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