonic tens i tem we nmo 3
o
s u c h o bondin
h e p l kan odbilal J
3 pes
m:D-(7n). and amii
mconlir -

bonding
M
M.0 (6 and A), 2n Th encsny thee
m0. ( 6 and the f O l o i
6ondin M0
bohding pded by
nfon orhitls ane apre 18
mole
oiosrmw
eketio»
By absoption of e n y
trasitim occo
m.o
oom boncling
Y monbondiug m-0.o uioccupied
amtibonding m0*

Amang theae frenition 6-6

OCe mad probabu
amd 1-7 0
han n-6 amd n-s 6
afloned
ahe Aymmtry
Jon m e y .
innsily dau 5 t h lransi i
transition thirefore
u be ton
 namek- Cmdn Prnup
Jna elechronic spectzunm thure anenumber df
vwell
appeon
ppean the vinsity
ond Aiferemt linto is
expluined y remk- Tndon poniple
Stolimtnl*
mansive Compae lbo
aduS0o much
Becase nuclei cam moE
euchone Axamsifton nuclei
eleon , dwung
aspond. R
miernuclkan distane
uDwwna eletronuc taomsifion ramsitim oecul
wmchamaRd be cewa eleofroni
eml troositim
l0l6 See )tham vibytunal
much foMir t

"Allowed elecionic toamsi tienm in potetid encrm

dicam b nepresended key veviual line."
Explamum
To explaun thy prinuple Consider thu fottowing
Cano-

low amd uppey eleetorue stal maviug sama

Cse-1
îemulkan distaml.

elutsontc eniitutitnb
a

Dwwng
absoptio photem nelewle gom e'
Stali fromv 9oud S4ale
E o
lo enited
In guund Stali vi0 Stal+ is
rwatved and ma leunl tramsi
in mot ( a .
rom v"zo V ' 0
0tha trmsi fion may olto be
V123.
posible frow =0
der naclen diMenu
as thure i some chama of fendi ng
tha motul at thu entrume Gv»o. ,
fettswina tramsjticm m Possible
(O,0), (o), (20), (3.0)
 Anuong
Among thu transittm în tae df (0,0) tYvnsit m
atl
the iemudksn distamu emouin umchamge and p
isupesented ey.ventic) line Jhenafeve afe lö
P-c phimuipe inlamsiky f thiy pechm une niu
iqh Cowpane l5 they tromsikm.
COvbe- Opper elechronic Stal Masiua slahily 9Waler
inenucleondistunte than round Stole

Heve, ot/oiug tvansifioov an

pos1ba-0.0),CLO), (2,0),(38) e
a m u o g l l th
tramsi teon 0nly (}0) Aomsitom
S F - nlloaed amd 0theysau
mo as fhey Caint be konn+
veriud ini.So, (2,0)
by
romsition niu,be Stsong irnleute.
1esrmcleavdhemu

Siali howing slighily So Lone

Cse-0 upper elecronue
distame t h e n
9round
temuclean

(0)
Ameng (o,0), (Up), (2,02 ftn
osifim omy (3,0) tromsi
Fc h
Ove ollowed oye o
intensili Ril be higa
&o

4
e
 elucsonie stat auing cosidennbu renk
Co- Uppex
miesnuclen distame thom gUumd ewel

htn upper eleuhonic stali havig

inderrucea
Considurrnkle gvenlo
tie msteunls Mey
dirtomee fhen E
disouated out the trasj t
the F-C Thle. The
which allns absovb e n r r
disounlkd
Proclu
amd imureaaR
15
Conttmusly

eniyy sintt K:£.K

Kinc
ntnatised
the &o, peelum
Cumtum
v o h o m în
become cmiuan

icsotietio .

amd
Disms,case -
elechonie 8tuli
stasu.
. h r xu lid enuilid
haNi nG w inima presemb then Stal
Meule by obsorbiug phstin runsit T| huwing no

330 r u d Stali euled Stalk E mim.

thi molku
hwis io muma then matcude
e digou ded a s s0m as
hay the
ach lo ttuh, stale, Casejuealy,
pedhum f thiy rmsi tim 1S Groumd
Lhttww at beg inning wmhl- Stoli
Jin afadwu. 1ndernuclear distan
Cntnuw

VD
 redissociati
In 1921, Hkn y obsevved tlat iv cse Of peumm
8tme molimls(NO2)So, Mt3, a cHo) Ceataiv Ygim
Lwud and fenaly
t h e petruw is difue, amd hugh wR, n
loner
Cttum is Coming amd Comtuin Fem Btoudog
speifum,
h a that lifuae hih aawe ump
o h dire lE uue and lo ery m a Tte
Jhe untt
Hhuxe isftnel Contnum
a mole dasoialid
nledkesouialg
molecnle
indicnl, l a t
mdex hulioli nuwe no. o t 1ndicoed Trom
befene i s Lrue disoictrom
c i s o i a t s w of
the neoleule
Conktnuuw, Ihig
f nal 1desmeoliali tduwe no. iS Kownv s preAso-
ad t e
- ciaaw Ihiy k khawnv
i e structuu Predissouiakco-vw fimsfrele Diesoüolsn
ULL
C7,0) ) 1,o) (2,0)
Enomple i e e of S» vapouY diffuas, blwned anel
ttie
COntinum of the Apeitum is dbsexved m
w e uyh regigm 2799
lb 274I beyomd thu^
Rota ad rsar acue leugR fene structua i
olissouaksu occu
o bserved. 'FRnaly f r u CvoesoveY potnf
CR) P n t

Explamat Cse-1:
Excited Stal hawig Eiss B)
resuur inferunelea E
disamu amd he
mi hi ma
toEasFats
efenad

idemeu dietm
Ch-u (xosove Ypt
E ruded Strli havi ng
qreater îdernuckean
t a m e Omd wihord
huèima. EE
well dnjened

enutfeam ditiu -

epnsicloiug poievuod enerm

Jho Com be enplained îmwotoed
erited Sta. Here
dir om
of qruwnd stocli amndstali is qvomud
mainly
Ahne elechonic A, B, and.A Stali
amd c o eiteol eleehomic
eleetoni Stali, B pt is R
eacheothen nd Cross oveY
Coupe i e haniug wett cfeud
1v Cse-T,thi eeited sfale
Cose-Tt not 2lnuet
6edteP minimua omd
vible
h e noleulesabso photon from W- and
they g0 o Al stali a,bje (CAse-7)
or fg(
agun they
ag un
is Obsesveo
a, b.co .Case- them fine 3tuctwre Stali lo highsy
prom * Jroumd
Fmoleumlke migsali Contentm is 0bseyvel
e n r Stuli {han
dhem a
ru AiBotuatOn gf
toninw nolicale
nd h
woleinl
ow 1 the noleule miqruli lo ihad leuel
e. dl,e,f Thon
Dhith is cloxex l5 CYosover poin (R)
Stale
Hhee is a chamc of ronofex the moletule from
B lo stale C t ough Cro8s ovev pt. Nas, tte
moltml ot ths e Stali having ënrry grentr
 ham oli so i otëon enerm af thuy stali. &, ultima
6 the mo lnl is isouatow. Cumsqneily spechum
o s o ve pt
oluwung trmsition nean the twfinum,
amd feally
betomi dffuas, bwved
Jhe disect romsi fton of
hua leiuwle from A ls
lo Franchondm ponupl
is nat possible /e isouulë before
but h r o h B L5 C h
Cam

r u digsotiocton,
henu hy s predisotiotecn
JablonsKis diagvCm
Bythe absovpfi f raotialim molemle g0as o
exuiid Stoli.som th3tai they lo0se absorbek

Stola. 3h photophytl ro uses Cam be vepregemid

e Jablonsi
Commugnily bY aoiorum noum
m temino Bo
To mdexstcomd tuy dicrcm
- lory oue verj esmii. n tta 9trund Stali nos{
Lom (olnat all oxqauc
dior poy ottmic moleule
4 elerkrons Dik paired
molewle) u t i n wem mo.e's
F ta S= 2 4=0. She
pin.Lo, lot Apm
(25t) = 4.1t i Calleod Sinae'
Men l t p l i u l molatule is
Thun grtund Sta dF inglil, dlno led
Jhw
So
342 ks adwppen
elemG

loaer elechouc
Stal
Tot&l S Singlet sUumd
2Stl 3
S4ali (So) Total S=0
Triplet e iled 2S+I
Stale (7) Sing ut eveilu
2,3 S at (Sn)
 By u absoptiom of photon of suitalle ene ry
uiy
moleun g04s lo upper elufso uic Sfali. Dweng
ronsifim Juso pin elottms
ame possYLte
Jhe psomoti em eleefron cav have cme sp/v 1
Stola wik f* oiginal pantnes then &pin
upper =1. Thiy Stali is colles
multepliuky become (25t1)
when nsL2/3- Then
ingut entleel Stali (S»). eu lad Hal.
Si,SaS2 - ~ a e st, 2nd , 1hird Siglet
pih îw uper
have paaltol
J h e promotion dfe.com
Totl Apin multpliula
Atnli wk grrwnd: stali.
(24)+3Cnlledtriplat exited stali (T Here
alco posibla T, 7,13
Gwthy, e emr Sn S 9 c r
ham Tv SoEs >Et, and Es, >ET, efe,
eca se isinglef stale elechow a u im amh-
pin Dw l5 hy fc l5 Hund sule
pohdlli
1nieråtion occw athiy Sta .
p pin
stal eleitrom ane i panalll
h e n e h s . i tuplut
oathca is miimum.
hexe pm
S, spin
p uatum

TE Cam a o be socplained r m
mschanuind Codmlbhm

By th abropton of photon öithi fenl

slhds (1615 Sec). gos lö enuited Stale (S) from
în J. D. by
rrundSingletSti (So),th shawm
th
Hrom elunn
they
stula
uppeshecd straiqht amaar. thaouh
Stali by releasing absorbed enurom
orumd I t cossified inls
dujfeneit photopkyicnl proeantn
two Cotasoruks Nam radiative TM A.
traasiton hed
) Radhative tramsitien a
rookahio
 S3 T.5.
SI T
E
T2
T-SC
absoptto T
155se) luovesceme Phosphoyesiem 2
4(10Sec 10 S Sec)

O Non adiotiie romsiton o

Prom dle nit ted lall, moleule loase kk e n n
QL wmatvenied os srtvet moltule, conme f r m
highen mNm,eruited Stulë o atwers eMUN eriuted
Stola. Thiy rnsitecn Is CaRlad monyediebroe
transiton Tt imvatues LunpRS d romsi trm-
Inteynal Conwerrion (Ic) Singlu
Moleunle fram hiaher &eited Stale (S2,5,S4) Come
owe nited Angtit (S1) by J0081mg {s euero
as ahe 1s Callad mlernal Comyetsiom. 9E is &krn
t h e dingsom by wy ayow
donTdl.1t mayofto
ntos aysteun Cxo0sèng Cise)
In case df some
moleunla *amsiNcn may possibl
wexcited singul He o Coore&p moleng
fruplel8tale by Toosina engX exeited
ramsifion is Cald Tsc.Sina, i£ is spm Ao.Jhiy
transi tim 6o it ik slGA. Showm -foxbilon
by dotlde aT
Radiaäve Tramsi tm
Fsm exuied atcdi moleule nuluwvno o c u a
stak by DosiugA ne3m as vadiattpn Collld
adi oti ve Artonsiko. IF is FAso jpe3

Fluones wnue
leuls goes lo
By onbsoption of vadiolon mo

eleurouie Bxited state, from thej by IC, me lo

wppey The ife ¥inme afexitod
Mteol eloo nic 8lali (SD.
SAali is lo8 lo ( Sec. From 1huj talz
moleunle of Si n i t w lo
okule loose ps emeYm as
a qfo
Coulled fhuorescemu,
atate. This prouan is
Aingul gstund
Simgut e n i l Stali Singu exuilkgSo
Mou+ hi
(Sn) (n=2,3,4-) 168to1
1t is show by lowAn heoded vorw om Simalet 3eund Staa
SI l So tha diarsw,

Phosphorusame
Fyom tiput eni ke Stali (T) moleui velwvw
gvcund Ainglut stnti (So) y Joosirg enay a
Youliat on Wmow an phosphores cemu. 1t occans within
165 5 1 5 Sec. Senu, ih i pin fovbicdalem treasittm
0 ould be a dow pxota.1t is horm by l670

Singlek oxuited Stali

ISC Tipler exeilid Stal
Molule + i CSnn L,2,3.)rFe wel,2,3.--)
| TC
1oto Tniput exüld stale
( Staa
Singet ground l63 See CT
 QLDS 0f Photochenmistay
O Gauhs Drapers lan ley eacin
Ondy those vodiatton aksobed
Stadene eleduve fo% poocLOg pho
s
mo leenl
Chemucal Chumges.
lioht 1nidemt on amallul
In ofheY wordo tShen
inidene igh is absorbeol e
Cenrtain fratro Gf radi ohon is YPponsjble
the moleiule. Jhu absovbed
chamges. Refleded amd tramsme Ha-i
Jo photochemi c l photochemicad .
Sadiotiom ae not wetved
epanaken Ths Laus meams Mal nithont absorpton f
adiootiom mothulk comt foke pot i phofo-
Chemic psoUs. Bnl the rewexse is mot true Tf am
.

muolkule absoyb vadicctiom, t . m l nat take pant in

photothenmicnl prou% Jhe moleme moy lo0se 1Fs nRYY
by Aet oy vaoliohon CFusvescamu amd Pho sp horeidn
Ondsn such uYmstwnus absobed oediatom
ane hrt fectue for phooehemecnf ehomges.

Thusydhis. lan is: pwty qualitatue. There is

no uamti totuve velatim bety moumi ligpl
apiobecdl ond amouml photo homec ehomges
OCc
StekEinsiein kas of photo chamical EquivaWeuta i
Extemoliug
the q uantum Theony oaolictin
Emstei st aded thof-"l he primay 3 lip
photoche micnl pro Ua, One moleLn is
by absoptim i auwala
0ne_photon m amd visi ble
Juqm df adiotion"
plamatin, di ww comsi der a mo leuule AB bsorb ne
photon amd foxm exited noleiu AB" 1w
prmay
proa hon v
AB+ h7 ABT

The ativcded uo leule Com dirn ckly toke ponl

Tphotoche micd chanse o give the produut. Tn thi
cML mo mol i k deat oill be equal to mo. f photen
pant în chain
absobeol. Sf t h ativeded uolele takebe
no oF moleuiles nea will grealir tham
JUpn hem
mo. photon bsobed. When activoded molkule oleackivelid
coith F Othe molkunle
collisim omy 0fhm nay Ahen
tham h0. of.
no. phofon bsorbeol oiu bi guodiy
u t . Jhm th law does hot mean thot me
molewl
mollnl i u vw Ce by bsorhing one phofon b n~ 0L
woenle nil be acti veled by ovsorbing 0 photd.
euantum Yield ()
Jhe effiieuy of a photochemiCcl neackion Is Mesuud
unlberr
a lm Which îs pre esed a the oiaio
a t a given teme lo number
molcnltn niau o r fohm Pime
3ame is
Oi qUale absoxbeol at the
ot phbton
Caled uantunmield,
oleruatiol Ley
Mafhemoduenlly ,
o. 04 moltulus veat ox form in a Ce tuinn tinn
ov photon absovbec oit t a t
fème
: 09 uamta
No X mo. H molta 4moleules niul-
No F photon absoYRd
X no
umbey o nuoleul
mo Subfane = No
h7
Er ne photon
imste 1e. awo9nolvo F huoleu no. No h
EmYo
nar yy of 1 male photon ix.collnd 1Einsten
EEnary
1t is iha umit f phstocheui coad intesid
 Numbex fMuoles zeael oy foym of sudden t u
Nwmwhly einsteinabsohed a t the 8ome teme

Sali 6f Joton
ok,
E1m6tetn ohsovbeol or xnlö f absopttondf aou
ele fxeactits

d
1abs
mo lenime moles/eins tein
P eite/tim Molelen / Photm
.

DeteY manoton d quamtum Yield

To deiynu'ne. tar fados regireol
Mebswwmenl of Nali ruocin
(u Meosunanunt indensid G absovbed radioleo
) Deter mintim 0 nali of v u a l i n e t
Roli a a supn Com be miA wd by ithrading
mintwu time o tima amd malyse thL
ofuatamt 0 p%oolil- demouis, o Joxm af faamount
lina
b tha Erwtiom Auu dba
neagRiut. hý m ouq also be
roy detey minaion pysIcod popey tios that a e
ulafed lo Comp08ition amd eh amqes wh
peufic Sus{okion fmwLxtion fCane. fime
MeDOWwwmet gmiens bsoybed aadioton Sugon.
Fon the mesrument 03abs the
Kemehi
schenaHic veprerdation f anramgemenl
instummlis given belo. af
 2unte tel

W &elicko

Sownu F Filir
Tuaciom
Momochomator wuinluy
Na-lamp TheywioStalk
-lup opticnl window
PhotouuThermepile chemuid
ackinomelis
acinonek
Woking pnuple of Cheuuical
is measwned ley
Jhe iniemsilg o enary Of Yadiorthon
photo chemueal Ilattion ama oletoniposi ttm
deviu using an hemicsl
1n the devia Krwin
6f The moduiil presemibe diiferenË ipet-One f the
aebnomelix. Ihg may is Urany
uatol cheu cal aatnomeli
most ucently
t Contais diluli sdy df oxclic
oxalali acttnometes. Aulphal BJN (0-01 M). Thin
arid (0.04 M) amd uramy 4340 A° inuident on
lighthawingtdcuwe loyth 2540A lo e a t i o n becun
- -

dolloing photochemtcal
the miutwi
>Uo,* +S04Akivatian)
"Sa+ h? + co+ o2 + 4,0 deónpasiti)
Uo,2t
9 U +H22041
wacton 0 58.
thij
lon vemcuins unchcmqeol, acds os a emurn
Hore, wamyl
oxokc aeid dletD napOsea is meaownid
Connis Jhe amounl af
y tetakion wik KMn04 t loto + 8 H%o
SH904 +2 KMm O +9K S04 K3S04 +2M»Sty
=

f oxalic dOcomposeod we Camn

Fho the amo mt
ftnd oul indensily on eningy df radiakon
Some ofhws acenomelers art -
evuit Oxolaliathnomeler: 1t costoims potoBiwn
fevuc oxoitle.
ML actno nmely Malaclili qneun Leucocy amid
s aehnonelir. [mg)3 (H), (NCS)
Reineuke