Stark Effect in Atomic Spectra

The splitting of atomic spectral lines as a result of an externally applied electric

field was discovered by Stark, and is called the Stark effect. As the splitting of
a line of the helium spectrum shows, the splitting is not symmetric like that of the
Zeeman effect.
The splitting of the energy levels by an
electric field first requires that the field
polarize the atom and then interact with
the resulting electric dipole moment. That
dipole moment depends upon the magnitude
of Mj, but not its sign, so that the energy
levels are split into J+1 or J+1/2 levels, for
integer and half-integer spins respectively.
The Stark effect has been of marginal benefit in the analysis of atomic spectra,
but has been a major tool for molecular rotational spectra.
Atomic Properties
The electrons associated with atoms are found to have measurable properties
which exhibit quantization. The electrons are normally found in quantized energy
states of the lowest possible energy for the atom, called ground states. The
electrons can also exist in higher "excited states", as evidenced by the line spectra
(e.g. the hydrogen spectrum) observed when they make transitions back to the
ground states. The existence of these excited states can be demonstrated more
directly in collision experiments like the Franck-Hertz experiment .

Other properties associated with the electron energy levels such as orbital angular
momentum and electron spin are also quantized and give rise to the quantum
numbers used to characterize the levels. These quantized properties are associated
with periodic table of the elements, and the requirements of the Pauli exclusion
principle on the quantum numbers can be viewed as the origin of the periodicity.
The periodic table provides a convenient framework for cataloging other physical
and chemical properties of atoms. While the hydrogen electron energy levels are
found to depend only upon the principal quantum number, the energy levels in
other atoms are found to have strong dependence upon the orbital quantum
number. These levels show a smaller amount of dependence upon the total
angular momentum. This dependence may arise from interactions within the atom
such as the spin-orbit interaction or may arise only when external fields are
applied. When magnetic fields are applied, there is splitting of atomic energy
levels from the Zeeman effect, and in response to electric fields there is splitting
called the Stark effect.

For light atoms with multiple electrons
outside a closed shell, we can combine
the orbital angular moments to give a
resultant angular momentum L.
Considering the vector model, we
expect that we can get different values
of L for a given set of individual orbital
angular momenta. It turns out that the
largest possible L value has the lowest
energy. This is sometimes referred to as
the "orbit-orbit effect" (Hund's Rule #2)
With multiple electrons there is an additional source of splitting of the electron
energy levels which is characterized in terms of another quantum number, the
total anglular momentum quantum number J. The source of the splitting is called
the spin-orbit effect. For light atoms, the spins and orbital angular momenta of
individual electrons are found to interact with each other strongly enough that you
can combine them to form a resultant spin S and resultant orbital angular
momentum L (this is called Russell-Saunders or LS coupling). The S and L are
combined to produce a total angular momentum quantum number J, and it is
found that higher J values lie lower in energy (Hund's Rule #3)
When an external interaction such as a magnetic field is applied, then further
splitting of the energy levels occurs, and that splitting is characterized in terms of
the magnetic quantum number associated with the z-component of angular
momentum. This splitting is called the Zeeman effect. Effects on energy levels
from applied electric fields are called Stark effects.

Orbital Angular Momentum
The orbital angular momentum of electrons in atoms associated with a given
quantum state
is found to be quantized in the form

This is the result of applying quantum theory to the orbit of the electron. The
solution of
the Schrodinger equation yields the angular momentum quantum number. Even in
the case
of the classical angular momentum of a particle in orbit,

the angular momentum is conserved. The Bohr theory proposed the quantization
of the
angular momentum in the form


and the subsequent application of the Schrodinger equation confirmed that form
for the
orbital angular momentum.
The spectroscopic notation used for characterizing energy levels of atomic
electrons is
based upon the orbital quantum number.
Total Angular Momentum
When the orbital angular momentum and spin angular momentum are coupled, the
total
angular momentum is of the general form for quantized angular momentum


where the total angular momentum quantum number is


This gives a z-component of angular momentum


This kind of coupling gives an even number of angular momentum levels, which
is consistent with the multiplets seen in anomalous Zeeman effects such as that of
sodium. As long as external interactions are not extremely strong, the total angular
momentum of an electron can be considered to be conserved and j is said to be a
"good quantum number". This quantum number is used to characterize the
splitting of atomic energy levels, such as the spin-orbit splitting which leads to the
sodium doublet.

Magnetic Interactions and the
Lande' g-Factor
A magnetic moment experiences a
torque in a magnetic field B. The
energy of the interaction can be
expressed as

Both the orbital and spin angular
momenta contribute to the magnetic
moment of an atomic electron.

.where g is the spin g-factor
and has a value of about 2,
implying that the spin angular
momentum is twice as
effective in producing a magnetic moment. The
interaction energy of an atomic electron can
then be written which when evaluated in terms
of the relevant quantum numbers takes the
form






Evaluating the Lande' g-Factor
The Lande' g-factor is a geometric factor which arises in the evaluation of the
magnetic interaction which gives the Zeeman effect. The magnetic interaction
energy which is continuous in the classical case takes on the quantum form

which is like a vector operation based
on the vector model of angular
momentum
The problem with evaluating this scalar product is that L and S continually change in
direction as shown in the vector model.
The strategy for dealing with this problem is to use the direction of the total angular
momentum J as a coordinate axis and obtain the projection of each of the vectors in
that direction. This is done by taking the scalar product of each vector with a unit
vector in the J direction. These vector relationships must be evaluated and expressed
in terms of quantum numbers in order to evaluate the
energy shifts. Carrying out the scalar products above
leads to









"Anomalous" Zeeman Effect
While the Zeeman effect in some atoms (e.g., hydrogen) showed the expected
equally-spaced triplet, in other atoms the magnetic field split the lines into four,
six, or even more lines and some triplets showed wider spacings than expected.
These deviations were labeled the "anomalous Zeeman effect" and were very
puzzling to early researchers. Their explanation gave additional insight into the
effects of electron spin. With the inclusion of electron spin in the total angular
momentum, the other types of multiplets formed part of a consistent picture. So
what has been historically called the "anomalous" Zeeman effect is really the
normal Zeeman effect when electron spin is included.

For magnetic field in the z-direction this gives

Considering the quantization of angular momentum , this gives equally spaced
energy levels displaced from the zero field level by

This displacement of the energy levels gives the uniformly spaced multiplet
splitting of the spectral lines which is called the Zeeman effect. The magnetic
field also interacts with the electron spin magnetic moment, so it contributes to the
Zeeman effect in many cases. The electron spin had not been discovered at the
time of Zeeman's original experiments, so the cases where it contributed were
considered to be anomalous. The term "anomalous Zeeman effect" has persisted
for the cases where spin contributes. In general, both orbital and spin moments are
involved, and the Zeeman interaction takes the form

The factor of two multiplying the electron spin angular momentum comes from
the fact that it is twice as effective in producing magnetic moment. This factor is
called the spin g-factor or gyromagnetic ratio. The evaluation of the scalar product
between the angular momenta and the magnetic field here is complicated by the
fact that the S and L vectors are both precessing around the magnetic field and are
not in general in the same direction. The persistent early spectroscopists worked
out a way to calculate the effect of the directions. The resulting geometric factor
gL in the final expression above is called the Lande g factor. It allowed them to
express the resultant splittings of the spectral lines in terms of the z-component of
the total angular momentum, mj.

Term Symbols
The heirarchy of labels for the electrons of multi-
electron atoms is configuration, term, level, and state.
The term uses the multiplicity 2S + 1, total orbital
angular momentum L, and total angular momentum
J. It assumes that all the spins combine to produce S,
all the orbital angular momenta couple to produce L, and then the spin and orbital
terms combine to produce a total angular momentum J.
Different terms will in general have different energies, and the order of those
energies is usually that given by Hund's Rules, although there are exceptions. The
different terms for a given configuration are obtained by forming the different
combinations of angular momenta for the electrons outside closed shells, making
sure the Pauli Exclusion Principle is obeyed


Hund's Rules
1. The term with maximum multiplicity lies lowest in energy
2. For a given multiplicity, the term with the largest value of L lies lowest
in in energy.
3. For atoms with less than half-filled
shells, the level with the lowest value
of J lies lowest in energy.
Hund's rules assume combination to
form S and L, or imply L-S (Russell-
Saunders) coupling. Note: Some
references, such as Haken & Wolf, use
Hund's Rule #1 to apply to the nature
of full shells and subshells. Full shells
and subshells contribute nothing to the
total angular momenta L and S. If you call this Hund'e Rule #1, then the above
rules will be bumped up one in number. I don't know which is the more common
practice.
Hund's Rule #1
The term with the maximum multiplicity lies lowest in energy.
Example: In the configuration we expect the order
The explanation of the rule lies in the effects of the spin-spin interaction. Though
often called by the name spin-spin interaction, the origin of the energy difference
is in the coulomb repulsion of the electrons. It's just that a symmetric spin state
forces an antisymmetric spatial state where the electrons are on average further
apart and provide less shielding for each other, yielding a lower energy. The
sketches below attempt to visualize why that is so.




These sketches are conceptual only. No attempt has been made to do any realistic
scaling. Note that the energies we are discussing here are electric potential
energies, so that a negative electron in the vicinity of a positive nucleus will have
a negative energy leading to a bound state. Any force between the electrons will
tend to counter that, contributing a positive potential energy which makes the
electrons less tightly bound, or higher in potential energy.
Hund's Rule #2
For a given multiplicity, the term with the largest value of L lies lowest in energy.

The basis for this rule is essentially that if the electrons are orbiting in the same
direction (and so have a large total angular momentum) they meet less often than
when they orbit in opposite directions. Hence their repulsion is less on average
when L is large. These influences on the atomic electron energy levels is
sometimes called the orbit-orbit interaction. The origin of the energy difference
lies with differences in the coulomb repulsive energies between the electrons.




For large L value, some or all of the electrons are orbiting in the same direction.
That implies that they can stay a larger distance apart on the average since they
could conceivably always be on the opposite side of the nucleus. For low L value,
some electrons must orbit in the opposite direction and therefore pass close to
each other once per orbit, leading to a smaller average separation of electrons and
therefore a higher energy.
Hund's Rule #3
For atoms with less than half-filled shells, the level with the lowest value of J lies
lowest in energy.

When the shell is more than half full, the opposite rule holds (highest J lies
lowest). The basis for the rule is the spin-orbit coupling. The scalar product SL is
negative if the spin and orbital angular momentum are in opposite directions.
Since the coefficient of S L is positive, lower J is lower in energy.