UNIT 7 MOLECULAR

SPECTROSCOPY - I
Structure
7.1 Introda,.'on
Objectives
7.2 Energy Levels in Molecules
7.3 Types of Molecular Spectra
7.4 The Intensity of Spectral Lines or Bands
7.5 General Features of Absorption Spectrometer
7.6 Requisite for Microwave Absorption .
7.7 Theory of Rotational Spectra
7.8 Rotational Spectra of HC1 Molecule
7.9 Summary
7.10 Terminal Questions
7.1 1 Answers

7.1 INTRODUCTION
In Unit 6, we studied the correlation between some of the molecular properties and molecular
structure. Presently, we take up the study of molecular spectra with a view to obtain more
direct information about molecular structure. It is worth recollecting that in Unit 1, we have
seen how atomic spectra are useful in the understanding of the electronic arrangement in
atoms. The transitions of the electrons between the various energy levels of the atom result
in emission or absorption of electromagnetic radiations. Corresponding to energy difference
between the levels, the spectral lines occur in different regions, and this gives rise to atomic
spectra. Just as atomic spectra give information about the structure of the atom, molecular
spectra give information regarding the molecular structure. We may define molecular
spectroscopy as the study of the interaction of electromagneticradiation with molecules.
In this unit, first of all we explain different types of energy levels in molecules and the
conditions under which transitions occur among these levels. Then we describe various types
of ?bsoption spectra and general features of a spectrometer used in obtaining absorption
spectra. We then explain how rotational spectra can be used to calculate simple molecular
parameters like bond length and moment of inertia. In the next unit. we shall study how
infrared, visible and ultraviolet spectra can be used to obtain some more molecular
parameters.

Objectives
After studying this unit, you should be able to :
define different types of energy levels in molecules,
state various types of molecular spectra,
explain the reason for the difference in the intensity of spectral lines,
describe the general features of an absorption spectrometer,
I state the pre-requisite for exhibiting rotational spectra,
explain the theory of rotational spectra, and
calculate the parameters like bond length and moment of inertia of a heteronuclear
diatomic molecule using microwave spectra.

7.2 ENERGY LEVELS IN MOLECULES

-

We have already discussed in Unit 1 the energy changes in an atom, accompanying the
transfer of electrons from lower energy levels to high energy levels and vice versa. The
electronic transitions in an atom are due to absorption or emission of electromagnetic
radiation. We have further stated that electronic transitions in an atom are quantised and the
resulting line emission spectra correlate with the difference between the electronic energy
levels.
 Structure of hlrtter-11 There are more possibilities for transition between various energy levels in the polyatomic
molecules than those in individual atoms. The total energy of a molecule is the sum of four
different types of energy, viz., translational, rotational. vibrational and electronic. Therefore.
absorption or emission of energy (electromagnetic radiation) may cause changes in some or
all of these types of energy, and molecular spectra provide a method of measuring these
roulld about arrow in fig. 7,1a changes. Before going into further dxails of molecular energy changes, their measurements
indicates the rotatio~iofthe molecule and interpretation, let us fust define the energy types present in molecules.
about an axis(indicated as dotted
lille) passing through centre Translaiional Energy (E,,,) is concerned with the overall movement of the molecules
of gravity. The arrows attached to along the three axes. It is significant only in gases and to a lesser extent for liquids. In
each atom in figure 7.lb -d show solids, translational energy is minimum.
the direction of its ~ n o t i oduring
~~
half of the vibration. Rotational Energy (Em, ) involves the spinning of molecules about the axes passing
through their centre of gravity (see Fig. 7.1 a).

*,
Vibrational Energy (E,,) is associated with vibrations within a molecule such as the
stretching or the bending of bonds (see Fig. 7.1 b, c and d ). In stretching
length varies but in bending type, bond angle varies. .
the bond

Electronic Energy (E,,,,) involves changes in the distribution of electrons by the

promotion of electrons to higher levels on absorption of energy. This is similar to elecmriic.
energy changes in atoms.
I
cL3
C* ;' a 5 I A
(b'
,
(c)
,A (4
*/
(a)

Fig. 7.1 : Rotation and vibration within molecules: (a) shows rotation aboul two
different axes; (b). (c), and (d) show vibrations. (b) and (c) are referred to u
stretching and (d) as bending.

Now, if E is the energy of a molecule, it can be expressed as the sum of translational,

rotational, vibrational and electronic conmbutions.
Moleculv energies in increasing order E = EVMs+ Em, + Evib+ Eel= ...(7.1)
of their magnitude : Em, < E vib
< Eslec. The translational energy levels of a molecule in a container are so close that they can be
considered as continuous. The other three forms of energy are considered to be quantised in a
manner similar to the electronic energy in atoms. The magnitude of the various forms of
energy and the difference between adjacent levels vary considerably. Calculations indicate that
the difference between the energy levels for electronic energy change is about 100 to lo4 kJ
mol-I, for vibrational energy changes, it is generally between 1 and 100 kJ mol-I, and for
rotational changes, it is between 0.01 and 1 kJ mol-I. On the other hand, at room
temperature, the average translational energy of gas molecule is about 1CFZ1J molecule-'.
We may use two different conventions to i1:ustrate molecular energies further. The tirst
shows a plot of energy of the molecule v-rsus interatomic distance, as illustrated in Fig. 7.2.
This figure shows how the energy,of the molecule changes with the interatomic distance.

Internuclear distance ( r )
Fig. 7.2 : Representative plot for the potentla1 energy of a diatomic molecule.
28
The two curves npresmt the ground and the first excited electronic state or electronic energy Molecular Spectroscopy-I
level. The individual. narrow lines indicate the allowed quantum vibrational and rotational
kvels. The mokcule can reside in any one of the quantised rotational, vibrational and
elcclronic energy levels that are indicated in this figure. A diagram such as this is usually
used only for diatomic mokcules because, for polyatomic molecdes, there are too many
diffneat interatomic distances to be represented.
The second convention is to represent the energies of molecules as exemplified in Fig. 7.3.
We show camparative spacing of energy levels of different types of energy. It is clear that
electronic levels ate much more widely spaced than vibrational levels, which in turn are more
widely spaced than rotationallevels.

Rotational

F m excited
elsftronic ante .S

Vibrational
kveb

Fig. 7.3 : Diagranmatk npresenhtion of W b k quantised energy levtb and energy

cbangn within a n o l u u k .

As in the atomic spectra, quantised energy changes within a molecule are associated with the
emission or absorption of electromagneticradiation and these can be detected in the form of
spectra using an insmunent, known as spectrometer. The energy changes in a molecula
a ~ specified
e in terms of fiqutncy (v). wavelength (A) and wave number (i) as per Eq.7.2.
Energy change (AE ) = hv = hc /A = hc F ...(7.2)
where h is the Planck's constant and c is the velocity of light.
You can find a list of units normally used in representing these quantities in Table 7.1. We
use these quantities to express the position of a line or band in the absorption or emission
spectrum. "
Tabk 7.1 : Paramcterr Commonly U d for Representing Wavelength. Frequency and
Wave Number

Parameter Symbol Unlt

Wmknah I ~ 1 @ m

Frssuary v Hz a s-'
-
W m number v m-' (or m a t
commonly m-')

Further. the choice of the unit of a particular quantity depends on how far it can be expressed
as a convenient small number. For example, 'nm' unit for wavelength is chosen to represent
absorptions in ultraviolet and visible regions of electromagnetic spectrum since values of
wavelength in this region lie between U K ) - 800 nm.We have already discussed
electnomagnetic spectrum and its regions in Unit 1,
1 structure d Matter-I1 You should try the following SAQ to be convinced that ? ,v or AE values are not quite
convenient in exoressin~absorptions in ultraviolet region.
SAQ 1
Calculate the following corresponding to A = 200 nm :

a) AE (in kJ mol-l)
b) v
c) 9

7.3 TYPES OF MOLECULAR SPECTRA

As you know, the molecules can exist in specific molecular energy levels. The rotational,
vibrational and electronic energies are quantised in a manner similar to quantisation of
electronic energy of an atom. As a result, spectra from even simple molecules exhibit large
number of lines. To illustrate this, the emission spectrum of N, in the ultraviolet region is
given in Fig. 7.4.

(a)

Fig. 7.4 : Spectra of nitrogen molecule : (a) bands of Nz at low resolution; (b) bands or
N 2 resolved into individual lines corresponding to transitions between rotational-
vibrational sublevels of the electronic states.

Specm can k ma&d in hvuways. In this case, unlike atomic spectra, molecular spectra appear as bands at low resolution (see
The frat method is to depict
photogmphicllly the aress of greater Fig. 7.4a). At high resolution, one finds that instead of the bands, the spectrum is composed
and lesser exposure i d ~ c w n gthe of sharp lines. These lines arise from the presence of vibrational and rotational energy levels.
light intensity at each wavelength or Since there are many such levels, a large number of individual lines are possible for a single
wave numbex a &apemy (Sec
spectrum of Nzin Fig. 7.4); The electronic transition. Such a high resolution spectrum is shown in Fig. 7.4b. This figure can
otha method is to plot a graph with give you an idea as to how complex the whole spectrum would look, with many electronic
v
A o r v or inthex-axisand , energy transitions, interspersed with vibrational and rotational changes.
absorbsncJ trummi~ancein they -
axis. (See the speCtrum of bcnza~ In solid or in liquid phase, even at high resolution, these individual lines are broad and are
given in Pi.7.5).
known as tmresblved bands. All the spectra that we use for analysis of condensed media
(liquids and solids) have bands due to large number of unresolved spectral transitions. This is
illustrated in Fig. 7.5. Notice that the absorption bands are more sharp for benzene vapour
rather than for its solution in ethanol.
 Molecular Spectroscopj-l

(a) (b)
Fig. 7.5 : Absorption spectrum of benzene in ultraviolet region : (a) benzene vapour ;
(b) benzene in ethnnoL

Now we will consider molecular spectra in detail. Depending on the method of obtaining
molecular spectra, it can be classified into three types, viz:,
i) Emission spectra
ii) Absorption spectra
iii) Spectra through scattering, such as, Raman spectra.
Let us study each of these types in a brief manner.
i) Emission Spectra
Molecules give emission spectra when subjected to intense heat or electric discharge. By this
process, the molecules obtain the necessary energy to become excited. On returning to their
lower energy state, molecules may emit radiation. Such emission is the result of a transition
of a molecule from an excited state to one of lower energy, usually the ground state. This
excess energy is emitted as a photon and the corresponding frequency is recorded as the
emission spectrum. If the transition is from upper energy level E2 to lower energy level
E,, the frequency ( v ) of the emission spectrum is given by,
E2-E1 AE
v
h
= ---
- h
...(7.3)
As an illustration, a portion of the emission spectrum of N, molecule is given in Fig. 7.4.
The different spectral series in the atomic spectra of hydrogen discussed in Unit 1 are
examples for atomic emission spectra.
ii) Absorption Spectra
When a substance is irradiated with electromagnetic radiation. the energy of the incident
photons may be transferred to the molecules, raising them from the ground state to an
excited state. This process is known as absorption and the resultant spectrum is known as
absorption spectrum. Energy absorption occurs only when the energy difference between
the ground state and higher energy level is exactly match& by the energy of the incident
electromagnetic radiation. The frequency of the absorption spectrum is also given by the
Eq. 7.3.
The difference between emission and absorption spectra is that in emission spectre, the
molecule passes on from higher energy level to lower energy level ; in absorption spectra, it
is raised from lower energy level to higher energy level. The energy absorbed, AE, by a
molecule may bring about changes in one or more of its energy levels such as.rotational,
vibrational and electronic.
In an absorpt~onspectrum, it can be seen that molecule absorbs some of the wavelengths (or Relat~onsh~p between absorCan~eand
frequencies or wave numbers) of electromagnetic radiation while the rest of it is transmitted. % transm'ttancecan be by
the relation:
We can plot either absorbance ( A ) or percent transmittance (%T ) vs. wavelength or
frequency or wave number to get the absorption spectrum. The plot of absorbance ( A ) vs. 100
A =log( *)=2-log(%T)
wavelength or frequency or wave number is illustrated in Fig. 7.6a. In thls figure you can
see that two maxima occur, corresponding to the points (i) and (ii), denoting inten'se
absorptions at the corresponding wavelengths, frequencies and wave numbers. If the
Structure ad Matter-ll absorptions are to be represented as % transmittimce (%T)VS. wavelength or f r e q or~
wave number, the plot will look like Fig.7.6b. Minima appear in Fig. 7.6b comsponding
to the maxima of Fig.7.6a. We will discuss absorbance and transmittance in detail inunit 8.

(a)
Flg. 7.1 : Presentallon d abrwptlos rpactral data.
,
iii) Raman Spectra

d.
Besides the above two types of spectra, anotner variety is also observ When a substance is
irradiated with electromagnetic radiation, some of the radiation may scatted as shown in
Fig. 7.7.
Trammined
rdish

rk

Spectrometer Scattered
+ - ]i-
A

-p.
radiation
Raman spectra 14

Incident
radiation
Fig. 7.7: Origin of Raman Spectra in scattered Ilght.

Al-isadcvicc~ poducaan The scattered radiation shows some lines of higher and some of lowet frequency than that of
incident radiation. This arises because incident radiation can lose energy in exciting the
coherent light. A laser bum mnalns
a n m pencil of l~gt even aner molecules or can alternatively gain energy from molecules already excited. The resulting
tnvelling a dime. word spectrum SO obtained is known as Ramrm Spectrum. The lines of lower frequency
' l a d scndP for light amplificat~on called Stokes lines; those of higher frequency are known as antkstokes lines. The
by the stimulated em~ssionof experimental method of obtaining Raman spectra is different because the lines are very weak,
rad~atm. but the use of lasers for the incident radiat;on has made the technique easier and of wider
application.
Absorption spstra are studied e x t e q d e ~in~order to elucidate the structure of molecules.
We shall concentrate only on absorption s,ectroscopy in this and the next unit. The
molecular spectra are more complicated than atomic specrra; they range over wider regions of
the electromagnetic spectrum and their interpretation is often more difficult. We divide
absorption speclra into different types on the basis of the radiation absorbed. In th~sand the
next unit. we are concerned with three types of molecular absorption spectra as given below:
Microwave Spectra: Reglon of electromagnetic specaum (3 x 101° to 3 x 1012Hz or 1
cm-' to 100cm-') is concerned with the energy'changeof rctational levels which are of the
order of 0.01 to 1 kJ mol-'. Microwave radiation does not affect vibrational and electronic
energy levels as it changes only the rotational energy and the resulting niolecular spectra is
called rotational spectra The principles and the information given by rotational spectra
will be dealt in sections 7.6 to 7.8.
 Molecular Spectroscnp~ ;
Infritrccl Spectra: Electrornitgne~icratliario~iirt the itll'r:rrcct region of the spectrum
(3 x l O l 2 10 3 x 10" Hzor 100 ctn-I to 104cnl-I) results in ch;~ngesofthe vibrational
energy ol.n~olecules.Tllr energy ch;ulge required Ihr niolecu1:rr vibrations is of the order of I
to Itlo kJ mot-'. and chanses in vibr:ttional energy levels are ;rccompanied by transitions
&tween rot;~~ional levels too. So. in a vibrational spcctrunr. each line is accompanied by the

i
rot;lt!,vr;ll I.irlr structilres. Such ;I spcctruni is evidently ktwwn as vibrational-rotational
spectrum. IFwe do not considcr thc rotational fine structure. absorption spectrum is called
vibrational . ;ectrum.
Ultruviolet m d Visible Spectra: Electromagnetic radiation in the ultraviolet and
visible icgions ( 3 x 1 0 1 4 -3 x 1 0 1 " Hz or IIW)O - 1 0 nnl) of the Spectrum results in cbnees
in [he rlectrollic structure of molecules. The energy change observed in this region is of [he
ordci of lo() - l(p kj nlol-'. This type of absorption spectra is also called electronic
spwtra. The vibrational and rotali'>nal transitions also aCCOmpiiny elecuonic transitions
and tllrse transitialls appear as broad band absorption spectra. In practice, [he region
o ( ) - ~ ( ) onnl is generally used by chemists to observe electronic spectra..In Table 7.2, we
summ;llise the types of absorption spectra and information available from each type.

'I.abl~7.2: Types of Absorption Spectra and the Information obtained from these

Radiation absorbed Effect on the molecule lnformat ion deduced

Micmwavc
' r~=~x#)~"-3xlO'~Hi! Change in mlational energy Calculation of bond
1. =I-100cm-' leveis of the molecule length, bond angle, etc.
d = t cnl - 0.01 cn1
1; = 0.01 - 1 kJ mol-'

Change in the vibrational and Detection of functional

rotational energy levels in groups in compounds,
d = 0.0 1 cn~ ION) nm
- the molecule calculation of force
E = 1 - It10 kJ mat-' constant, bond length and
bond angle, etc., and in
quantitative analysis.
U!tr:l~i~lCtand Visible
v = 3 x 1014-3~ IO'~HZ Change in electronic energy In qualitative and
5 = I @ - ldcm-I levels within the molecule. quantitative analysis.
I = 1tWK)nm- IOnm Vibrational and rotational
E = 100- l # k J mol-I transitions are also brought
about: but their resolution is
not possible in solid and
liquid states.

..
YOUQ' the following SAQ, which is based on the above discussion.

Indicate the type of energy change brought about. when a gaseous rnolecuIe is exposed to the
following radiation. Write your answer in the space provided.
a) I n W
....................................................................................................................
b) Ultraviolet
................... .................................................................................................
c) Microwave
............................
........................................................................................

..........................................................
........................................:..........,......
33
 - -- -
Structure of Matter-I1
7.4 THE INTENSITY OF SPECTRAL LINES OR
BANDS
In the previous section, we have discussed the origin of spectral lines or bands in a spectrum.
Now, in this section we are going to focus our attention on the factors which are responsible
for the number and intensities of spectral lines or bands.
The number and the intensities of lines or bands which may appear in a spectrum are
determined by the factors such as population of the energy levels and quantum mechanical
selection rules.
The number of molecules present at each energy level is known as the population at that
energy level. A large population at a particular level indicates that a large number of
molecules may undergo a particular transition giving rise to an intense absorption band.
Quantum mechanical selection rules help t.s in deciding whether a particular transition is
allowed or not. Again, the molecules, undergoing a transition which is permitted by the
selection rules, give rise to an intense absorption line or a band. Forbidden transitions are
those which are not permitted by the selection rules and give rise to weak absorption pattem.
In our study of molecular spectroscopy, we will not go into the detailed reasoning for
intensity pattem of spectral transitions; instead we will pay more attention to the
applications of different types of specea. Before taking up the details of the microwave
spectra, let us first consider some features of an absorption spectrometer.

7.5 GENERAL FEATURES OF ABSORPTION

' SPECTROMETER
Let us now study the instruments used for obtaining molecular spectra. The instrument
which we use to record-the spectra of molecules, is called a spectrometer. The exact design
of the instrument varies according to the spectral region being examined. But the basic
features of all spectrometers are similar. A generalised schematic representation is shown in
Fig. 7.8.

Source of. Analysing

chawristic 3
radiation monochmmrrtor integrator

(a) (4
Fig. 7.8 : Schematic layout of spectrometer.

The essential features of an absorption spectrometer are fairly simple. It consists of a

suitable source of electromagneticradiation, a system to analyse the radiation or a
monochromator and an appropriate detector to detect the intensity of the radiation absorbed.
Depending on the technique, the sample may be positioned between (a) and (b) or between
(b) and (c). These features are summarised in Table 7.3 for the different spectral types.
The final absorption spectrum is displayed either on a video screen or, more generally,
recorded on a chart paper. In this manner, we can measure the extent to which a substance
absorbs radiation at each wavelength (or frequency or wave number).
Table 7.3 : Gtnernl Ftalures of Absorption Spectrometer
L

Ultraviolet Visibk Jnhrzd Microwave

H~mc%en Tungsten Elecaically Klystron

A high fmquency radio valve is called Source d~schage filament h&airod valve
alilystmn valve which can be turned lamp lamp of rare
to emit monochromatic radiation over (a) earth oxides
a limited range of frequency in the
microwave ngion. Systm System of muiun and rotating Systcm of Frequency
of graung to selkt appropriate mirmrsMd v&d
The busteen ekments from Ce to Lu mating fling e1strmWY
Analysis wavdlength.
arc knownas renearth elanatts.
Cb)
I
 Molecular Spectroscopy-l
solutions but Gases, liquids Gases or
gases can be used. Quartz cell dilute solutions, Vapours

II I
uscd'in ultraviolet region.
1I solids ground with
KBrandpressed
into discs.
I I

With this background, we take up the study of microwave spectra in this unit. We shall
study infrafed, visible and ultraviolet spectra in the next unit.
--
7.6 REQUISITE FOR MICROWAVE ABSORPTION

We have mentioned earlier that absorption in the microwave region of electromagnetic

spectrum can cause transition of the absorbing molecule from one rotational level to another.
Therefore, the microwave spectra is also known as rotational spectra. The condition for a
molecule to exhibit rotational spectra is that a molecule must possess permanent dipole
moment. When a molecule having permanent dipole moment rotates, it generates an electric sprlctra.
n'mcn' although
can a'w these an: a
field which can interact with the electric component of the microwave radiation. During this .(;, ,,this uni,, shall b,,,,,,UL,
interaction, energy can be absorbed or emitted and thus the rotation of the molecule gives only tfic s ~ c t r a o f m o l e c u l c which
have permanen1 d i p l c rncnncnt.
s 1
rise to a spectrum. If molecules do not have permanent dipole moment, interaction is not
quite prominent and these molecules are said to be "microwave inactive" . Examples of
microwave inactive molecules are HZ,Cl,, etc. On the other hand, the molecules like HCI,
CH,CI, etc., which possess permanent dipole moment are "microwave active".

- bond
k t US now see how microwave w c t r a can be utilised to derive information regarding
- I
length. Before that, answer the following SAQ.
SAQ 3
I
Which of the following molecules can absorb in the microwave region? Write YES or NO in
the space given.

a) CO .........................................................................................................

b) SO, ........................................................................................................

6) CI, .........................................................................................................

\ ..-.

7.7 THEOR'Y OF ROTATIONAL SPECTRA

-
. -
. -..

1 We have already mentioned that rotational energy, like other forms of molecular energy, is I
quantised. The permitted energy values (energy levels) may be calculated for any molecule by
solving the Schriidinger equation for the molecule. For simple molecules, the derivations
involved.are somewhat simple while for large systems, it is more complicated and requires

I
gross approximations. We are not concerned with tedious derivations of the expressions like
Eq.7.4, but we will only apply the same to simple cases such as heteronuclear diatomic
molecules. For such a system. the rotational energy levels, as obtained by solving thc
Schriidineer euuation. are eiven bv the ex~ression.
1I Structure of Matter-I1
of Era
' where.
.- - 7

h = Planck's constant (6.626 x J s),

17
n-
: ~ n ~ t o f - J ( J + 1)
8$1 I = Moment of inertia (kg m2),
--J2 s2
- k g m2 J = Rotational quantum number which has values 0, 1 , 2. 3, etc. It is dimensionless.
Note that J (italicised) stands for the
rotational quantum number whereas J By the application of simple mechanics, we can define moment of inertia. Consider a
(roman) srandsforthe energy unit, diatomic molecule AB, in which atomic masses of the atoms A and B are m ,and m,,
Joule Here standsforthe energy respectively. Suppose that these two atoms are joined by a rigid bond of length r- . Let the
unit, joule , *lso
11(1a1itum
.. Ihe rotationa1
nurrioer J 1s a mere nurnocr
two atoms A and B be at distances r, and r,, respectively, from the centre of gravity G of the
I.....r m ,...:. molecule about which the moleculerotate~end-overas shown in Fig. 7.9.

I ,,r~cc,the unit of
J? s2
Erot = -
kg m2 ,
I 1 -2

Fig. 7.9 : Simple model for rotational motion of a diatomic molecule.

It is evident that the bond length r must be eaual to the sum of r-, and r;.

In this case. the moment of inertia. I. about the axis of rotation is defined by.

Since G is the centre of gravity, moments mlr, and m2r2,must be equal.

On rearranging this expression, we get,

. using the characteristics of proportions, we can write,

Similarly, rearranging Eq.7.7 as,

we get.

On substituting Eqs. 7.8 and 7.9 in Eq. 7.6, we obtain the following expression,
Rearranging, we get.

where p is the reduced mass of the diatomic molecule and its value is y = n11ni2/(m1+n12).
The unit of reduced mass is kg. Eq. 7.1 I defines the moment of inertia in terms of atomic the PuTose of introducing the term,
nurses and bond length. reduce mass, is to simplify the
rotation of a two partical system
Now consider again Eq. 7.4. which ex.presses the allowed energies in joules; we, however, (Of masses m l ) into thar
of a one partical systeni (of mass CI )
generally express rotational energies, in terms of wave number. Since E = h c i , Eq. 7.4 can
be written as:
- h"
v=---J(J+ 1)
8z' fhc
--
- J ( J + I)
8 z2fc
where c. is the velocity of light expressed ill in s-I and the unit of wave number is reciprocal
meter or m-I .

Further, we generally write B for h /87rLlc; so, Eiq.7. 12 can be expressed as,
- - h
v = B . I ( J + I) . ..(7.13) Unit of v = unit of --
8a 21c
J (J + i ;

- J s
where B is called the rotational constant. The literature values for B are in cm-I unit. - kg m' nl s-'
You can convert the values in cm-I unit into m-' unit, if you remember the relationship, Remember, the rotatiortal quantum
1 m-l = (10'cm)-' = I @ ~ c ~ - I number, J , has no unit.
Unit "f - = -- J s
We shall illustrate this conversion in Sec. 7.8. kg m3 s-I
kg -
-- m2s-'s
From Eq. 7.13, by using integral values 0, I, 2, 3, 4, 5, etc. for J we can show the allowed kg m%-'
rotational energy levels diagrammatically, as in Fig. 7.10.
= "1-1

Rotatiorial Allowed rotational energy

number (3) value in 5 unit

Fig. 7.10 : The allowed rotat~onal energy levels of a rigid diatomic molecule.

In order to predict the rotational spectrum, we now need to consider the difference between
the rotational energy levels. The energy differewe between two levels will be given by,

where J = lower quantum number, J' = higher quantum number.

When a molecule moves from one energy level to another, M g i v e s the amount of energy
absorbed or emitted. This energy is detected by the spectrometer in the form of spectral lines.
Since, we prefer mentioning the rotational transitions in wave number units, we can rewrite
Eq. 7.14 as,
 - w,,, h'
v J+J' - he - 8 x 2 1 h c [Y(J1+ I) -.I (J + I)]
--
- [J'(J'+ I ) - J ( J + I)]
8 x l1c
=B[J1(J'+ 1 ) - J ( J + I)]

When J = 0 and J'= 1, Eq. 7.15 becomes

.
Thus, for J = 0 to J' = 1 transition, an absorption line will appear at 2B. If the molecule is
raised from J = 1 to J' = 2 level by the absorpiion of more energy in the microwave region,
then the wave number corresponding to this transition is given by,

It means that corresponding to the transition, J = 1 to J' = 2, an absorption line will appear
at 4B. In general, when the molecule is raised from the level .I to J + 1, the wave number for
the transition is,

From Eq. 7.16, it is clear that stepwise, raising of rotational energy results in an absorption
spectrum consisting of lines at 2B,4B,6B, etc. The allowed energy transitions, the general
pattern of rotational spectrum and rotational lines in the absorption spectrum of hydrogen
chloride are shown in Fig. 7.1 1.
Rutational energy
J (in terms of B ) Energy transition
5 30B
Note a constant difference of 38 between adjacent lines ; this value, 2B. is called rotational Molecular ~pectroseopy-1
spacing. In the case of the spectra of 'H'5CI molecule. the rotational spacing is equal to
21 18 m-I or 2 i . 18 cm-I. It is assumed here that the moleculc is rigid. Such a.system k also
called rigid rotator.

Selection rule for rotational spectra :

I n the above discussion. we have not considered the sequence of transitions, J = 0 -+ .1'= 2.
.I = 2 +.IJ = 4. etc. We considered transitions only to the immediate'neighbouring energy
Icvel. It can be shown using quantum mechanics that only those transitions are possible in
which J changes by one unit. a11 other transitions being spectroscopically forbidden. Such a
result is called selection rule. Therefore. for rigid diatomic rotator, selection rule is:

For absorpt~on\pectra. A .I = + I ;similarly, for emission, A J = -1. That is, the allowed
transition for abwrption is .I -+ .I + 1 .
So far. we have discussed the theory of microwave spectra. In the next section, we shall
consider the application of rotational spectra taking HCI molecule. as an example.
- - -

7.8 ROTATIONAL SPECTRA OF HCl MOLECULE

The rotational spectra of HC1 molecule is shown in Fig. 7.1 Ic. Let us now'apply Eq. 7.16
to this spectrum to calculate the rotational constant. moment of inertia and bond length of
the niolecule.
The first line corresponding to J = 0 to .I' = 1 appears in the rotational spectrum of HCI at
21. I 8 cm-I. Hence. from Eq.7.16.

or B = 10.59 c n - I . Since the literature values of B are given in cm-I. whereas we use SI
units throughout. it is better to convert B also into SI units.

Since, B = -
h
.
,y I = h l8rr'Br.
8IT-I(
B and c.
substituting the values of h . ~r.

= 9.646 x IO-" kg ni'

Since the nionient of inertia of HCI is known, we can calculate its bond length using the
steps described below :

Mass of a CI atom =------ --

kg
6.022 X 10"

Thus, the reduced mass,

111 , 111 ,
v=--( 1 1 1 + t ? ~ -- - x 35.45 (kg)
I .008 (ke)
- X
I @-
=
.1 . O.L-I-- .
X 1U-.
--77 .Kg
( 1.008 + 35.45) (kg) 6.022 x 10"

3.646 x - m')
(kp
-
1.627 x (kg)

*I. = 127.3 nni. 3Y

 Structure of Matter41 From the above discussion, it follows that rotational spectra can be used to calculate simple
molecular parameters such as moment of inertia and bond length. Besides this, we can also
obtain information regarding molecular symmetry and bond angle.
To test your understanding of the above discussion, try the following SAQ.

SAQ 4
The lowest wave number absorption line in the rotational spectrum of ' H ' ~ Fis at
41.1 1 cm-I. Answer the following questions.
a) What is the value of the lowest frequency of absorption in the rotational spectrum of
HF?
b) Which are the two energy levels involved in this transition?
c) What is the value of the rotational constant (B) for HF?
d) Calculate the moment of inertia for HF molecule.
e) Calculate the bond length of HF molecule.
- -

I
I
7.9 SUMMARY
I
I

In this unit, we have briefly described the principles of molecular spectroscopy with special
reference to rotational spectra. We are summarising below what we have studied so far :
a Molecules have different types of quantised energy ;e.g., rotational, vibrational and
electronic.
Molecular spectra are more complex than atomic spectra ; the fonner can be classified
into three types on the basis of the method to obtain them, namely, emission spectra,
absorption spectra an< Raman spectra.
Different regions of electromagnetic radiations are used for different types of absorption
spectra.
The condition for a molecule to exhibit rotational spectra is that it must possess
permanent dipole moment.
The rotational spectra of a diatomic molecule is a series of equally spaced lines of wave
numbers 2B,4B, 6B, etc. The wave numbers of the line can be used to provide accurate
value of bond length.

- 7.10 TERMINAL QUESTIONS

-- - - -- -

1. Calculate AE, v and 7 for visible radiation of wavelength 800 nm.

2 . CO absorbs electromagnetic radiation at about 6.4 x 1013 Hz.
a) In which region of the electromagnetic spectrum does tills frequency lie?
b) Which type of molecular energy is likely to be affected?
3. What is the selection rule for the microwave absorption spectra?
4. Complete the Table given below:
Rotational qbantum Energy Energy
number transition
0
 Molecular ~pectroscopy-I
7.11 ANSWERS

SAQs
1. a) To calculate the energy Der mole. multi~lvhclA bv Avogadro constant ( N , )

2. Radiation Molecular energy changes

a) lJlfmd Vibrational and rotational
b) Ultraviolet Electronic, vibrational and rotational I
C) Microwave Rotational
4 Visible Electronic, vibrational and rotational
3. a) Yes b) Yes c) No d) No e) Yes
4. a) First convert the unit of v into m-I ; then substitute this value in the equation,
v =Vc.
Hence, v = 1.232 x 1012Hz.

b) The lowest frequency absorption arkes due to the transition from J = 0 level to
J = 1 level.

c) 2 B = 41.1 1 cm-', therefore B = 20.56 cm-I I

= 1.363 x kg m2

e) To calculate the bond length of HP molec"le, first calculate reduced mass. LI ; I

(1 + 19) x 6.022 x 10"
"0

= 1.578 x 1 0-27kg
From Eq. 7.1 1, bpnd length can be calculated as-follows:
 1.363 x (kg m2)
1S7.8 x (kg)

Terminal Questions
1. bE = 149.5 kJ mol-' ; v = 3.748 x 1014HZ;

2. a) Infrared
b) Vibrational and rotational.
3. A J = + 1.

Rotational quantum Energy Energy transition

numbkr
.-

5. Use Eq. 7.1 1 to calculate the moment of inertia.

I=@
m ~ m ~ r l o kg (Atomic mass of hydrogen is 1 and that of ,
P = m~ + m,, X
6.022 x
bromine is 80)

Once I is known, we can calculate B using the equation,

- 6.626 x (J s)
8 x (3.142)' x 3.260 x (kg m2) x 2.998 x 10' (rn s-I)

For the transition J = 1 to J'= 2 , T = 4B = 34.34 cm-';

For the transition J = 2 to J'= 3, t = 6B = 5 1.50 cm-I.