INFRARED SPECTROSCOPY

NORMAL MODES OF VIBRATION

The complex vibrations of a molecule are the superposition of relatively simple
vibrations called the normal modes of vibration. Each normal mode of vibration has a fixed
frequency. It is easy to calculate the expected number of normal modes for a molecule made
up of N atoms.
For a molecule with N atoms,
Linear molecule: Normal modes = 3N – 5
Nonlinear molecule: Normal modes = 3N – 6
All diatomic molecules (N=2) have only a single vibrational mode corresponding to
the vibration of the bond. A linear triatomic molecule such as CO2 possesses four vibrational
modes, while a nonlinear triatomic molecule such as H2O possesses only three vibrational
modes.
As an example, water has a symmetrical bent structure. It has three atoms and three
normal modes of vibration (3 x 3 - 6 = 3). Pictures of the three normal modes are shown
below.

These vibrations involve the movement of the nuclei against the forces that tend to
maintain the equilibrium configuration of the molecule. Of these three normal modes, two
are stretching vibrations and one is the deformation. For water molecule, symmetric (v1),
asymmetric (v3) and bending vibrations (v2) are IR active since all the vibrations involve
change in dipole moment, and they are observed at 3650, 3760 and 1595 cm-1 respectively.

APPLICATIONS OF IR SPECTROSCOPY
Diatomic molecules have only one vibration along the chemical bond; its frequency is
given by

where K is the force constant, c the velocity of light, and  the reduced mass which is equal to
.
The above equation shows that for diatomic molecules, the frequency is directly
proportional to the force constant (or the bond strength); and is inversely proportional
to the reduced mass.
The observed frequencies of some diatomic molecules and ions are listed below. It
show several interesting trends in frequencies and force constants.
For example, for a series of hydrogen halides, we observed that that:
HF HCl HBr HI
-1
(cm ) 4138.5 > 2991 > 2649.7 > 2309.5
K (mdyn/Å) 9.66 > 5.16 > 4.12 > 3.12
 For complexes or compounds of the type AB2, triatomic molecules, the following
trends in frequencies are observed (Table 1). From these data, we can easily correlate the
relation of frequencies and reduced mass (i.e., the frequency of vibration is inversely
proportional to the reduced mass).

Table 1: Vibrational Frequencies of AB2 Type Compounds

Compound Structure 1 2 3
-
[CuCl2] (s) Linear 300 109 405
-
[CuBr2] (s) Linear 193 81 322
-
[CuI2] (s) Linear 148 65 279
-
[AgCl2] (s) Linear 268 88 333
-
[AgBr2] (s) Linear 170 61 253
-
[Agl2] (s) Linear 133 49 215
CdF2 Linear 555 121 660
CdCl2 Linear (327) 88 419
CdBr2 Linear (205) 62 319
CdI2 Linear (149) (50) 269
(2 is bending mode, 1 and 3 are stretching modes)

Figure 1 below illustrates the four normal modes of vibration of a tetrahedral XY4
molecule. All four vibrations are Raman active, whereas only v3 and v4 are infrared active.

1 2 3 4
s(XY) d(YXY) d(XY) d(YXY)

Fig. 1. Normal modes of vibration of tetrahedral XY4 molecules.

Table 3 lists the vibrational frequencies of some tetrahalogeno compounds. In the

solid state, v3 and v4 may split into two or three bands because of the site effect. In the same
family of the periodic table, the MX stretching frequency decreases as the mass of the atom
increases.

Table 2. Vibrational Frequencies of Tetrahedral Halogeno Compounds (cm-1)

Molecule 1 2 3 4
-
[BF4] 777 360 1070 533
[BCl4]- 405 190 670 274
-
[BBr4] 243 117 605 166
CF4 908.4 434.5 1283.0 631.2
CCl4 460.0 214.2 792, 765 313.5
CBr4 267 123 672 183
CI4 178 90 555 123
 SiF4 800.8 264.2 1029.6 388.7
SiCl4 423.1 145.2 616.5 220.3
SiBr4 246.7 84.8 494.0 133.6
SiI4 168.1 62 405.5 90.5
-
[FeCl4] 330 114 378 136
-
[FeBr4] 200 — 290 95
2-
[FeCl4] 266 82 286 119
2-
[FeBr4] 162 — 219 84
2-
[FeI4] — — 186
Two important trends in frequency are noted in Table 2. First, the MX stretching
frequency decreases as the halogen is changed in the order F > Cl > Br > I. Second, the
effect of changing the oxidation state on the MX stretching frequency is seen in a pair such
as [FeX4]- and [FeX4]2- (X = Cl and Br); the MX stretching frequency increases as the
oxidation state of the metal becomes higher.

METAL AMMINE (NH3) COMPLEXES

The free NH3 molecule which has a point group symmetry C3v retains the same local
symmetry in (1:1) M—NH3 complexes. The normal modes of vibration of free NH3 are shifted
on coordination to a metal.
The NH3 stretching frequencies of the complexes are lower than those of the free NH 3
molecule for two reasons. One is the effect of coordination. Upon coordination, the NH bond
is weakened and the NH3 stretching frequencies are lowered (shifted to lower wave
numbers). The stronger the M-N bond, the weaker is the NH bond and the lower are the
NH3 stretching frequencies if other conditions are equal. Thus the NH3 stretching frequencies
may be used as a rough measure of the M-N bond strength. The anion also may weaken the
N—H bond through hydrogen bonding. As a result of coordination, the NH 3 deformation
vibrations of free NH3 are shifted to higher frequencies. The symmetric bending of free NH3 is
most sensitive to coordination while degenerate bending mode is least affected.
The other reason is the effect of the counter ion. For example, the NH3 stretching
frequencies of the chloride are much lower than those of the perchlorate. This is attributed to
the weakening of the NH bond due to the formation of the NH….Cl type hydrogen bond in
the former.
The effects of coordination and hydrogen bonding mentioned above shift the NH 3
deformation and rocking modes to higher frequencies. Among them, the NH3 rocking mode is
most sensitive, and the degenerate deformation is least sensitive to these effects. Thus the
NH3 rocking frequency is often used to compare the strength of the M-N bond in a series of
complexes of the same type and anion.

In regard to [M(NH3)4X2] and [M(NH3)3X3] type halogeno-ammine complexes, one

interest has been the distinction of stereoisomers by vibrational spectroscopy. The trans-
MN4X2 (D4h) isomer exhibits one MN stretching and one MX stretching, while cis-MN4X2
(C2v)) shows four MN stretching and two MX stretching vibrations in the infrared.
Vibrational spectra of the planar M(NH3)2X2-type complexes [M = Pt(II) and Pd(II)]
have been given in Table 3 with the observed frequencies and band assignments of their
skeletal vibrations. As expected, both the PdN and PdCl stretching bands split into two in the
cis-isomer while the trans-isomer exhibits one MN stretching and one MX stretching vibrations.
 TABLE 3. SKELETAL FREQUENCIES OF SQUARE-PLANAR M(NH3)2X2 TYPE COMPLEXES
(CM-1)
Complex (MN) (MX) Bending
trans-[Pd(NH3)2Cl2] 496 333 245, 222, 162, 137
cis-[Pd(NH3)2Cl2] 495, 476 327, 306 245, 218, 160, 135
trans-[Pt(NH3)2Cl2] 572 365 220, 195
cis-[Pt(NH3)2Cl2] 510 330, 323 250, 198, 155, 123

METAL HALOGEN COMPLEXES

Terminal Metal-Halogen Bond
Terminal MX stretching bands appear in the regions of 750-500 cm-1 for MF, 400-200
cm-1 for MCl, 300-200 cm-1 for MBr, and 200-100 cm-1 for MI. Several factors govern (MX). If
other conditions are equal, (MX) is higher as the oxidation state of the metal is higher.
For example, in case of [FeCl4]- and [FeCl4]2-; [FeBr4]- and [FeBr4]2- (as already given in Table
3):
Molecule 1 2 3 4
-
[FeCl4] 330 114 378 136
-
[FeBr4] 200 — 290 95
2-
[FeCl4] 266 82 286 119
2-
[FeBr4] 162 — 219 84

If other conditions are equal, (MX) is higher as the coordination number of the
metal is smaller. Table 4 indicates the structure dependence of (NiX).
The MX vibrations are very useful in determining the stereochemistry of the complex.
It is possible to determine the stereochemistry of a halogeno complex by counting the
number of (MX) fundamentals observed. E.g., trans-planar complexes give only one while cis-
planar complexes give two (MX).

TABLE 4. STRUCTURAL DEPENDENCE OF NiX STRETCHING FREQUENCIES (CM-1)

Stretching Linear trans-Planar cis- Planar Tetrahedral trans-
Frequency Triatomic Octahedral

(NiCl) NiCl2 Ni(PEt3)2Cl2 Ni(DPE)Cl2 Ni(PPh3)2Cl2 Ni(py)4Cl2

521 403 341, 328 341, 305 207
(NiBr) NiBr2 Ni(PEt3)2Br2 Ni(DPE)Br2 Ni(PPh3)2Br2 Ni(py)4Br2
414 338 270, 266 265, 232 140
(Nil) Ni(DPE)I2 Ni(PPh3)2I2 Ni(py)4I2
260, 212 215 105
DPE= 1, 2-bis(diphenylphosphino)ethane

SQUARE-PLANAR COMPLEXES. In the vibrational spectra of planar M(NH3)2X2 [M =Pt(II)

and Pd(II)] have already given in Table 3. The trans-isomer (D2h) exhibits one v(MX),
whereas the cis-isomer (C2v) exhibits two v(MX) bands in the infrared.
BRIDGING METAL-HALOGEN BOND:
Halogens tend to form bridges between two metal atoms. In general, bridging MX
stretching frequencies [v(MXb)] are lower than terminal MX stretching frequencies
[v(MXt)].

Table 4 lists the v(MXt) and v(MXb) of bridging halogeno complexes containing other
ligands. The trans-planar M2X4L2-type compounds (C2h) exhibit three infrared-active v(MX)
modes: one v(MXt) and two v(MXb). For the latter two, the higher-frequency band
corresponds to v(MXb) trans to X, whereas the lower-frequency mode is assigned to v(MXb)
trans to L since it is sensitive to the nature of L. Strong coupling is expected, however, among
these modes since they belong to the same symmetry species. [subscript t is for terminal and
b is for bridging]

TABLE 4. TERMINAL AND BRIDGING METAL-HALOGEN STRETCHING FREQUENCIES (cm-1)

Compound v(MXt) v(MXb) v(MXb)/
v(MXt)
trans- Pd2Cl4L2 360-339 308-294 0.86
283-241 0.75
trans-Pt2Cl4L2 368-347 331-317 0.91
301-257 0.78
Pd2Br4L2 285-265 220-185 0.74
200-165 0.66
Pt2Br4L2 260-235 230-210 0.89
190-175 0.74
Pt2I4L2 200-170 190-150 0.92
150-135 0.77
L = PMe3, PEt3, PPh3, and so on.
X****************************X****************************X

RAMAN SPECTROSCOPY
INTRODUCTION. Rotational and vibrational frequencies of a molecule can be conveniently
studied by Raman spectroscopy. Raman effect, an adjunct to electronic and infrared spectra,
was predicted by A. Smekal (1923) and discovered by C.V. Raman (1928). Raman effect may
be defined as a phenomenon due to which the scattering of light has a slightly different
frequency from that of incident light and there occurs a change in the atomic oscillations within
the molecule. Raman effect has been important as a method for the elucidation of molecular
structure, for locating functional groups or chemical bonds in the molecules.
Raman spectroscopic measurement is usually carried out in the visible region (4000-
7000 Å) of electromagnetic radiation where high dispersion is easily available with less
expensive instruments. Today, lasers are used as they produce greater power with a much
greater degree of monochromaticity. The He—Ne laser line at  = 623.8 nm is generally used.
The blue line becomes more sensitive than the red line in such a laser. Raman spectrum can
be used for finger print identification like the IR spectrum. Transformation of energy is
considered in terms of stoke's and antistoke's lines in Raman spectroscopy.
COMPARISON OF RAMAN SPECTROSCOPY AND INFRARED SPECTROSCOPY
SIMILARITIES
1. Raman and IR spectra provide finger prints of the molecular structure at the purely
empirical level and permit the quantitative and qualitative analysis of individual compounds.
2. Both these methods are used for determining the internal vibrations of molecules, in terms
of normal vibrations of the constituent atoms.
3. These methods are predominantly applicable to the analysis of covalently bonded
molecules rather than to ionic structures.
DIFFERENCES
Although IR and Raman spectra have many similarities, they are not exact duplicates. Both
the techniques yield complementary types of information.
Sl.No. Raman Spectra Infrared Spectra
1. It is due to the scattering of light by It is due to absorption of light by
the vibrating molecules. vibrating molecules.
2. It can be recorded only in one It requires two runs with different
exposure. prism to cover the whole region of
infrared.
3. Polarizability of the molecule will The presence of a permanent dipole
decide whether the Raman spectra will moment in a molecule may be
be obtained or not. regarded as a criterion of infrared.
4. Optical systems are made of glass or Optical systems are made up of
quartz. crystals such as NaBr, CaF2 etc.
5. In Raman effect vibrational frequencies Vibrational frequencies of very large
of large molecules can be measured. molecules cannot be measured.
6. Concentrated solutions must be Generally dilute solutions are
utilised to increase the intensity of preferred.
weaker Raman lines.
7. Water can be used as a solvent. Water cannot be used as a solvent
because it is opaque to IR radiation.
8. Homonuclear diatomic molecules are Homonuclear diatomic molecules are
often found to be active. not found to be active.
9. Sometimes photochemical reactions Photochemical reactions do not take
take place in the regions of Raman place.
lines and create problems.
10. Substances under investigation must This condition is not rigid.
be pure and colourless.
11. The method is very accurate, but is not The method is accurate and very
very sensitive. sensitive.

THEORY OF RAMAN SPECTROSCOPY

When a beam of monochromatic exciting radiation passes through a transparent medium,
the photons of energy hv collide with the molecules of the medium. When a photon is
absorbed by a molecule in the ground vibrational state, the absorbed photon raises the
energy of the molecule to a state which is higher than the vibrational energy level. This is
unstable energy state (called virtual state in fig. to distinguish it from the real excited state)
for the excited molecule. Now two processes can occur.
(i) The excited molecule may return to its ground state and emits a photon with same
energy and frequency as the exciting photon (inc = scat ). This is called Rayleigh scattering.
(ii) When a molecule is excited due to absorption of photon, some of the excited
molecules may return, not to the ground state, but to a different vibrational state and emits
photons which are lower in energy (larger wavelength or lower frequency) than the incident
photon (inc > scat ), it give rise to Stokes lines.
In this case of Raman scattering a change in frequency occurs due to the interaction
between the incident photons and vibrational energy levels of molecules. It is not just
absorption but transfer of a portion of energy of the photons to the molecule or vice versa.
In some other case, if the molecule is initially in the first excited state, the photon
absorbed by such a molecule raises to some high unstable energy state (virtual state). This
molecule then returns to the ground vibrational state and in doing so emits a photon which
is higher in energy (shorter wavelength or higher frequency) than the incident photon (inc
< scat ). This gives rise to Anti-stokes lines. The latter two phenomena (Stokes and Anti-
Stokes scattering) are known as Raman scattering and give the Raman lines. In both the
cases of Raman scattering the energy difference between the scattered photon and the incident
photon is always equal to the energy difference between the initial and final vibrational states.
Thus the lines whose wavelengths have been modified in Raman effect are called
Raman lines. Raman lines in the spectrum are symmetrically displaced about the parent lines
(incident excitation radiation). When the temperature rises, their individual separations from
the parent lines decrease.

The frequency difference between the incident excitation radiation (inc) and the
Raman scattered radiation (scat) is called as Raman shifts, designated as Δν. Raman shift
may be calculated by using the following formula:
 (in cm-1) = inc - scat
or  (in cm-1) =  -  x 107 ….(3)
where  and  are the wavelengths (in nanometer) of incident excitation radiation and
Raman scattered radiation (Raman lines) respectively. The eq. (3) is used to calculate stokes
lines. For antistokes lines, the signs in the above equation are reversed. Note that the Raman
shift does not depend on the frequency of the incident light (incident excitation radiation);
and the Raman shift only depends on the excitation energy of the excited state. Therefore, in
reporting Raman spectra, only Δν is recorded.
Thus Stoke's lines have wavelengths greater than Rayleigh lines and Anti-stoke's
lines have a wavelength less than Rayleigh lines. In other words if molecules gain rotational
energy from photons during a collision, we get lines of low wave number which are known as
Stoke's lines. If a molecule loses energy to photons the lines which are on the high wave
number are Anti-stoke's lines. The relative intensities of Stoke's and Anti-stoke's lines are
determined by the relative population of electrons in the ground and excited states. The
probability of a molecule being in the first excited state is always lower as compared to its
being in the ground state. That is why the intensity of Stoke's lines is always greater than the
Anti-stoke's lines while intensity of Rayleigh lines is much stronger than that of the Stokes
lines.
CHARACTERISTIC PROPERTIES OF RAMAN LINES
The lines observed in Raman effect exhibit a number of characteristics which are given below:
(i) The intensity of the Stoke’s lines is always greater than the corresponding anti-Stoke’s
lines. With the rise of temperature, the intensity of anti-Stoke’s lines increases.
(ii) Raman shift, Δν, generally lies within the range of 100 to 3000 cm-1 which lies in far and
near infrared region.
(iii) The Raman lines are symmetrically disposed about the parent line. When the temperature
rises, their individual separations from the parent lines decrease. The intensity of the Stoke’s
lines falls off much rapidly with the increase in separation from the parent line.
(iv) The frequency difference between the parent line and the modified line represents the
frequency of the absorption band of the material.
INTENSITY OF RAMAN PEAKS
The intensity or power of a Raman peak depends on the following factors:
(i) Intensity of source.
(ii) Concentration of the active group.
(iii) Polarizability of the molecule.
The effect of the incident light is important because the intensity of Raman scattering
increases as the fourth power of the excitation frequency. To get a large signal, we want to
use the highest frequency light source possible. If the wavelength is Raman spectroscopy is
halved (e.g., from 1064 to 532 nm) or frequency is doubled, the intensity of the scattered
light will increase by a factor of 16. Raman intensities are directly proportional to the
concentration of the active species. Raman spectroscopy closely resembles fluorescence than
absorption, where the concentration intensity relationship is logarithmic. Generally strong
bands in the infrared correspond to weak bands in the Raman spectrum and vice versa. This
complementary nature of infrared and Raman spectra is because of electrical characteristics
of the vibrations.

APPLICATIONS RAMAN SPECTROSCOPY

The mutual exclusion principle states that if a molecule has a centre of symmetry
then any vibration that is inactive in IR will be active in the Raman and vice versa. It is also
possible that there may be vibrations which are inactive in IR and Raman spectrum. But if the
same vibration appears in both IR and Raman it is fairly certain that the molecule lacks a
centre of symmetry.

Structure of CO2. CO2 shows two very strong bands [at 2349 (asymmetric stretching) and
668 cm-1 (bending-doubly degenerate)] in its IR spectrum, whereas it shows only one strong
band [at 1389 cm-1 (symmetric stretching)] in its Raman spectrum. Since none of these bands
is present in both the spectra, the molecule of CO2 must have a centre of symmetry
according to the mutual exclusion principle. For triatomic molecules, this observation shows
that the molecule is linear and symmetric. Thus the molecular structure of CO2 is of the type
O—C—O. The above mentioned three bands, two in the IR and one in the Raman spectrum,
represent the three fundamental frequencies of CO2.

Structure of N2O. N2O is isoelectronic with CO2. If N2O is symmetrically linear it should show
Raman spectrum similar to CO2, but if it is unsymmetrical then N2O would become active
both in IR and Raman. The three fundamental frequencies (at 2225, 1285, 589 cm-1 which are
asymmetric stretching, symmetric stretching and doubly degenerate bending modes) appear
in the IR, and two of them (at 2225 and 1285 cm-1) appear in the Raman spectrum. The
frequency 589 cm-1 could not be recorded due to weak intensity. Thus, according to the
mutual exclusion principle, the molecule has no centre of symmetry because two bands are
common in both IR and Raman spectra. Hence N2O has the unsymmetrical structure,
N—N—O, and not N—O—N.

Structure of SO2. If SO2 is symmetrically linear it should show Raman spectrum similar to
CO2, but if it is unsymmetrical then SO2 would become active both in IR and Raman. The IR
and Raman spectra of SO2 in the vapour phase show three bands at 520, 1150 and 1300 cm-1
corresponding to the bending, asymmetric stretching and symmetric stretching vibrations
respectively. Since all of these bands are present in both the spectra, the molecule of SO2
does not have a centre of symmetry according to the mutual exclusion principle. For
triatomic molecules, this observation indicates SO2 molecule has bent structure.

Nitrate ion ( NO3- ). Nitrate ion (NO3-) is a tetra-atomic ion. The band assignments in Raman
and IR spectra are given in table (band positions may differ in different nitrate compounds):

Infra-Red (cm-1) Raman (cm-1) Assignment

680 690 4 (asymmetric bending)
830 - 2 (out-of-plane symmetric bending)
- 1049 1 (symmetric stretching)
1350 1355 3 (asymmetric stretching)

Both the 3 and 4 vibrations are IR and Raman active. A band at 1049 cm-1 (symmetric
stretching) is only seen in Raman while a band at 830 cm-1 (out-of-plane symmetric bending)
is only observed in the IR spectra. For tetra-atomic molecule, this observation clearly
indicates that NO3- ion has a planar structure.
Chlorate ion ( ClO3- ). Nitrate ion (ClO3-) is a tetra-atomic ion. The band assignments in
Raman and IR spectra are given in table (band positions may differ in different chlorate
compounds):

Infra-Red (cm-1) Raman (cm-1) Assignment

434 450 4 (asymmetric bending)
624 610 2 (out-of-plane symmetric bending)
950 940 1 (symmetric stretching)
994 982 3 (asymmetric stretching)

It is observed that all the vibrations are both IR and Raman active. For tetra-atomic molecule,
this observation clearly indicates that ClO3- ion has a pyramidal structure.