QUANTUM CHEMISTRY: The Determination of Energy Eigenstates

NACruz Q4 09-10
Steps in the measurement of energy eigenstates
1. Define an initial state, , with energy, .
2. Allow the system at to interact w/ an external stimulant of
known properties. This causes a change in state from to
with a corresponding energy change from .
3. Applying conservation laws, means = , i.e.,
the is measured.
Remarks
The measurement of a physical variable involves indeterminacy.

& .
,
.
The energy, , of the initial state, , is well-defined, i.e., is an
eigenstate of the energy operator corresponding to .
Problem: Most systems contain many components, e.g., molecules,
whose energy states change rapidly over time. Some components
have lowest energy, , some have energies greater( ) than this.
Facts: # of components having is a constant.
The higher the temperature, the greater the # of components
having .
The mean translational energy of colliding molecules is given by

.

Collision obeys conservation laws and causes the ff

.
many have .
& many
molecules
have
, , . . , their energies are NOT WELL-DEFINED.

QUANTUM CHEMISTRY: The Determination of Energy Eigenstates

NACruz Q4 09-10
For physically constrained systems, the energy eigenstates are
discrete.
The energy spectrum is made up of discrete eigenvalues, =
, , , , usually represented by an E level diagram (fig 1).
Remarks
Horizontal lines represent eigenvalues.
Energy changes represented by arrows (transitions) occur as a
response to external stimuli.

Fig 1
Examples
System
Eigenvalue equation

Particle in 1D
=
box
2
For = 1, 2, . . ,
Vibration of

1
a diatomic
= +
molecule
2
1
+
2
For = 0,1, . . ,
Eigenstates

=
of H
24
For = 1,2, ,
2

Remarks
Only energy corresponding to
can cause a transition
Constrain the molecule only
vibrational motion is manifested.
=
= . .

=
=
=

QUANTUM CHEMISTRY: The Determination of Energy Eigenstates

NACruz Q4 09-10

For H atom the ff energy levels are generated from the eigenstate
equation in the table.

values

4
-0.0850
3
-1.511
2

-3.400

-13.597
Fig 2