12-1

Normal Modes of Vibration A molecule having N atoms will have 3N degrees of freedom For a nonlinear molecule: 3 degrees correspond to x, y, z translations 3 degrees correspond to Rx, Ry, Rz rotations The remainder (3N-6) are vibrational motions (normal modes) These normal modes form basis functions for a 1-D representation in the molecular symmetry group. (An irreducible representation) In general, all normal modes can be resolved into either one or a combination of these normal modes. For Linear Molecules, all vibrations can be resolved into 3N-5 normal modes Consider SO2: 3(3)-6 = 3 vibrational (normal) modes
S O O O S O O S O

S O O O

S O O

S O

1 Symmetric Stretch

2 Asymmetric Stretch

3 Bend

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Experimentally (cm-1) 519 606 1151 1361 1871 2305 2499 assignment 2 1-2 1 3 2+3 21 1+3

difference band combination band combination band

Convention for Designating Vibrations - symmetric/antisymmetric stretch - Bends (in plane) -Bends (out of plane) Subscripts as asymmetric s symmetric d - degenerate
For CO2:
O C O O C O

3N-5 = 4 normal modes

O C O

Exptl/cm -1 - 2349 3 -1340 1 -667 2

(degenerate) 2

Note: For linear molecules, 3N-5 degrees of freedom

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By convention 1 sym. Stretch 2 sym. Bend 3 asym. Stretch 4 asym. Bend Consider 1 (1340 cm-1) and 22 (667 2 = 1344 cm-1) are nearly degenerate. The wavefunctions describing these states will interact causing a resonance.
E B 1 1388 cm-1 2 2 ~ 1340 cm-1 A & B are now admixtures of these vibrational modes cannot call either "" or "22"

1286 cm-1 called: Fermi Resonance

How does one assign vibrations? Optional Material Normal coordinate analyses solves the problem of the vibrating molecule wavefunctions in terms of internal coordinates
Example: H2O L11
H O

L22
O

L11, L22 are internal coordinates for OH bonds F11 & F22 are corresponding four constants L , F - bending motion

The wavefunctions & force constants can be related by a series of secular equations/determinant. GF-E = 0 Where: G matrix contains information about the kinetic energy of the molecule

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G-matrix can be calculated from bond distances/angles F-matrix elements describe the potential energies of the vibrations F-matrix is usually incomplete because force constants are not well established. While =422 (from experiment) If meaningful force constants can be obtained, then the vibrational wavefunctions are determined by multiplying by the basis sets (internal displacements). GF-EL = 0 G = 33, F = 33, L = 31 (L11, L22, L) E = unit matrix This yields the wavefunctions for the normal modes: For H2O 1 = NL + N(L11 + L22) A1 symmetric stretch 2 = N(L11 + L22) + NL A1 symmetric bend B1 asymmetric stretch 3 = 1 (L11 L22)
2

For N >> N For a diatomic molecule: all matrices are 11 therefore where F11 is only unknown F11G11 - = 0 This becomes:
F11

= 422 =

F11 4 2

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Raman Spectroscopy visible photons to obtain normal modes Energy Level Diagram molecule scatters a photon off at energies h O
vibrational state

2 1 12 0

1. Stokes Shift: h-o (o virtual state) 2. AntiStokes Shift: h + o (1 virtual state) 2 produces much weaker transitions because there are fewer molecules in 1 than o

antistokes Rayleigh line h-o stokes ** Stokes lines are always at energies = 1 vibrational quantum lower than Rayleigh line

h + o

h Raman Shift/ cm-1

Rayleigh line is the elastic scattering (h = h) and very intense. Raman lines (stokes and antistokes) do not result from absorption and reemission scattering phenomenon (T 10-15 s) Keypoint: h - o = vibrational energy for given normal mode (h + o) too weak to use as probe *very useful for large molecules that absorb broadly in IR region, but only 1 in 106 Raman photons produced inefficient

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Selection Rules for Raman Intensity f() molecule polarability

ij Intensity of scattered radiation: I = CIos4 ij

where: C- constant Io- intensity of incident radiation s- frequency of scattered radiation (I is greater for blue photons) For a Raman active vibration, there must be a change in the polarizability of the molecule during the vibration Polarizability is a measure of deformability: Consider CO2 (1)
O

extended

equilibrium

compressed

Now: Consider 3 (asymmetric stretch)

O C O O C O

- Not changing polarizability (but dipole moment changes : IR active)

Summary for CO2 1) Symmetric Stretch: Polarizability changes () Raman allowed; Dipole constant (), IR forbidden 2) Asymmetric Stretch: - constant, Raman forbidden; - changing, IR-active Note: 1. If molecule has an inversion center, no vibrational mode can be both IR & Raman active 2. Raman bands that originate from the highest symmetry vibrations of a pt. group (A1, A1g, A1, etc) are polarized (Input of polarized excitation gives polarized scattering).

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Quantum Mechanically: The polarizability of a molecule by radiation along the direction ij (recall xx, yy, zz polarizability along x, y, z) ij =
1 h

[
e

(Mj) me(Mi)en (Mi) me(Mj)en + ] e o e + s

Where: m & n are initial & final states; e is an intermediate excited state (virtual) Mi & Mj are transition moments (electron) along i & j; e is energy of transition to e; s & o represent scattered & incident radiation Therefore: dependent upon o, Mij In order for a vibration to be Raman active:
r re

0 (must be a change in )

where: r is displacement along normal mode

Can plot vs. r obtain

A o re r

B o re

If If

r r

near re is small, Raman inactive mode (B) near re is larger, Raman active (A)