Use displacements of the left oxygen, carbon and right oxygen along a common positive direction. In this harmonic model the kinetic energy and elastic potential energy are
Thus the generalized eigenvalue problem for small oscillations is , where
The normal modes of three masses connected by two equal springs give the three independent solutions
The second row follows by holding the centre fixed and moving the end masses oppositely. In the remaining internal mode the end displacements are equal, and zero displacement of the centre of mass gives , yielding the third row; substitution verifies its frequency. Both nonzero modes have fixed centre of mass. In the symmetric stretch the two bond-length changes are equal; in the antisymmetric stretch they are opposite.
Figure 1.
Longitudinal mode directions of the free three-mass molecular model; the zero mode translates every mass together
. Details.
The zero mode occurs because a uniform translation changes neither spring length, so . It represents free center-of-mass motion, not an additional restoring vibration. Its general time amplitude is . Only one translational zero mode exists in the restricted one-dimensional model; transverse and rotational motion are outside its specified coordinates.
For the initial impulse, all displacement amplitudes at zero time vanish. Resolve the initial velocity into these three mode shapes:
Writing and gives the impulse on an end mass of a free symmetric three-mass chain:
In particular
where . The initial derivatives are , as required. The carbon dioxide model therefore drifts uniformly while undergoing both internal stretches. Its total momentum is the initial ; omitting the zero mode would incorrectly hold the centre of mass fixed.
Use displacements from an equilibrium, so the two spring extensions are and . The kinetic energy and elastic potential energy are
Thus and , with the small-oscillation mass and stiffness matrices
If instead denote absolute positions, the appropriate natural spring lengths must first be subtracted from the differences in . They do not affect the equations for displacements.
Euler-Lagrange equations give , so a normal mode obeys the generalized eigenvalue problem for small oscillations . Reflection symmetry separates antisymmetric shapes from symmetric shapes . In the antisymmetric sector the end equation is , giving . In the symmetric sector the two independent equations are
Twice the first plus the second gives . If , then . Otherwise , and substitution into the first equation gives . Thus the three independent shapes are:
For both springs retain their lengths, so this is uniform translation. For the end masses move oppositely and their forces on the middle mass cancel. For the end masses move together, while the middle mass moves oppositely so the centre of mass remains fixed. Direct substitution verifies all three eigenpairs; for positive the three eigenvalues are distinct and exhaust the three degrees of freedom. These are the normal modes of three masses connected by two equal springs.
A useful normalization is the weighted inner product induced by . Since the squared mass norms are , and , respectively, take
If ordinary Euclidean unit eigenvectors are intended instead, divide by , respectively. The frequencies and physical motions are independent of this normalization choice. The zero-frequency coordinate has general motion rather than an oscillation.
Substitution of into the normal modes of three masses connected by two equal springs gives
The corresponding shapes are , , . For example, , verifying the third eigenvalue directly.
Their relevant orthogonality uses the kinetic matrix :
This is mass-matrix orthogonality of normal modes. It also follows by subtracting from its transpose and using the symmetry of . Ordinary Euclidean inner products need not vanish: in fact .
Figure 1.
The three normal modes for a free spring chain with middle mass ; amplitudes are relative and the zero mode is translation
. Details.