ULTRA-VIOLET AND VISIBLE SPECTROSCOPm

vibrational and roational level

Clearly, during promotion, the electron moves
oational level within the nesil electron
t possible transitions (close together) respotsabie Io
e in electronic. roational anl vibrational levels Hence, not just one but a
wavelengths which are close enough will be absorbed resulting in the Tomlion t n n
of aloms, lhe mullipcaty of vibrational sub
cunpiesoccles which comtan a
large numiber
hus, brd bands are
u e coccss fesulls in the discrele bands to coalesce anl

2.6 Theory of Electronic Spectroscopy

When the oleciule absorbs ultraviolet or visible light, its efectnns get pro
ground state to the higher cnergy tatc. ln, he s
nolecular orbital are eseatally pa i of thee clectons
e in
paired, then it is called an e c c u
g e inle state is always lower
the excifed stale ae
Ptc
in
efoe. triplet state is more stable as
chceEy t e trinlet
evcited stale, electrons are farther apalt t p
electron eoulsion is minimised. Normally the absorption of ullraviolet or V
liehi reualts in singlet ground state to excited singlet stale transition, 1.e Cc
emiss
he retention of spins. An excited singlet state is converted to cxcited triplet stale wilh tne
f energy as light. The transition from singlet ground state to excited iiplet state ymy
molecular orbitals and also
forbidden The highier energy stüles are
designated as
high cnergy
Called anlabonding ofDitals. The highiy probuble transstion due to absorption of quantiscd enetgy
molecular orbital to the Jowest
nvoves t e prototon ot one electron from the highest occupicd
an h e
Im tOnt of the Ccses, severll tasitions occur fesultng
avaabieunicu
hoecuar orDlat,
fomation of several bands.

2.7 Types of Electronic Transitions

when a molecule is excited by the absorption of
According lo the molecular orbital theory,
or Visible1igh), s clectrons are
cnergy (U
romoted from a boding to an antibonding orbital.
is assoczated
0) The antibonding orbital which
with the exCitation of a electron is called

orbital. So a to o
antibonding
O
transition takes place when o (gma)

electron is promoted to antibonding ( )

orbital. t is represented as G 0

transition
(i) When a non-bonding electron (a) gets

if n trinsntot
(a'), then represents 0
n) Samitarly - ransition represents he
Fig 25 Electronc ecitation energies
prototion of t elccirons lo an antibonding

orbital, Le, t" orbital, (See Fig 2.5)

fcalled sigma astetik

1Unshared pair of electrons,
 16 ELEMENTARY ORGANIC SPECTROSCOPY
Similarly, when an n-electron (non-bonding) is promoted to antibonding t orbtal, it
n T transition. The energy
represents
required for various transitions obey the following order
O a > n 0 >7-T" >n

Antibonding
Antibonding
Nonbonding

Bondi
Bonding
Fig. 2.6. Electronic excitation
energies
Let us now consider the various transitions involved in ultraviolet spectroscopPy.
aj
The organc
o-o tramsitions. It is
high energy process since a bonds are, in general, very strong
a
compounds in which all the valence shell electrons are involved in the
lormation of
sgma bonds do not show absorption in the nornal ultra-violet
saturated hydrocarbons, like methane.
region, Le.. 180-400
mu. For
propane etc. absorption occurs near 150 mu (high energY)
Consider 0 0 ansition in a saturated
hydrocarbon

n-a

C-C
CC C-O
Fig 2.7. Various transition
involved in Electronic
spectroscopy
Such a transition
requires radiation of very short wavelength
usual spoctroscopic technique cannot be uscd below 200 (High energy). See Fig. 2.7. The
to absorb strongly. lo mu. since oxygen (present in air) begins
must be
study such high energy transitions (below 200 m), the entire path lengh
evacuated
Thus, the region below
200 mu is
region. The excitation of sugma bond
electron to o
commonly called vacuum ultraviolet
(antubonding) level occurs with net
retention
Air must be excludod from the instrument so as to avoid absorption due to
oxygen.
 SPECTROSCOPY 17
ULTRAVIOLET AND VISIBLE
stale wich ay, in turn, gets convertcd to excited
of clevtronic spin, n is
calel excicd snglet
plet suae hs fepn h less
nformative
0 tmit Ths ype 01 Transito0 takes place i saluratcd conpounds containing

ne hetero lon with unhurcu Ct

h
ye of Ansitins u a siin Wuie
ansibos eue coparacy c a
absorhs at l6/ mjl, ncthyl alcoho at 174 my and methyl chloride absorbs at l09 m

la suturatc alkyt halhdles, the enciy required lor such a transihon decTeascs wit he nerease

ia the süze of the hakogen aiom (or decrease in the electuonegaivity of he a l ,

- -
Let us compare n-ot iransition in methyl chloride and methyl iodide. Due o the reer
electinegativily of chorine ilon, the n e l r c
The abhotaon as
vul Since this transition is more
WM ethwl indide, itw nolar extinction also higher c
A r coefficient
CRnction coefficienr 5s also nig
chle
ies absod compured to alchols and hence the extinction
a
waecs
oefl
be aer g transitions
are veiy sensitive to liydrogen bog
Alcohols as well as amines form hydrogen bonding with the solvent mölecules. Such assocatot
accurs due to the presence of non- bonding clectrons on the hetero om and thus, traon
to sarier
qures grealcr c e t 3 yaurogen bonding
sitts he unraey10let absorptrons
wavelengttis. (For detaily ee soven effects
the
tralon 1his type or
irunsufion ocCurs in tne nsatiuraice Cenies o
C e , e a n coaNS COing
dounic
ple bds and al t aromalics, 1he etcitation
C e c t r o n tequirc S a l c r cncrEy and hencc, transton ot this type o c u s at longcr wavelcngn

Ar electron of a double bond is excited to z orbital For exanple. akenes, aly u

COInpouds, cyanidkes, a 7 0 c o n p d s c c . sow C n n

C1C C1C
This transition requines still lesser energy as compared to 0 rantion and therelore,

m uncoialed akenes, aburIOn baids appear anound 170-190

ta-Volet spectroplhotonictct.
nd
m la carbonyl conpounods, he band due
to
ani appean arouna
p
o s t intense, ie, the valuce of extincton coetticich
e
gn alut en The
linkage prc a
alkyl group and the stereochemistry aboul the double bond.
n this type of transition, an electron of unstared electrom pair on
tero stom gets excied 1o anibonding orbital. This type of trisition requires leas no
of energy out of all the tranistioms discussed above andd hcnce Occun at ongor Wavelehg

show bodh the of tratsitions, fe, fow energy n an

Saturated aldehydes C0:1 types

Sshilt neanle kungr wavekengl

18 ELEENTARY ORG ANIE sPICTRCsCOP
UR TRAVIOETA
isn n since the evtntion cavtliciens fiw the luwe is uuite lre as o
that of the laner The exact electhone stnactiane of the milecules in the ecitel stute tby t abugtm

o ele tu whin the lecule la caboyt oompu a b h energy o anstiom al h i i

CCUs aral stesse Thiis.
s qusle salatall calt s a s take h l l n fie t

eakb-Rhand 9 The Chro

In curbonst compounds, the shift in the ahorption depenbs upon the poolany t u e
hne ounis
2.8 Transition Probability iwinalls
ectaon t an elevtro0 takes plice lom a tonlng orbita4

E t can be shown that

Ealncton coeticet

The ahipiii o
where

s found that the values

of 10 A or 10 cm The chromophore with low transition probubilily will have , value hel Chomophs
PHence, thene a direet relationship betwen the ane of the chromophore and the absonpti Such hro
csy a j t e , there are seome other factors alio which govern the ramition probahility
L T T E upot tue ymhetiy and the Value ol e the tratsitios can be classcd as

Htatalee Trasitins

allowed
a 217 mu 21000 is an exumple of allowedl iransition. vacus ra
he forbidden tranhilioe ih a tesull of he cacitatoa ol s e eiecirOn Tron he lonc puit pee
on the hetcialosn to an
a in5 al hea t a 190 n as a
resil
waltc betwect 0 s
the result t
Jorbidalct transMl Tle valocs
There e n t
transitions obuervel in tie Cosldc cnzoplhenone. The T the iictiy

252 mu
2000KU tallowed)
0loetocn
T h etranition lallowed or forbidder
elated wsth he pcohetes of the lawer and the fhigfct enery nolecular orbitals and also
amolecules have noe restrhictioms on t

lecule. Thus, many restrictions appely to the electone tm

thas, ei r t n spectnum is sngle. For a totally unsymmetrical molccule, no symne Anbp
R-hanide (Radikalantig-Cierman