MOLECULAR

SPECTROSCOPY

Spectroscopy

Study of the Interaction of Electromagnetic

Radiation (Energy) and Matter

When energy is applied to matter it can be

absorbed, emitted, cause a chemical change
(reaction), or be transmitted.

Electromagnetic Spectrum!
Cosmic (Gamma) X-Ray
Ultraviolet isi!le "#$rare%
Micro&ave Ra%io

lo" high #re$uency ()
Energy
X-RAY ULTRAVIOLET INFRARED
MICRO-
WAVE
RADIO FREQUENCY
Ultraviolet Visible
Vibrational
inrare!
N"#lear
$a%neti#
resonan#e
&'' n$ ('' n$ )'' n$
&*+ $ ,+ $
, $ + $
short long Wa%elength ()
high lo"
&'E E(E)&R*M+,-E&I) S.E)&R/M
&'E E(E)&R*M+,-E&I) S.E)&R/M
-LUE RED

T'E SOLAR SPECTRUM

"S"(LE SPECTRUM
(&avele#)t*s o$ vario+s ra%iatio#s)

Violet: 400 - 420 nm

Indigo: 420 - 440 nm

Blue: 440 - 490 nm

Green: 490 - 570 nm

Yellow: 570 - 585 nm

Orange: 585 - 620 nm

Red: 620 - 780 nm

Ele#tro$a%neti# ./e#tr"$
nuclear spin flips* >1 mm <3x10
11
radio waves
molecular rotations, electron
spin flips*
1 mm-! "m 3x10
11
-10
13
mi#rowaves
molecular vibrations ! "m-$! "m 10
13
-10
1%
in&rared
outer electron molecular
vibrations
$! "m-'!0 nm 1x10
1%
-%x10
1%
near-in&rared
outer electron '!0 nm-%00 nm %-'$!x10
1%
visi(le
outer electron %00 nm-1 nm 10
1!
-10
1'
ultraviolet
inner electron 1 nm-1 )m 10
1'
-10
0
*-ra+s
nuclear <1 )m 10
0
-10
%
gamma-ra+s
,+)e o& ,ransition
-avelengt.
Range
/re0uen#+ Range
1234
,+)e o&
Radiation
, $or e#er)y levels s-lit !y a ma)#etic $iel%

A ty-ical s-ectro-*otometer (or)
s-ectrometer

./e#tros#o/0 T0/es.
/ Ultraviolet ./e#tros#o/0 1UV2 3 Electronic Energy States
Use Conjugated Molecules; Carbonyl Group, Nitro Group
/ Inrare! ./e#tros#o/0 1IR2 3 Vibrational Energy States
Use Functional Groups; Compound Structure
/ N"#lear Ma%neti# Resonan#e 1NMR2 3 Nuclear Spin States
Use !e number, type, and relati"e position o# protons
$%ydrogen nuclei& and Carbon'() nuclei
/ Mass ./e#tro$etr0 1M.2 3 %i'Energy Electron *ombardment
Use Molecular +eig!t, ,resence o# Nitrogen, %alogens

UV Spectroscopy

*bser%ed electronic transitions
Ener%0

n
+tomic orbital +tomic orbital
Molecular orbitals
*ccupied le%els
/noccupied le%els

U-S-ectrosco-y

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.ossible electronic transitions of p, s, and n
electrons are

UV Spectroscopy
#rom the molecular orbital diagram, there are se%eral possible
electronic transitions that can occur, each of a different relati%e
energy
Ener%0

n
n

al0anes
carbonyls
unsaturated cmpds.
*, -, S, halogens
carbonyls

U tra#sitio# ty-e

,*445 transitions. $or com-o+#%s &it* 1 !o#%

o#ly2 *i)* 3E2 s*ort 4 (5 677 #m)8

A--ears i# sat+rate% *y%rocar!o#s &it* 1 or!ital a#%

tra#sitio# to a#ti!o#%i#) 1, or to molec+lar Ry%!er)
or!ital (*i)*er vale#ce s*ell or!itals2 9s2 9-2 :s2 ;)2
a#% i#volves lar)e 3E2 a#% small 4
ma<
t*at a--ears i#
$ar-U re)io#8

E).- cyclo-ro-a#e 4
ma<
=>7 #m8

cycloal?a#e 4
ma<
=9@ #m8 (vac+m U)

U tra#sitio# ty-e

&* n65 transitions 7 t*e e<citatio# o$ a#

electro# o# a# #o#!o#%i#) or!ital2 s+c* as
+#s*are% -air eAs o# O2 B2 S288to a#
a#ti!o#%i#) C,2 +s+ally i# a# %o+!le !o#%
&it* *etero atoms2 s+c* as CDO2 CDS2 BDO2
etc8 A sym8 $or!i%%e# a#% lo& i#te#sity
tra#sitio#8

E<.- sat+rate% al%e*y%es a#% ?eto#es . 4

ma<
at
=E@-977 #m8

U tra#sitio# ty-e

8*665 transitions 7 $or com-o+#%s

co#tai#i#) %o+!le2 tri-le !o#%s2 or aromatic
ri#)s0 a C electro# is e<cite% to a#
a#ti!o#%i#) C, or!ital8 T*is is +s+ally a sym8
allo&e% a#% *i)* i#te#sity tra#sitio#8

Et*yle#e . a!sor!s at =F6 #m (=7777)2 i#

vac++m U8 E<te#%e% co#G+)atio# lo&ers2
3E2 a#% i#crease i# 4
ma<
2 i$ e<te#%e% !eyo#%
@ %o+!le !o#%s t*e# )etti#) i#to visi!le
re)io#8

U tra#sitio# ty-e

(* n45 transitions7 e<citatio# $rom

#o#!o#%i#) or!ital to a# a#ti!o#%i#) 1,
or!ital8
E<.- C'
9
O'(va-8) =E9 #m (H =@7)
BEt
9
(va-8) 66I #m (>77)
Me"(*e<a#e) 6@E #m (9E7)


Ter$s !es#ribin% UV absor/tions
=8 Chromophores functional groups that gi%e electronic
transitions.
1.Auxochromes substituents "ith unshared pair e3s li0e *',
-', S' ..., "hen attached to 4 chromophore they generally
mo%e the absorption ma5. to longer 6.
7.Bathochromic shift shift to longer 6, also called red shift.
8.Hysochromic shift shift to shorter 6, also called blue shift.
9.Hyperchromism increase in : of a band.
;.Hypochromism decrease in : of a band.

UV Spectroscopy
)hromophores

+. <efinition!
Remember the electrons present in organic molecules are
in%ol%ed in co%alent bonds or lone pairs of electrons on atoms
such as * or -
Since similar functional groups "ill ha%e electrons capable of
discrete classes of transitions, the characteristic energy of these
energies is more representati%e of the functional group than the
electrons themsel%es
+ functional group capable of ha%ing characteristic electronic
transitions is called a chromophore (color loving)
Structural or electronic changes in the chromophore can be
$uantified and used to predict shifts in the obser%ed electronic
transitions

UV Spectroscopy
I. )hromophores
+. *rganic )hromophores
Alkanes = only posses !bonds and no lone pairs of electrons,
so only the high energy > transition is obser%ed in the far
/?
&his transition is destructi%e to the molecule, causing clea%age
of the !bond

C C
C
C

UV Spectroscopy
I. )hromophores
+. *rganic )hromophores
Alcohols, ethers, amines and sulfur compounds = in the
cases of simple, aliphatic e5amples of these compounds the n
> is the most often obser%ed transition@ li0e the al0ane > it
is most often at shorter than 1AA nm
-ote ho" this transition occurs from the '*M* to the (/M*

CN

)-
n
- sp
7
C N
C N
C N
C N
anitbon!in%
orbital

UV Spectroscopy
I. )hromophores
+. *rganic )hromophores
Alkenes and Alkynes = in the case of isolated e5amples of
these compounds the > is obser%ed at BC9 and BCA nm,
respecti%ely
E%en though this transition is of lo"er energy than >, it is
still in the far /? = ho"e%er, the transition energy is sensiti%e to
substitution

UV Spectroscopy
I. )hromophores
+. *rganic )hromophores
Carbonyls = n > transitions (D1E9 nm)@ > (BEE nm)

)*
transitions omitted for clarity
O
O
C O
It has been
determined from
spectral studies, that
carbonyl o5ygen
more appro5imates
sp rather than sp
1
F

hexane
hexane
200
360
205
255
n
55
> *
n
55
> *
Methyl
bromide
Methyl
Iodide
C-X X!r
XI
ethanol
ethanol
"7
5#000
275
200
n
55
> $*
$
55
> $*
%itromethan
e
%&
hexane
hexane
"5
"0#000
290
"80
n
55
> $*
$
55
> $*
'thanal C&
hexane "0#000 "80 $
55
> $* "-(exyne C)C
hexane "5#000 "7" $
55
> $* 'thene CC
6olvent 7
8
max
9 nm
:x#itation :xam)le ;.romo).or

UV Spectroscopy
I. )hromophore
+. Substituent Effects
General = from our brief study of these general chromophores,
only the "ea0 n > transition occurs in the routinely obser%ed
/?
&he attachment of substituent groups (other than ') can shift
the energy of the transition
Substituents that increase the intensity and often "a%elength of
an absorption are called auxochromes
)ommon au5ochromes include alkyl, hydroxyl, alkoxy and
amino roups and the haloens

I. )hromophores
+. Substituent Effects
,eneral = Substituents may ha%e any of four effects on a
chromophore
Bathochromic shift (red shift) = a shift to longer @ lo"er
energy
Hypsochromic shift (blue shift) = shift to shorter @ higher
energy
'yperchromic effect = an increase in intensity
'ypochromic effect = a decrease in intensity
677 #m I77 #m

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*+ ,b-or.tion- /or -ome i-olate 0hromo.hore-

UV Spectroscopy
!!!" !nstrumentation and Spectra
+" Instrumentation !
B. &he construction of a traditional /?!?IS spectrometer is %ery
similar to an IR, as similar functions = sample handling,
irradiation, detection and output are re$uired
1. 'ere is a simple schematic that co%ers most modern /?
spectrometers
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< n$
mo#oc*romatorJ
!eam s-litter o-tics
U-"S so+rces

1AA 11A 18A 1;A 1EA 7AA 71A
B;
B8
B1
BA
E
;
8
"a%elength(mu)
Molecular
E5tinction
)oefficient(")

APPL"CAT"OBS OK U ABL
"S"(LE SPECTROSCOPY

UJis s-ectrosco-y is ro+ti#ely +se% i# t*e

M+a#titative %etermi#atio# o$ sol+tio#s o$
tra#sitio# metal io#s a#% *i)*ly co#G+)ate%
or)a#ic com-o+#%s8

Or)a#ic com-o+#%s2 es-ecially t*ose &it* a

*i)* %e)ree o$ co#G+)atio#2 also a!sor! li)*t i#
t*e U or visi!le re)io#s o$ t*e
electroma)#etic s-ectr+m8

T*+s UJ"S s-ectrosco-y ca# !e +se% to

%etermi#e t*e co#ce#tratio# o$ a sol+tio#8

A//li#ations

N+a#titative %etermi#atio# o$
c*romo-*ores co#ce#tratio#s i# sol+tio#

"m-+rity %etermi#atio# !y s-ectr+m

s+!tractio#

Letermi#atio# o$ reactio# ?i#etics