Vibration of Diatomic Molecules

We will limit our discussion of vibrational

transitions to diatomic molecules. The
vibrational modes of polyatomic
molecules are more complex, but involve
the same principles. In addition,
vibrationalvibrational-rotational spectra describes
molecules in which both vibrational and
rotational modes need to be considered
simultaneously.
90

Vibration of Diatomic Molecules (contd)

Quantum mechanics can account for this, but
we are going to limit our discussion to
vibrational transitions in which there is no
rotation.

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Molecular Vibrations of a
Diatomic Molecule
As we previously considered,
molecular vibrations can be
modeled after harmonic
oscillators where the
potential energy is
approximated by the
parabolic equation:
equation:
V=1/2 kx2
Where x=Rx=R-Re
k is the force constant
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Force Constant
The force constant
of the bond can be
thought of as the
stiffness of the bond.
The steeper the walls
of the potential, the
greater the force
constant.
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If we use the parabolic approximation for the

potential energy of the relative motion of two
atoms, the Schr
Schrdinger equation is as follows:
h 2 d 2 1 2
+ kx = E
2meff dx 2 2
Where meff is the effective mass calculated by:

meff =

m1m2
m1 + m2
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Since the Schr

Schrdinger equation is the
same as we previously obtained for a
harmonic oscillator, the permitted
vibrational energy levels are:
=(k/meff)
E=(
=(+)
)
=0,1,2,. . .
The vibrational terms of a molecule
are the energies of its vibrational states
expressed in wave numbers. The
vibrational terms are denoted G(
G().
95

Since E=hcG(
hcG() the~ vibrational term can be
written as:
G(
G()=(
)=(+)
)~
1/ 2
Where ~=

v~ =

1 k
2c meff

96

Vibrations
The vibrational terms
depend on the
effective mass of the
molecule. Consider
the following
vibration for 1HF and
2DF and 1HCl and
2DCl:
97

Selection Rules
The gross selection rules for the absorption
of radiation by a molecular vibration is that
the electric dipole moment of the molecule
must change when the atoms are displaced
relative to one another. These are infrared
active.
active.
The molecule does not need to be polar,
polar, but it
needs to have polar bonds.
bonds.
98

If the molecule has only nonnon-polar bonds,

such as O2 or H2, the vibrations are
infrared inactive.
inactive.
Question?
Which of the following are infrared active?
CO2, F2, H2O, OCS, H2C=CH2
99

Specific Vibrational Selection Rule

The specific vibrational selection rule has been
obtained by detailed analysis of harmonic
oscillators. The resulting selection rule is as
follows:
=1
Transitions where =+1 correspond to
absorption.
absorption.
Transitions where =-1 correspond to
emission.
emission.
100

Specific Vibrational Selection Rule

The wavenumbers of allowed vibrational
transitions, Gv+1 for the transition
+1
+1 are:
G+1 = G(
G(+1) - G(
G()=
)=~
Most molecules haves wavenumbers,
wavenumbers, ~ ,
for vibrational transitions in the infrared
region of the electromagnetic spectrum.
101

Specific Vibrational Selection Rule

(contd)

At room temperature, most molecules are in

their ground state since thermal heat at room
temperature is not going to provide molecules
with enough energy to be in their excited
state.
As a result, room temperature IR spectra will
have a dominate spectral transition where
from =0 to =1 is called its fundamental
transition.
transition.
102

Anharmonicity
We expect differences in
energy levels for a harmonic
oscillator to be constant for
all transitions as given by
the equation:
E+1-E=
However, as we have noted
earlier, the parabolic nature
of a harmonic oscillator is
only an approximation of
molecular vibrations.
103

Consider the true nature of the potential

energy curve for a diatomic molecule, such
as H2.
There is an optimal energy value related to the
distance between the atoms.
If the atoms move closer, the potential
energy increases due to the repulsive
forces of the two positively charged nuclei.
If the atoms move apart, they do not
share the electrons as well and they
eventually dissociate and the bond is
broken.
104

Anharmonicity
The harmonic oscillator
does not take this into
consideration, it is just
an approximation.
A real molecular vibration
does not vibrate
harmonically, instead
the motion is
anharmonic.
anharmonic.
105

Anharmonicity (contd)
This leads us to the
conclusion that the
energy levels are not
spaced equally
apart, but have
smaller spacing at
higher excitations.

106

Morse Potential Energy

To better predict energy levels, we can use another
function rather than the function of a parabola. The
Morse potential energy function is given by:

V = hcDe 1 e a ( R Re )

Where De is the depth of the potential minimum as

seen in the illustration.
1/ 2

meff 2

a=
2hcD
e

107

De

108

Morse Meets Schrdinger

The Schrdinger
Schrdinger equation can be solved for the Morse
potential and the permitted energy values a-e
G(
G()=(
)=(+)
)~ -(+)2xe~
where

xe =

a 2h
v~
=
2meff 4 De

Xe is the anharmonicity constant.

For a Morse oscillator, the number of vibrational levels
is finite and v=0,1,2,...vmax.
109

110

Morse Oscillator
The Morse oscillator is a useful theorectical
model. However, a more practical expression:
G(
G()=(
)=(+)
)~ -(+)2xe~+(
+(+)3ye~ +
Where xe, ye, . . . are empirical constants
characteristic of the molecule used to fit
experimental data.

111

Transitions Forbidden by
the Selection Rules
Additional weak absorption lines corresponding
to =0 to =2, =0 to =3, etc. transitions
occur even though these overtones are
forbidden by the specific selection rule.
Recall that the specific selection rule was based
on a harmonic oscillator. The anharmonic
nature of true molecular vibrations allows for
these forbidden overtones.

112

Why is Water Blue?

These forbidden overtones are responsible
for the blue color of water. See article at
http://www.dartmouth.edu/~etrnsfer/
water.htm

113

The Birge-Sponer Plot

Since we needed to use the
Morse potential oscillator
to account for the reality
of dissociation, it is
expected that we may
want to use vibrational
spectroscopy to provide
us with information about
dissociation energy.

114

The Birge-Sponer Plot

A graphical technique called
a BirgeBirge-Sponer plot may
be used to determine
dissociation energy.
The basis of the BirgeBirgeSponer plot is that the sum
of the successive intervals
Gv+1 from the zerozero-point
level to the dissociation
limit is the dissociation
energy.
115

The Birge-Sponer Plot

G
G+=Do=G+G/2+ G5/2 + . . .

v
A linear extrapolation is a good
approximation of Do, but is typically a bit
of an overestimate of the true value.

116