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Molecular vibrations
A basis to describe vibrations
Molecular vibrations: the relative motion of atoms with respect to one another
These vibrations are an energy state of the molecule
We should be able to use group theory to figure out which vibrations the molecule can actually
have.
1
C2v
of unshifted atoms
C2
v (xZ )
V' ( yz )
2: Use the following equation to calculate the contribution to the character per unshifted atom of the
representations
360
E = 3, i 3 , S =-1+2 cos( n ) ,
n
C2v
Contribution to character
1,
C n =1+ 2 cos(
360
)
n
C2
V' ( yz)
-1
1
2
3: The reducible representation for the displacement coordinates is the multiplication of the number of
unshifted atoms and the contribution to character
E
C2v
C2
V' ( yz )
of unshift atoms
Contributions to character
-1
-1
3N
1
aA1= 4 ((9 11)+(-111)+(111)+(311)) = 3, aA2= 1 , aB1= 2 , aB2= 3
3A + A2 + 2B1 +3 B2
3N
Exercise Use the reduction formula to work out how many times each of the irreducible representations
appears in
3N
of H2O
Displacement coordinates tell us how each atom moves relative to the others in molecule
atoms move in the same direction at once translation along an axis A , B , B
1
rotation A , B , B
2
In the 3 N representation, six of the irreducible representations correspond to translations and rotations
of the molecule.
every non-linear molecule has 3N-6 vibrations , where N is the number of atoms.
The irreducible representations of vibrations vib
vib = 3 N - T - R =(3A 1 +A 2 +2B 1 +3B 2 ) - (A 1 +A 2 +2B 1 +2B 2 ) =2A 1 + B 2
NH3
Step 1, Use displacement coordinates.
Step 2, What is the point group of NH3
Step 3, Generate a reducible representation
Exercise Using displacement coordinates of each atom come out reducible representation for each
5
2C
# of unshifted atoms
Contribution to character
3 N
12
3V
3N
of NH3
3 N =3A 1 +A 2 +4E
6
*Each E representation corresponds to a doublely degenerate state, 2E represents four energy states
vib = 3 N - T R =(3A 1 +A 2 +4E 3 )-(A 1 +A 2 +2E) = 2A 1 +2E
(3N - 6= 3 4 6 = 6)
How can we use these results to help explain the properties of molecules?
What do the vibrations actually look like?
Can group theory help us to the examine the vibration in more detail?[Yes]
Internal Coordinates
Vibration of water molecule: vib =2A +B
1
r : the displacement of one atom with respect to another along the line of the bond
# of unshifted coordinates
C2
V'
NH3
# of unshifted coordinate
2C3
3 v
aE = 6 (3 2 1) =1
str =A1+E vib = str + bend 2A1+2E = A1+E+ bend bend =A1+ E
9
# of unshifted angles
2C3
3 v
bend = A1 + E
The same answer as we got from the difference method ( bend = vib - str )
Sometime, generating bend from the angles of the molecule, does NOT give the same answer as
difference method. A redundant coordinate is found in the bend representation, which is often A1.
When this occurs it can be simply removed from the bend representation.
10
11
Projection Operators
Q: Can we use group theory to analise the vibrations further, and also provide a link with experiment?
A: We can use these results and use group theory to let us see what the vibrations look like
Projection operators
Px [ ( R ) R ]x ( R1 )x ( R2 )x ... ( Rh )x
R
r1
r1
C2
C2v
C2
A1
C2v
C2
1 r1
1 r2
1 r2
1 r1
C2v
r1
r2
r2
P r1 =1 r1 1 r2 +1 r2 +1 r1 = 2 r1 +2 r2
normalized
1
2
( r1 + r2 )
13
r1 + r2 is know as a symmetry adopted linear combination (SALC)
Exercise Please use r2 as generating coordinate and find out the SALC for A1. [ r1 + r2 ]
r1
r1
C2
C2v
C2
B2
-1
-1
C2v
r2
r2
r1
14
C2v
- r2
r1
C2
- r2
r1
P r1 = r1 - r2 - r2 + r1 = 2 r2 - 2 r2 normalize
1
2
( r1 - r2 )
B2 vibration in water is the one where the r1 coordinates is reducing whilst the r2 coordinates is
increase, and vice versa.
Exercise Please use r2 as generating coordinate and find out the SALC for A1. [ r1 - r2 ]
15
NH
C3v
(C3v)
E
r1
C32
C3
r1
r2
r3
r2
r3
r2
C3v
C3
C32
A1
-1
-1
For A1 P r1 =( r1 + r2 + r3 ); For E P r1 =2 r1 - r2 - r3
The letters A and B are used for the symmetry species of
one-dimensional irreducible representation E is used for 2-D T is
used for 3-D. The E vibration is doubly degenerate and should have
different types of vibrational motions.
Use r 2 and r3
P r2 =2 r 2 - r1 - r3 ; P r3 =2 r3 - r 2 - r1
These three linear combinations are not linearly independent. In
fact, their vibrations are the same.
Try to find a linear combinations of the three combination
P( r2 - r3 ) = P r2 - P r3 = 2 r 2 - r1 - r3 -2 r3 + r 2 + r1 = 3 r 2 -3 r3
r2 - r3 is orthogonal to the first one. It is the second E vibration.
Use the projection operator method to determine the SALC for
the bending vibration of NH
C3v
C3
C32
17
C3v
C3
C32
A1
-1
-1
For A1 1 + 2 + 3 + 2 + 1 + 3 =2 1 +2 2 +2 3
For E 2 1 - 2 - 3
P( 2 + 3 ) = P 2 +P 3 = 2 - 3 [(2 1 - 2 - 3 )]
Exercise Please use, 2 and 3 as generating coordinate and find out the SALC for A1 and E.
18
AuBr (D )
4h
4h
# of unshifted coordinates
2C
C
0
2C
2
'
2
2C
"
2
2S
19
aA1g = 1 ; aA2g = 0 ; aB1g = 1; aB2g = 0 ; aEg = 0; aA1u = 0; aA2u = 0; aB1u = 0; aB2u = 0; aEu =1
st = A1g + B1g + Eu
E
C41
C43
C2
S41
S43
v d
r1
A1g
B1g
E
P r2 = r2 - r4 [( r1 - r3 )]
Exercise Please use r2 , r3 as generating coordinate and find out the SALC for Eu.
20
Exercise
For PCl5, determine the SALCs for the stretching vibrations of the molecule. Use the
21
*
i
T f d
Infra-red spectroscopy
In infra-red spectroscopy, a molecule can be excited from its ground vibration state to a fundamental
vibration using infra-red radiation. This all occurs if there is a dipole moment change in the molecule
upon absorption.
22
*
i
T f d i f d
1.
f : A1 or B2
2.
i : A1
All we have to decide is whether the symmetry of the appropriate parts of the equation all multiply
together to give a non-zero result, without having to do the integration.
In group theory language all we need to decide is whether the multiplication of the symmetries gives the
totally symmetric representation (e.g. A1, A1g) or not.
23
A1 B1 A1
A1 B2 A1
A1 A1 A1
To multiply irreducible representations together, we need to use the Direct Product Rules.
A1 B1 A1 B1
A1 B2 A1 B 2
A1 A1 A1 A1
A1 is included in one of the answer, and we can conclude that absorbance due to transition from the
ground state to A1 vibrations in H2O will be observed in the infra-red spectrum.
24
Raman spectroscopy
2
2
2
T : x , y , z , xy, yz, xz
Consider H 2O
x 2 , y 2 , z 2 A1 , xy A2 , xz B1 , yz B2
If f = A1
B1
B1
B2
B2
A1 A1 A1 = A1
A
A
2
2
One equation contains the A1 representation, hence we expect to see bands in the Raman spectrum
corresponding to the A1 vibrations.
25
If a band due to a vibration appears in the infra-red spectrum, the vibration is known as infra-red active
If a band due to a vibration appears in the Raman spectrum, the vibration is known as Raman active.
In H 2 O , we expect to see three fundamental vibration bands, all three of which are Raman and infra-red
active.
To assign vibration spectra of molecule, we need one rule and one rule-of-thumb.
Rule : polarized bands can only come from A1 vibrations
Rule-of-thumb : stretching vibration usually appear at higher frequency.
Any molecule which possesses a centre of symmetry, i, is subject to something know as the mutual
exclusion rule. This rule states that any vibration in such a molecule cannot be both IR-active and
Raman-active
26
Infra-red spectrum ( cm 1 )
Raman spectrum( cm )
____
218 depolarized
305
324 depolarized
____
458 polarized
768
762 depolarized
1. point group Td
2. consider displacement coordinates
3.
27
1
[(15 1 1) (1 1 3) (1 1 6) (3 1 6)] 1
24
a A = 0, aE 1 aT 1 aT 3
a A1 =
2
3 C2
6 S4
6 d
# of unshift coordinate 4
str
Td
28
str = A1 T2
bend = E T2
8C
3C
6S
# of unshifted coordinate 6
bend
bend = A1 E T2
The extra A1 is redundant coordinate and can be ignored str A1 E T2
bend E T2
x,y,z T2
for f A1
A1 T2 T1 T2
f T2
A1 T2 T2 A1 E T1 T1
f E
A1 T2 E T1 T2
2
2
2
xy,yz,zx T2 ; x , y , z E & A1
For f A1
A1 A1 A1 A1 (Raman active); A1 E A1 E , A1 T2 A1 T2
For f T2
A1 A1 T2 T2 ; A1 E A1 T2 , A1 T2 T2 A1 E T2 (Raman active)
For f E
A1 A1 E E ; A1 E E A1 E (Raman active), A1 T2 E T1 T2
Raman spectrum
____
305
_____
768
30