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Fundamental modes of vibrations in polyatomic molecules

Molecular Vibrations

  • In polyatomic molecules, atoms are not stationary but vibrate around their equilibrium positions.

  • These vibrations can be described as periodic motions and are quantized, meaning they occur at specific energy levels.

  • The two main types of molecular vibrations are:

1) Stretching Vibrations:

  • Involve changes in the bond length between atoms.

  • Symmetric Stretching: Bonds expand and contract simultaneously in the same direction.

  • Asymmetric Stretching: One bond shortens while another lengthens.

2) Bending Vibrations:

  • Involve changes in the bond angle between atoms.

  • Scissoring: Two atoms move toward and away from each other.

  • Rocking: Atoms move in the same direction, rocking back and forth.

  • Wagging: Atoms move up and down out of the plane.

  • Twisting: One atom moves up while another moves down, causing a twist.

Degrees of Freedom

  • Translational Degrees: Movement of the entire molecule in space (three degrees).

  • Rotational Degrees: Rotation of the molecule around its axes (three degrees for nonlinear, two for linear molecules).

  • Vibrational Degrees: Calculated using the formula:

  • Nonlinear Molecules: 3N−63N - 63N−6

  • Linear Molecules: 3N−53N - 53N−5

  • Where NNN is the number of atoms in the molecule.


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