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Stark Effect

The Stark effect is the shifting and splitting of spectral lines of atoms and molecules due to an external electric field. It can be divided into first-order and second-order effects. The first-order effect is linear in the applied electric field and seen in hydrogen-like atoms. The second-order effect is quadratic in the field and observed in many-electron atoms. The linear Stark effect results in symmetrical splitting, while the quadratic effect produces asymmetrical patterns with larger magnitudes.

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965 views5 pages

Stark Effect

The Stark effect is the shifting and splitting of spectral lines of atoms and molecules due to an external electric field. It can be divided into first-order and second-order effects. The first-order effect is linear in the applied electric field and seen in hydrogen-like atoms. The second-order effect is quadratic in the field and observed in many-electron atoms. The linear Stark effect results in symmetrical splitting, while the quadratic effect produces asymmetrical patterns with larger magnitudes.

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Stark Effect

Discovery

Splitting up of spectral lines in a magnetic field was discovered by Zeeman as


early as 1897. Some 16 years elapsed before anyone succeeded in showing that a similar
effect is produced when a source of light is placed in electric field.

In 1913, Stark demonstrated that every line of the Balmer series of hydrogen, when
excited in a strong electric field of at least 100000 volts per cm, is split into a number of
components.

The Stark effect is the shifting and splitting of spectral lines of atoms and molecules
due to the presence of an external electric field. The amount of splitting or shifting is
called the Stark splitting or Stark shift.

In general, one distinguishes first- and second-order Stark effects. The first-order effect
is linear in the applied electric field, while the second-order effect is quadratic in the
field.

Main Features

1] All hydrogen lines form symmetrical patterns, but the pattern depends on the
quantum number n of the terms involved. The number of Stark lines and the total width
of the pattern increases with n.

The line Hβ shows a large number of Stark components than Hα, the line Hγ still showing
more larger number.

2] The wave number shifts are integral multiple of a unit which is proportional to the
strength of the electric field, and the same for all hydrogen lines.

3] The hydrogen lines involving the lower energy states (small n), such as Hα, Hβ
show only a symmetrical splitting proportional to the field strength about their field free
positions. This is known as the first order or the linear Stark effect.
4] For the lines involving the higher states, such as Hγ, Hδ the Stark components
show unidirectional displacements proportional to the square of the field strength. This
is known as second order Stark effect.

The first order Stark effect is restricted to hydrogen like atoms and occurs only in field
large enough for the fine structure to become negligible. Other atoms show a second
order or quadratic effect which is generally very small.

What is Linear Stark Effect?


Linear stark effect is the series of spectral lines that are produced when transitions
between the energy levels are symmetric. In this type of effect, the difference between the
energy levels (∆ε ) is proportional to the applied electric field (E). The relationship is as
follows:

∝E
∆ε∝

Generally, the linear stark effect is characteristic of hydrogen that occurs in low strength
electric fields. Typically, the energy level of a hydrogen atom having a given principal
quantum number “n” tends to split symmetrically into 2n-1 sublevels. Moreover, we can
observe this type of stark effect in hydrogen-like atoms such as He+, Li+2 and Be+3.

What is Quadratic Stark Effect?


The quadratic stark effect is the series of spectral lines where the lines pattern is
asymmetric. In this type of stark effect, the difference between the energy levels (∆ε ) is
proportional to the square of the applied electric field (E). The relationship is as follows:

∆ε∝ E2

This type of stark effect is common in many-electron atoms. Typically, the magnitude of
the quadratic effect is comparatively small. Furthermore, this effect can be found in
atoms with asymmetry and a changing dipole moment.

What is the Difference Between Linear and Quadratic Stark Effect?


The Stark effect arises due to the interaction between the electric moment of the atom
and the external electric field. There are two types of Stark effect; they are the linear
stark effect and the quadratic stark effect. The key difference between linear and
quadratic stark effect is that the linear Stark effect occurs due to a dipole moment that
arises from a naturally occurring non-symmetric distribution of electrical charge,
whereas the quadratic Stark effect arises due to a dipole moment that is induced by the
external field.

Moreover, the magnitude of the linear Stark effect is comparatively high, while the
magnitude of the quadratic stark effect is comparatively small. In addition to these
differences, the linear Stark effect can be found in hydrogen and hydrogen-like low-
electron atoms, whereas the quadratic stark effect can be observed in many-electron
atoms.

The following infographic summarizes the differences between linear and quadratic stark
effect in tabular form.
Summary – Linear vs Quadratic Stark Effect
The Stark effect arises due to the interaction between the electric moment of the atom
and the external electric field. We can divide it into two categories as linear stark effect
and quadratic stark effect. The key difference between linear and quadratic stark effect is
that the linear Stark effect arises due to a dipole moment occurring from a naturally
occurring non-symmetric distribution of electrical charge, whereas the quadratic Stark
effect arises due to a dipole moment that is induced by the external field.
We have solved the Hydrogen problem with the following Hamiltonian

 
 = −


Now we want to find the correction to that solution if an Electric field is applied to
the atom. We choose the axes so that the Electric field is in the z-direction. The
perturbation is then:

 =
 =  ∙     =     = −    = −  
The first order Stark effect for the ground state of H-atom is zero.

The second order Stark effect for the ground state is non-zero.

The first order Stark effect for the first excited state is non-zero.

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