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CHEM F111 Lecture 14:

Molecular spectroscopy - Vibrational spectra

Review
VB and MO theories
Variation Theorem Resonance and configuration interaction Classification of MO based on energy, angular momentum and symmetry Molecular orbital energy level diagrams for hetero-nuclear diatomic molecules Molecular orbitals of polyatomic molecules Huckel theory for pi-electron system Molecular spectroscopy Rotational spectra of diatomic molecule using rigid rotor model
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Vibrational spectroscopy
Diatomic molecule A-B: Harmonic approximation: Expand molecular potential energy in power series about minimum, and truncate after quadratic term. V = k(R Re)2 k is the force constant with dimensions of N/m. The steeper the walls of the potential, the stiffer the bond, the greater the value of k In the harmonic approximation E = ( + )h , = 0, 1, 2, .. = 1/2 (k/ ) 1/2 where = mAmB/(mA + mB) is the reduced mass. In terms of wavenumber : E = ( + )hc , = 0, 1, 2,
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Vibrational spectroscopy

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Wavefunctions (Harmonic approximation)

Wavefunctions alternately symmetric and antisymmetric about the mean position (the functions are alternately even and odd)
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Selection rules
Vibrational transitions: At frequencies of 1013 to 1014 Hz, infrared spectroscopy. Transition probability m*n d2, transition dipole integral Gross selection rule: The electric dipole moment of the molecule must change during the vibration. Homonuclear diatomics are IR inactive. Specific selection rule: = 1 E = h Most important transition from = 0 to = 1.
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Anharmonicity
Anharmonicity: E = ( + )hc - ( + )2 hc xe + . xe is anharmonicity constant. Additional weak absorption lines or overtones corresponding to = 2,3,.. Appear.

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Vibrational spectra: Polyatomic molecules

For a molecule with N atoms, the number of coordinates required to specify the position of all the atoms is 3N. These 3N displacements can be thought of in terms of various degrees of freedom. Translational : 3 Rotational : 2 for linear and 3 for nonlinear molecule. Vibrational : 3N 5 for linear and 3N 6 for nonlinear molecule.

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Degrees of freedom

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Normal modes of vibrations

Description of vibration most convenient and simple in terms of normal modes. Normal mode Collective, independent, synchronous motion of group of atoms, that may be excited without exciting any other mode. Each normal mode may be approximated as a harmonic oscillator with a characteristic frequency and an effective mass. Any arbitrary displacement may be expressed as a superposition of the normal modes.

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Vibrational spectroscopy
Actual (total) stretching motion

Independent components contributing to the motion (Normal modes): symmetric and asymetric stretching

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Water:
Normal modes of vibrations

Symmetric stretch

Bend

Asymmetric stretch

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Carbon dioxide:
Normal modes of vibrations
Symmetric stretch inactive. Asymmetric stretch active, parallel bands. Bends active, perpendicular bands.

Two such modes

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Vibrational spectroscopy
Infrared spectroscopy powerful tool in identifying organic molecules. Some modes essentially motions of individual functional groups. Others are collective motions of the molecule as a whole fingerprint region of spectrum.

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