Molecular Energy Levels

o Rotational transitions

o Vibrational transitions

o Electronic transitions
 Molecular Energy Levels
The total energy of a molecule consists generally of the
sum of four contributions:
Electronic energy, Ee due to the motion of electrons
about the nuclei;
Vibrational energy Ev, due to the vibrational motion of
the nuclei;
Rotational energy Er, due to the rotational motion of the
molecule; and
(4) translational energy.

We will not consider the translational energy any further

since it is not usually quantized
 Bohn-Oppenheimer Approximation
o Born-Oppenheimer Approximation is the assumption that the electronic motion
and the nuclear motion in molecules can be separated.

o This leads to molecular wave functions that are given in terms of the electron
positions (ri) and the nuclear positions (Rj):

 molecule(rˆi , Rˆ j )   electrons( rˆi , Rˆ j ) nuclei (Rˆ j )

o Involves the following assumptions:

 wave function depends on nuclear positions but not upon their

o Electronic
velocities, i.e., the nuclear motion is so much slower than electron motion that
they can be considered to be fixed.

o The nuclear motion (e.g., rotation, vibration) sees a smeared out potential
from the fast-moving electrons.
PURE ROTATIONAL SPECTRA OF DIATOMIC MOLECULES

Basic concepts
Rotational energies of molecules are quantized (i.e. only have definite energies)
E = h
E, energy in J; h Planck’s constant, Js;  rotational frequency, Hz.

The range of rotational frequencies is about 8x1010 - 4x1011 Hz, which corresponds to
wavelengths,  ~ 0.75 - 3.75 mm. These wavelengths fall in the microwave region of
the electromagnetic spectrum.
•Note that rotational motion of molecules is quantized, like electronic and vibrational transitions
associated absorption/emission lines

• Absorption of microwave radiation causes heating due to increased molecular rotational

activity
 Molecular spectroscopy

o Electronic transitions: UV-visible

o Vibrational transitions: IR

o Rotational transitions: Radio , microwave region

Electronic Vibrational Rotational

Molecular rotations
 Rotational motion
o Must first consider molecular moment of inertia:

I   mi ri2
i Generally specified about three axes: Ia, Ib, Ic.

o Rotation of molecules are considered to be rigid rotors.

o The
 rigid rotor is a mechanical model that is used to explain rotating systems. An arbitrary
rigid rotor is a 3-dimensional rigid object

o Rigid rotors can be classified into four types:

o Spherical rotors: have equal moments of inertia (e.g., CH4, SF6).

o Symmetric rotors: have two equal moments of inertia (e.g., NH3).

o Linear rotors: have one moment of inertia equal to zero (e.g., CO2, HCl).

o Asymmetric rotors: have three different moments of inertia (e.g., H2O).

 Quantized rotational energy levels

o The classical expression for the energy of a rotating body is:

Ea  (1 / 2) I aa2

where a is the angular velocity in radians/sec.

o For rotation about three axes: E  1 / 2( I aa2 )  (1 / 2) I bb2  (1 / 2) I cc2

o In terms of angular momentum (J = I):

J a2 J b2 J c2
E  
2Ia 2Ib 2Ic
o We know from QM that AM is quantized:

J  J(J  1) 2
, J = 0, 1, 2, …

J ( J  1)
o Therefore, E J  , J = 0, 1, 2, …
2I

 Quantized rotational energy levels
o Last equation gives a ladder of energy levels.

o Normally expressed in terms of the rotational constant,

which is defined by:
2 h
B  B  2
2 Ihc 8π cI
o Therefore, in terms of a rotational term:

E ( J )  BJ ( J  1) cm
-1

o The separation between adjacent levels is therefore

E(J) - E(J-1) = 2BJ

o As B decreases with increasing I =>large molecules have closely spaced

o energy levels.

B is called the rotational constant for a given molecule. Its units are cm-1, since J is just a quantum
number (label).
 RIGID ROTOR

Figure 40-16 goes here. A diatomic molecule can rotate around

a vertical axis. The rotational energy is
quantized.
 THE RIGID ROTOR
A diatomic molecule may be thought of as two atoms
held together with a massless, rigid rod (rigid rotator
model).
• Consider a diatomic molecule with different atoms of mass m1
and m2, whose distance from the center of mass are r1 and r2
respectively

 r1 | r2 
o o
m1 m2
• The moment of inertia of the system about the center of mass
is:
I  m1r1 2
 m 2 r2 2
 Rotational levels
• The classical expression for energy of rotation is :In the
harmonic oscillator model, the energy was all potential
energy. In the rigid rotor, it’s all kinetic energy:
• I 2 L2
Er   where L angular momentum
2 2I
 h  • where J is the rotational quantum number
2

L    J ( J  1)
2

 2 
2
1  h 
E(J )    J ( J  1)  h c B J ( J  1)
2 I  2 
h
B  the rotational constant
8 c I
2
Assume a rigid (not elastic) bond
r0 = r1 + r2

For rotation about center of gravity, C :

m1r1 = m2r2 ( = m2 (r0 - r1) )
m1r1 = m2 (r0 - r1)
m1r1 = m2r0 - m2r1

m2r0 m1r0
r1  r2 
m1  m2 m1  m2
Moment of inertia about C:
IC = m1r12 + m2r22 = m2r2r1 + m1r1r2
= r1r2 (m1 + m2)

 = reduced mass,
m1m2 2 1 1 1
I r0  μr0
2
 
m1  m2 μ m1 m2
More detailed derivation:

IC  m1r1  m2r2
2 2

m r  m r 
 m1r1  2 2   m2r2  1 1 
 m1   m2 
 r1r2 m1  m2 
 m1r0   m2r0 
    m1  m2 
 m1  m2   m1  m2 
m1m2 2
 r0
m1  m2
 Quantization of Rotational Energy
Molecular rotational energy is quantized
By solving Schrödinger equation for rotational motion

rotational energy level is given by

Rotational energy of level J

h2J(J+1) Joules
EJ 
8π 2 I
Rotational energy level in wave numbers
(cm-1) h
B
8π 2I
 ROTATIONAL SPECTRUM
Selection Rule
DJ1, Gross rule- the
molecule should have a
permanent electric dipole
moment,  . Thus, homonuclear
diatomic molecules do not have
a pure rotational spectrum.
Heteronuclear diatomic
molecules do have rotational
spectra

Dj  1
Dj  1 (absorption)
Dj  1 (emission)

17
Appearance of rotational spectrum We can calculate
the energy corresponding to rotational transitions

D E=EJ’ –EJ for DJ  J final  J initial  1

Or generally:
JJ+1 = B(J+1)(J+2) - BJ(J+1)
= 2B(J+1) cm-1

Microwave absorption lines should appear at

J=0 J=1: ν = 2B - 0 = 2B cm-1

J=1 J=2: = = 4B cm-1

Note that the selection rule is DJ = 1, where + applies to absorption

and - to emission.
Find r(CO)

h 2.7992774 10  46
I  kgm2

8π2Bc B
= r2
B = 1.921175 cm-1 ;  = 1.1386378 x 10-26 kg

 = 1.131 x 10-10 m
I
 0.1131 nm r
μ

Answer: C-O bond length is 0.1131 nm.

 J level Energy
J=6 42B

J=5 30B

J=4 20B

J=3 12B

J=2 6B
J=1 2B
J=0 0B

Energy of rotational energy levels: (Not equally spaced)

 Molecular vibrations

o Consider simple case of a vibrating diatomic molecule, where restoring force is

proportional to displacement
(F = -kx). Potential energy is therefore

V = 1/2 kx2
o Can write the corresponding Schrodinger equation as
2
d 2
 [E  V ]  0
2 dx 2
2
d 2
 [E 1/2kx 2
]  0
2 dx 2

m1m2
where 
m1  m2
o The S.E resultsin allowed energies
k 1/ 2
Ev  (v 1/2)      v = 0, 1, 2, …
 

 Molecular vibrations

o The vibrational terms of a molecule can therefore

be given by
E (v)  (v  1 / 2)hv~
1/ 2
1 k
v~   
2 

o Note, the force constant is a measure of the

curvature of the potential energy close to the
equilibrium extension of the bond.

o A strongly confining well (one with steep sides, a

stiff bond) corresponds to high values of k.
 Molecular vibrations

o The lowest vibrational transitions of diatomic

molecules approximate the quantum
harmonic oscillator and can be used to imply
the bond force constants for small
oscillations.

o Transition occur for Dv = ±1

o This potential does not apply to energies

close to dissociation energy.

o In fact, parabolic potential does not allow

molecular dissociation.

o Therefore more consider anharmonic

oscillator.
Morse Potential

It is a better approximation
for the vibrational structure of
the molecule than the
quantum harmonic oscillator
because it explicitly includes
the effects of bond breaking,
such as the existence of
unbound states. It also
accounts for the
anharmonicity of real bonds.


V  hcDe 1  e 
 a ( R  Re ) 2
Morse Potential

The dissociation energy De

is larger than the true
energy required for
dissociation D0 due to the
zero point energy of the
lowest (v = 0) vibrational
level.
 Anharmonic oscillator

o A molecular potential energy curve can be

approximated by a parabola near the bottom of the
well. The parabolic potential leads to harmonic
oscillations.

o At high excitation energies the parabolic

approximation is poor (the true potential is less
confining), and does not apply near the
dissociation limit.

o Must therefore use a asymmetric potential. E.g.,

The Morse potential:
V  hcDe 1 e 
a(R R e ) 2

where De is the depth of the potential minimum

and
1/ 2
  2 
a   
 2hcDe 


 Anharmonic oscillator

o The Schrödinger equation can be solved for the Morse potential, giving permitted energy
levels:
E (v)  (v  1 / 2) v~  ( v~  1 / 2) 2 xe v~

where xe is the anharmonicity constant: a2

xe 
2
o The second term in the expression for E(v) increases with v => levels converge at high
quantum numbers.

o The number of vibrational levels for a Morse
oscillator is finite:

v = 0, 1, 2, …, vmax
 Vibrational-rotational spectroscopy
o Molecules vibrate and rotate at the same time =>
E(v,J) = E(v) + E(J)

E (v, J )  (v  1 / 2)v~  BJ ( J  1)
o Selection rules obtained by combining rotational
selection rule ΔJ = ±1 with vibrational rule Δv = ±1.

o When vibrational transitions of the form v + 1  v

occurs, ΔJ = ±1.

o Transitions with ΔJ = -1 are called the P branch:

v~P ( J )  E(v  1, J 1)  E(v, J )

o Transitions with ΔJ = +1 are called the R branch:

v~R ( J )  E(v  1, J  1)  E(v, J )

o Q branch are all transitions with ΔJ = 0
 Vibrational-rotational spectroscopy

o Molecular vibration spectra consist of bands of lines in IR region of EM spectrum (100 –

4000cm-1 0.01 to 0.5 eV).

o Vibrational transitions accompanied by rotational transitions. Transition must produce a

changing electric dipole moment (IR spectroscopy).
Vibrational-rotational spectroscopy
Various Types of Infrared Transition
 Electronic transitions

o Electronic transitions occur between molecular

orbitals.

o Must adhere to angular momentum selection

rules.

o Molecular orbitals are labeled, , , D, …

(analogous to S, P, D, … for atoms)

o For atoms, L = 0 => S, L = 1 => P

o For molecules,  = 0 => ,  = 1 => 

o Selection rules are thus

D = 0, 1, DS = 0, D=0, D = 0, 1

o Where  =  +  is the total angular momentum

(orbit and spin).