6.3 Frequencies of Free Vibration and Normal Coordinates •For the general solution !

•For the general solution !j(t) = " Ck a jk e #i$ kt , coefficients are

k
•For a system displaced slightly from equilibrium, the equations determined by the initial conditions at t = 0:
of motion Tij"˙˙ j + Vij!j = 0 (i = 1,2,3, … n) have the
oscillatory solutions: !j " Caje-i"t !j (0) = Re(Ckajk), Re stands for “real part of.”
"˙ j (0) = Im(Ckajk"!k ) Im stands for “imaginary part of.”
•In general, the secular equation gives n so called “free Equivalently,
! 1
vibration” or “resonant” frequencies, "k (k = 1, 2, ... n) Re Cl = " a jl T jk #k (0) ImCl = # a jl T jk $˙ k (0)
j,k "l j,k
!
•The general solution is a linear combination (i.e.,
superposition) of oscillations at all allowed frequencies.
!j(t) = " Ck a jk e #i$ k t Normal Coordinates
! !
k •General solution !j(t) = " Ck a jk e #i$ kt are the sum of simple
here ajk " eigenvector elements (make up columns and rows k
of “eigenvector matrix” A). Ck " a scale factor (complex). harmonic oscillations at all frequencies "k satisfying the
equation of motion. So the overall motions are coupled simple
!
• The general solutions in other forms: For each eigenvalue #k harmonic oscillations.
!
= $k2, seems as if there are 2 resonant frequencies: ± $k. So the
general solution can be written as •It is possible and quite useful, to transform from the
!j(t) = ajk ( Ck+ e +i" k t + Ck# e #i" k t ). generalized coordinates !j(t) to a new set of generalized
With the understanding that the actual motion is the real coordinates %j(t) called the Normal Coordinates, in which each
part of !j(t). !j(t) can also be written as %j(t) oscillates separately at only one of the resonant frequencies
!j(t) = fkajk cos("kt + #k) $j. Each %j satisfies a simple harmonic oscillator equation of
! motion at a different $j and there is no coupling between them.
The initial condition of oscillation will determine either
{fk, #k } or { Ck+ ,Ck"}.

!
By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.1 By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.2
Transformation to Normal Coordinates: !j(t) = aij%j
Let ! and % be the single-column matrices (vectors),
! = A% or % = A-1! = Ã!
where A = matrix of the eigenvectors.

•Both the KE T and the PE V are diagonal in the Normal

Coordinate representation. That is, a similarity transformation
with A diagonalizes both T and V. In terms of normal
coordinates,
T = 12 "˜˙"˙ = 12 # "˙i 2 , V = 12 "˜#" = 12 %$ k2" k2
i k
Note: factors of the masses are included in the definition of %i,
so the mass doesn’t appear explicitly in either T or V.
!The Lagrangian is: !
L = T - V = 12 (# "˙k2 $ #% k2" k2 )
k k
So the Lagrange’s equations of motion:
"˙˙ # $ k2" k = 0 (k = 1,2,3, … n)
The solution is!n uncoupled simple harmonic oscillations:
%j(t) = Ck e "i# k t
!
Therefore, each Normal Coordinate is involved in only one
of the resonant frequencies.
!

By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.3 By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.4
By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.5 By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.6
6.4 Free Vibrations and Normal Modes of a Linear
Symmetrical Triatomic Molecule •The secular equation is:
k " #2m "k 0
2
|V - $ T| = "k 2k " # 2 M "k =0
2
0 "k k "# m
The figure shows the equilibrium configuration of the molecule. which leads to a cubic equation in "2:
The generalized coordinators are x1, x2, x3. Equilibrium "2(k - "2m)[k(M +2m) - "2Mm] = 0
distances: x02 - x01 = x03 - x02 = b. The interatomic potential
between atoms is an ideal spring of spring constant k. Also, !
Obviously, the three eigenvalues (free vibration
consider only longitudinal vibrations (displacements in the x
frequencies) are:
direction).
"1 = 0, "2 = mk , "3 = mk (1+ 2m
M
)
*The PE: V = !k(x2 - x1 -b)2 + !k(x3 - x2 -b)2
Introduce a new set of general coordinates, which are the • " 1 = 0, what does the zero frequency mean? It means no
relative displacement from the equilibrium positions: oscillation of any kind! The normal coordinate %1 is actually a
!j " xj - x0j ! !
uniform translation of the molecule along the x axis. We can
V = !k(!2 - !1)2 + !k(!3 - !2)2 translate the molecule in this way without changing the PE.
= !k(!12 + 2!22 +!32 - 2!1!2 - 2!2!3) We’ve assumed the molecule has 3 vibrational degrees of
# k "k 0 & freedom. In reality, it has one translational degree of freedom
%
or by tensor V = %"k 2k "k (
( and 2 vibrational degrees of freedom. One translational
% ( normal mode and two vibrational normal modes.
$ 0 "k k '
• For "1 = 0, all displacements !i are equal !1 = !2 = !3 = 0,
*The KE: T = !m( x˙ 12 + x˙ 32) + !M x˙ 22 and V = 0. Since "1 = 0 does not affect other vibrational
= !m("˙ 12 + "˙ 32) + !M"˙ 22 modes, we could have done the problem from the beginning
! "m 0 0 %
$ ' to exclude this root. This could be done by imposing the
or by tensor
! !T = $ 0 !M 0 ' constraint that the CM of the molecule be stationary at the
$ ' origin, i.e.,
! ! # 0 0! m &
By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.7 By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.8

!
 m(x1 + x3) + Mx2 = 0
This constraint eliminates one of the coordinates xi (or one
of the displacements !i) from T and V and reduces the system to
2 degrees of freedom.

•"2 = k:
m
this is the frequency of oscillation for a single mass
m suspended from a single spring of constant k. Based on this,
we speculate that only two end atoms, m, are involved in the
oscillations associated with this mode. Expect the normal mode
! displacement % for eigenvalue " has end atoms moving and
2 2
center atom M stationary.
*For "2 = mk (two end atoms m vibrating and the center atom
Solving Eigenvectors M stationary):
•To get the normal mode displacements (eigenvectors), put "j a12 = 1/ 2m , a22 = 0, a32 = -1/ 2m
back into secular equation. We get 3 equations for each of the 3 The center atom is at rest. Since a12 = - a32, the two end
eigenvalues "j: !
atoms vibrate in opposite direction or 180° out of phase:
! !
(k - "j2m)a1j - ka2j +0 =0 •For "3 = k (1+ 2m ) :
m M
- ka1j + (2k - "j2M]a2j - ka3j =0 a13 = a33 = 1/ 2m(1+ 2m / M ) , a23 = "2 / 2M(2 + M / m)
2
0 - ka2j + (k - "j m)a3j = 0
The outer 2 atoms vibrate with the same amplitude and
In addition, have the normalization equation !
phase. The inner atom vibrates out of phase with them and with
m(a1j2 + a3j2) + Ma1j2 = 1 !
a different amplitude. !

•For "1 = 0 (uniform translation of entire molecule):

a11 = a21 = a31 = 1/ 2m + M . All 3 equal is what we
expect for uniform translational motion. As in the figure:
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!
Normal Mode Displacements
• Any general longitudinal vibration (excluding uniform
•Given the eigenvector components, we can compute the normal translation) of the molecule involves some linear combination
mode displacements. Use % = A-1! = Ã!. of the normal mode % 2 = m2 ("1 # "3 )=c2exp(-i"2t) at "2 =
k and the normal mode % 3(t) = mM [(" + " ) # 2" ]
1 3 2
• For "1 = 0: (Uniform translation). m 2(2m+M )
1 = c3exp(-i"3t) at "3 = k (1+ 2m ) .
%1 = (m"1 + M"2 + m" 3 ) m M
2m+M !

• For "2 = mk : (Two end atoms vibrating, the center atom ! •For example, D(t) = C2 % 2!(t) + C3 % 3(t), C2, C3 are complex.
stationary). Relative sizes and phases determined by initial conditions.
! !
% 2 = m2 ("1 # "3 ) General Motions of A Triatomic Molecule
! •In the above example, we only considered longitudinal (x
• For "3 = k (1+ 2m ) :
m M directed) displacements. A real molecule also has normal
! mM [(" + " ) # 2" ]
% 3 = 2(2m+M vibrational modes perpendicular to molecular axis. In general, 9
1 3 2
) degrees of freedom result in 9 normal modes. Complicated, but
doable algebra. The basic physics is similar to what we just
! went through. Without going to detailed math, we now do a
qualitative physics discussion of expected results.
!
•In general, for a molecule with n atoms there are 3n degrees of
freedom. The vibrational frequency eigenvalue problem will
have 3n frequencies as solutions. In general, there will be 6
frequencies for which " = 0. 3 of these correspond to the 3
translational degrees of freedom, in which the normal modes are
3 uniform translations along 3 mutually perpendicular axes.
Three (usually) correspond to the 3 rotational degrees of

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freedom in which the normal modes are 3 rigid rotations about 3
mutually perpendicular axes.
•For a linear molecule, things are a bit different: There are 3
translational degrees of freedom, corresponding to uniform
translations along 3 mutually perpendicular axes. However,
there are only 2 rotational degrees of freedom, in which the
normal modes are 2 rigid rotations about the 2 mutually
perpendicular axes perpendicular to molecular axis. Rotation
with the rotation axis being the molecular (x) axis itself makes
no sense, since the molecule (in this approximation) has no
extent in directions perpendicular to x. So, there will only be 2
normal modes corresponding to rigid rotations.
Number of vibrational degrees of freedom
= 9 - 3 (translational) - 2 (rotational) = 4
For linear triatomic molecule, we expect 4 vibrational
frequencies and 4 (non-zero) solutions to the eigenvalue
problem.
•2 of these 4 modes correspond to longitudinal vibrations.
These are the ones we’ve just computed. In fact, if coupling
between vibrations along the molecular (x) axis and vibrations
perpendicular to that direction is neglected, the solutions for the
frequencies and for the eigenvectors are EXACTLY the ones
we’ve already computed.
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•The remaining 2 of these 4 modes correspond to transverse
vibrations (vibrations perpendicular to x direction). If molecule
is axially symmetric, then no reason to expect a preference for
one perpendicular direction (say y) over another (say z). Thus,
the 2 frequencies corresponding to these 2 transverse vibrations
must be equal. The 2 transverse modes are degenerate.
•The 2 transverse modes are degenerate. They have the same
frequency. So, to determine the eigenvectors, we cannot directly
follow the procedure we used up to now, as degeneracy was
excluded. In computing the eigenvectors, any 2 mutually
orthogonal axes perpendicular to x axis can be chosen. The
motion of the molecule perpendicular to x axis depends on the
amplitudes and relative phases of these 2 degenerate modes.
•If both modes are excited, and if they vibrate exactly in phase,
the atoms will move in a straight line passing through the
equilibrium configuration. But, if they are out of phase, the total
transverse motion is an elliptical Lissajous figure (like the 2d
isotropic SHO). In this case, the motion in these modes is
actually a rotation rather than a vibration.
•From molecular symmetry: In all modes, the amplitudes of the
displacements of the end atoms must be equal. Detailed
calculation of the degenerate, transverse vibrational (rotational)
modes shows that, in this mode, the end atoms travel in the
same direction along a Lissajous figure. In order to conserve
angular momentum, the center atom must move (revolve) in the
By Prof. Juyang Huang, Texas Tech University. All rights reserved. CH6B.14
opposite direction. See figure (which is for the 2 degenerate
modes which are 90° out of phase).

• For large multi-atom molecules, group theory as well as

modern computational techniques are used to diagonalize
large matrices to find the vibrational normal modes of the
molecules.

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