110B -

Chapter 13

Molecular Spectroscopy

Instructor: Huong Tong Email adress: tonghuongz@gmail.com

Interrogate Molecules with Electromagnetic Radiation

Chapter 13

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Chapter 13

Interrogate Molecules with Electromagnetic Radiation

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Chapter 13

Interrogate Molecules with Electromagnetic Radiation

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Chapter 13

Interrogate Molecules with Electromagnetic Radiation

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Chapter 13

Interrogate Molecules with Electromagnetic Radiation

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Chapter 13

Molecules as Harmonoic Oscillators and Rigid Rotors

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Chapter 13

Molecules as Harmonoic Oscillators and Rigid Rotors

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Chapter 13

Molecules as Harmonoic Oscillators and Rigid Rotors

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Chapter 13

Molecules as Harmonoic Oscillators and Rigid Rotors

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Chapter 13

Interaction between Rotations and Vibrations

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Chapter 13

Interaction between Rotations and Vibrations

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Chapter 13

Interaction between Rotations and Vibrations

Calculations of Spectroscopic Parameters

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Chapter 13

Interaction between Rotations and Vibrations

Anharmonicity

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Chapter 13

Interaction between Rotations and Vibrations

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Chapter 13

Interaction between Rotations and Vibrations

Electronic Spectra

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Chapter 13

Interaction between Rotations and Vibrations

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Chapter 13

Rotational Spectra of Polyatomic Molecules

If the absence of external fields, the energy of a molecule does not depend up on the position of its center of mass or its orientation. The potential energy The potential energy of a polyatomic molecule is therefore a function only the (3N-5) or (3N-6) vibrational coordinates

The Vibrational Hamiltonian operator

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Chapter 13

Infrared Spectrum

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Chapter 13

Symmetry and Molecular Vibrations

A molecular vibration is IR active only if it results in a change in the dipole moment of the molecule. In Group Theory Terms: A vibrational motion is IR active if it correspond to an irreducible representation with the same symmetry as an x, y, z coordinate (or function). The three normal models of H2O

Symmetric stretch
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Asymmetric stretch

Bend
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Chapter 13

Symmetry and Molecular Vibrations

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Chapter 13

Symmetry and Molecular Vibrations

Group Theory can be used to characterized the various normal coordinates belonging to any molecule Water is C2v point group Qss belongs to the totally symmetric irrecducible representation A1.The bending mode also be shown to belong A1 Qss = Qss;

2Qss = Qss

vQss = Qss

vQss = Qss

Qas belongs to the totally asymmetric irrecducible representation B2 Qas = Q as; 2Qas = - Qas vQas = - Qas vQas = Qas

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Chapter 13

Symmetry and Molecular Vibrations

We can use group theory to determine how many normal coordinates belong to each

irreducible representation.
In three dimensional, N atoms in molecule, so 3N x 3N reducible.

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Chapter 13

Selection Rules
The spectroscopic selection rules determine which transitions from one state to another are possible. Schrdinger equation:

Where: In the absence time dependent perturbations:

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Chapter 13

Interation of Electronmagnetic Waves with Molecules

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Chapter 13

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