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PQRS BRANCHES IN

VIBRATIONAL M.Sc. 1
semester

SPECTRUM
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 Ro-vibrational spectroscopy
concerns molecules in the gas
phase.
 There are sequences of
quantized rotational levels
associated with both the
ground and excited vibrational
states.
 The spectra are of ten resolved
into lines due to transitions
from one rotational level in
the ground vibrational state to
one rotational level in the
vibrationally excited state.
 The lines corresponding to a
given vibrational transition
form a band.
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 In the simplest cases the part of the infrared spectrum
involving vibrational transitions with the same rotational
quantum number (ΔJ = 0) in ground and excited states is
called the Q-branch.
 On the high frequency side of the Q -branch the energy of
rotational transitions is added to the energy of the vibrational
transition. This is known as the R -branch of the spectrum for
ΔJ = +1 .
 The P-branch for ΔJ = −1 lies on the low wavenumber side of
the Q branch. The appearance of the R -branch is very similar
to the appearance of the pure rotation spectrum, and the P -
branch appears as a nearly mirror image of the R -branch.
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 Selection rules are same as that for each of the state
separately
 ∆𝑣 = − + 1, − + 2, − + 3 and ∆ 𝐽= − + 1
 We may have ∆𝑣=0 pure rotational spectrum
 Can’t have ∆ 𝐽 = 0 𝑏𝑒𝑐𝑎𝑢𝑠𝑒that means pure vibrational
spectrum that is not possible
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 The appearance of rotational fine structure is determined by
the symmetry of the molecular rotors which are classified, in
the same way as for pure rotational spectroscopy, into linear
molecules, spherical-, symmetric- and asymmetric- rotor
classes.
 The quantum mechanical treatment of rotational fine
structure is the same as for pure rotations
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 An analytical expression may be found out by applying
selection rule. Considering only the transitions from v=0→v=1

 Writing 𝝑 ° = 𝝑 𝒆 (1-2𝒙 𝒆 )

 ∆∈ 𝒋,𝒗 = 𝝑 ° + 2 Bm 𝒄𝒎 −𝟏
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 A general convention is to label quantities that refer to the
vibrational ground and excited states of a transition with
double prime and single prime, respectively.

 For example, the rotational constant for the ground state is
written as 𝑱 " and that of the excited state as 𝑱 ′ Also, these
constants are expressed in the molecular spectroscopist's
units of cm -1 .
ROTATIONAL VIBRATIONAL
SPECTROSCOPY
 This is Breakdown of Born Openheimer approximation
INORGANIC MOLECULES Vibrational
spectra for
SHAPES AND VIBRATIONAL Polyatomic
SPECTROSCOPY molecules
INORGANIC MOLECULES SHAPES AND
VIBRATIONAL SPECTROSCOPY

 Vibrational spectroscopy has extensive


applications in the determination of site of
coordination
 Classification of normal vibration is according
to point groups
 IR and Raman spectrum both complimentary
are employed to determine the structure
 Degrees of freedom (3N-6)
 Degrees of Freedom for linear diatomic
molecule (3N-5)
SYMMETRY GROUPS IN DIATOMIC
MOLECULES

There are typically two


symmetry groups
associated with diatomic
molecules:
𝑐αὐ , 𝐷αℎ both of them
belonging to the Curie
groups
INORGANIC MOLECULES SHAPES AND
VIBRATIONAL SPECTROSCOPY

Homonuclear Diatomic molecules ( 𝐴 2


Type)
No Permanent Dipole moment in their
equilibrium position.
Dipole moment derivative with respect to
normal coordinate is zero
Infra red inactive
INORGANIC MOLECULES SHAPES AND
VIBRATIONAL SPECTROSCOPY

Heteronuclear Diatomic molecules ( AB Type)


Permanent Dipole moment
Stretching vibrations are Infra red active
TRIATOMIC MOLECULES

 𝑋𝑌2 Type triatomic molecule bent or linear structure


 Bent molecule

 𝑐2ὐ type of point group


 Three normal modes of vibration, 02 stretching 01 bending
 During vibration change in dipole moment is observed , hence
all the three are IR active.
𝑋𝑌2 T YPE TRIATOMIC MOLECULE BENT……



Symmetric stretching


Bending


Asymmetric stretching
𝑐2ὐ T YPE OF POINT GROUP
TRIATOMIC X𝑌2 T YPE MOLECULES
Character table for D∞h point group

linear
functi
E 2C∞ ... ∞σv i 2S∞ ... ∞C'2 ons, quadratic
rotati
ons
A1g=Σ
+ 1 1 ... 1 1 1 ... 1 x2+y2, z2
g
A2g=Σ
- 1 1 ... -1 1 1 ... -1 Rz
g
-
E1g=Π 2cos( (Rx,
2 ... 0 2 2cos( ... 0 (xz, yz)
g φ) R y)
φ)
E2g=Δ 2cos( 2cos(
2 ... 0 2 ... 0 (x2-y2, xy)
g 2φ) 2φ)
-
E3g= 2cos(
2 ... 0 2 2cos( ... 0
Φg 3φ)
3φ)
... ... ... ... ... ... ... ... ...
A1u=Σ
+ 1 1 ... 1 -1 -1 ... -1 z
u
A2u=Σ
- 1 1 ... -1 -1 -1 ... 1
u
E =Π 2cos( 2cos(
TRIATOMIC X𝑌2 T YPE MOLECULES

 𝑣 1 and𝑣 2 belong to 𝐴 1 species, they would have mixed


Character, each mode will have character of the other
 𝑣 3 is the fundamental only pure mode in 𝐻2 O molecule
belonging to 𝐵 2 species, Such modes are pure and diagnostic
for structural determination
 Molecules are classified as 2 𝐴 1 + 𝐵 2 , which are both IR and
Raman active
TRIATOMIC MOLECULES Y-X-Y T YPE

 Linear molecules having point group 𝐷𝛼ℎ exhibit normal modes


distributed as σ+ +
𝑔 (𝐴 1𝑔 ) , σ𝜇 (𝐴 1𝜇 ) and ς𝜇 (𝐸1𝜇 )
 σ+
𝑔 (𝐴 1𝑔 ) mode is Raman active(normalized bonding LCAO)

 σ+𝜇 (𝐴 1𝜇 ) and ς𝜇 (𝐸1𝜇 ) modes are IR active(Normalized


antibonding)
 Molecule has inversion centre
 Mutual exclusion rule is applicable
 Mutual exclusion rule..For a molecule which has a centre of
symmetry, the vibrations are active in IR and inactive in
Raman and those which are inactive in IR are active in Raman
 None of the IR bands are coincident with Raman bands and
vice -versa
TRIATOMIC MOLECULES X-Y-Y T YPE

 Linear molecules possessing 𝑐 𝛼𝑣 point groups


 All the three vibrations (2 σ+ , ς )IR and
Raman active
 Example 𝑁2 O
 Bands in IR spectrum 588,1280 and 2220 𝑐𝑚 −1
 Bands in Raman spectrum 588𝑐𝑚 −1 line is very
weak while 1280 and 2220 𝑐𝑚 −1 lines are
intense. Bonds are also polarised in Raman
spectrum
 Consistent with structure of 𝑁2 O as N ≡ 𝑁 = 𝑁
TRIATOMIC MOLECULES Y-X-Z T YPE

 Linear molecules possessing 𝑐 𝛼𝑣 point groups


 All the three vibrations IR and Raman active
 Example HCN
 IR and Raman spectra exhibits bands near 3310,2100
and 720𝑐𝑚 −1 Bent
 Example ONCl
 Bent YXZ molecule
 Three normal modes of vibrations IR and Raman active
 Bands at 1800 and 603𝑐𝑚 −1 assigned to O-N and N-Cl
stretching. Bending vibration is assigned at 332 𝑐𝑚 −1
TRIATOMIC MOLECULES XYY AND XYZ T YPE
BENT

 Point group𝑐 𝑠
 Possess three vibrations (3A), which are IR and Raman active