The Zeeman effect (; in Dutch; Flemish pronounced as /ˈzeːmɑn/) is the effect of splitting of a spectral line into several components in the presence of a static magnetic field. It is named after the Dutch physicist Pieter Zeeman, who discovered it in 1896 and received a Nobel prize for this discovery. It is analogous to the Stark effect, the splitting of a spectral line into several components in the presence of an electric field. Also similar to the Stark effect, transitions between different components have, in general, different intensities, with some being entirely forbidden (in the dipole approximation), as governed by the selection rules.
Since the distance between the Zeeman sub-levels is a function of magnetic field strength, this effect can be used to measure magnetic field strength, e.g. that of the Sun and other stars or in laboratory plasmas.
In 1896 Zeeman learned that his laboratory had one of Henry Augustus Rowland's highest resolving Rowland grating, an imaging spectrographic mirror. Zeeman had read James Clerk Maxwell's article in Encyclopædia Britannica describing Michael Faraday's failed attempts to influence light with magnetism. Zeeman wondered if the new spectrographic techniques could succeed where early efforts had not.
When illuminated by a slit shaped source, the grating produces a long array of slit images corresponding to different wavelengths. Zeeman placed a piece of asbestos soaked in salt water into a Bunsen burner flame at the source of the grating: he could easily see two lines for sodium light emission. Energizing a 10 kilogauss magnet around the flame he observed a slight broadening of the sodium images.
When Zeeman switched to cadmium at the source he observed the images split when the magnet was energized. These splitting could be analyzed with Hendrik Lorentz's then new electron theory. In retrospect we now know that the magnetic effects on sodium require quantum mechanical treatment.[1] Zeeman and Lorentz were awarded the 1902 Nobel prize; in his acceptance speech Zeeman explained his apparatus and showed slides of the spectrographic images.[2]
Historically, one distinguishes between the normal and an anomalous Zeeman effect (discovered by Thomas Preston in Dublin, Ireland[3]). The anomalous effect appears on transitions where the net spin of the electrons is non-zero. It was called "anomalous" because the electron spin had not yet been discovered, and so there was no good explanation for it at the time that Zeeman observed the effect. Wolfgang Pauli recalled that when asked by a colleague as to why he looked unhappy, he replied, "How can one look happy when he is thinking about the anomalous Zeeman effect?"[4]
At higher magnetic field strength the effect ceases to be linear. At even higher field strengths, comparable to the strength of the atom's internal field, the electron coupling is disturbed and the spectral lines rearrange. This is called the Paschen–Back effect.
In the modern scientific literature, these terms are rarely used, with a tendency to use just the "Zeeman effect".Another rarely used obscure term is inverse Zeeman effect,[5] referring to the Zeeman effect in an absorption spectral line.
A similar effect, splitting of the nuclear energy levels in the presence of a magnetic field, is referred to as the nuclear Zeeman effect.[6]
The total Hamiltonian of an atom in a magnetic field is
H=H0+V\rm,
where
H0
V\rm
V\rm=-\vec{\mu} ⋅ \vec{B},
where
\vec{\mu}
\vec{\mu} ≈ -
\mu\rmg\vec{J | |
where
\mu\rm
\vec{J}
g
\vecL
\vecS
\vec{\mu}=-
\mu\rm(gl\vec{L | |
+ |
gs\vec{S})}{\hbar},
where
gl=1
gs ≈ 2.0023193
g\vec{J}=\left\langle\sumi(gl\vec{li}+gs\vec{si})\right\rangle=\left\langle(gl\vec{L}+gs\vec{S})\right\rangle,
where
\vec{L}
\vec{S}
If the interaction term
VM
VM
H0
H0
If the spin–orbit interaction dominates over the effect of the external magnetic field,
\vecL
\vecS
\vecJ=\vecL+\vecS
\vecJ
\vecJ
\vecS\rm=
(\vecS ⋅ \vecJ) | |
J2 |
\vecJ
and for the (time-)"averaged" orbital vector:
\vecL\rm=
(\vecL ⋅ \vecJ) | |
J2 |
\vecJ.
Thus,
\langleV\rm\rangle=
\mu\rm | |
\hbar |
\vec
J\left(g | ||||
|
+
g | ||||
|
\right) ⋅ \vecB.
Using
\vecL=\vecJ-\vecS
\vecS ⋅ \vecJ=
1 | |
2 |
(J2+S2-L2)=
\hbar2 | |
2 |
[j(j+1)-l(l+1)+s(s+1)],
\vecS=\vecJ-\vecL
\vecL ⋅ \vecJ=
1 | |
2 |
(J2-S2+L2)=
\hbar2 | |
2 |
[j(j+1)+l(l+1)-s(s+1)].
Combining everything and taking
Jz=\hbarmj
\begin{align} V\rm&=\mu\rmBmj\left[
g | ||||
|
+
g | ||||
|
\right]\\ &=\mu\rmBmj\left[1+
(g | ||||
|
\right], \\ &=\mu\rmBmjgj \end{align}
where the quantity in square brackets is the Landé g-factor gJ of the atom (
gL=1
gS ≈ 2
mj
s=1/2
j=l\pms
gj=1\pm
gS-1 | |
2l+1 |
Taking
Vm
(1) | |
\begin{align} E | |
\rmZ |
=\langlenljmj|
' | |
H | |
\rmZ |
|nljmj\rangle=\langleVM\rangle\Psi=\mu\rmgJB\rmmj \end{align}
The Lyman-alpha transition in hydrogen in the presence of the spin–orbit interaction involves the transitions
2P1/2\to1S1/2
2P3/2\to1S1/2.
In the presence of an external magnetic field, the weak-field Zeeman effect splits the 1S1/2 and 2P1/2 levels into 2 states each (
mj=1/2,-1/2
mj=3/2,1/2,-1/2,-3/2
gJ=2
1S1/2
gJ=2/3
2P1/2
gJ=4/3
2P3/2
Note in particular that the size of the energy splitting is different for the different orbitals, because the gJ values are different. On the left, fine structure splitting is depicted. This splitting occurs even in the absence of a magnetic field, as it is due to spin–orbit coupling. Depicted on the right is the additional Zeeman splitting, which occurs in the presence of magnetic fields.
\left | \frac, \pm\frac \right\rangle | \left | \frac, \pm\frac \right\rangle |
\mu\rmB | ||||
\left | \frac, \pm\frac \right\rangle | \left | \frac, \mp\frac \right\rangle |
\mu\rmB | ||||
\left | \frac, \pm\frac \right\rangle | \left | \frac, \pm\frac \right\rangle | \pm\mu\rmB | ||||
\left | \frac, \pm\frac \right\rangle | \left | \frac, \pm\frac \right\rangle |
\mu\rmB | ||||
\left | \frac, \pm\frac \right\rangle | \left | \frac, \mp\frac \right\rangle |
\mu\rmB |
The Paschen–Back effect is the splitting of atomic energy levels in the presence of a strong magnetic field. This occurs when an external magnetic field is sufficiently strong to disrupt the coupling between orbital (
\vec{L}
\vec{S}
s=0
When the magnetic-field perturbation significantly exceeds the spin–orbit interaction, one can safely assume
[H0,S]=0
Lz
Sz
|\psi\rangle
Ez=\left\langle\psi\left|H0+
Bz\mu\rm | |
\hbar |
(Lz+gsSz)\right|\psi\right\rangle=E0+Bz\mu\rm(ml+gsms).
The above may be read as implying that the LS-coupling is completely broken by the external field. However
ml
ms
\Deltas=0,\Deltams=0,\Deltal=\pm1,\Deltaml=0,\pm1
\Deltaml=0,\pm1
\DeltaE=B\mu\rm\Deltaml
More precisely, if
s\ne0
Ez+fs=Ez+
mec2\alpha4 | |
2n3 |
\left\{
3 | |
4n |
-\left[
l(l+1)-mlms | |
l(l+1/2)(l+1) |
\right]\right\}.
In this example, the fine-structure corrections are ignored.
\left | 1, \frac\right\rangle | +2\mu\rmBz | \left | 0, \frac\right\rangle | +\mu\rmBz | |
\left | 0, \frac\right\rangle | +\mu\rmBz | \left | 0, \frac\right\rangle | +\mu\rmBz | |
\left | 1, -\frac\right\rangle | 0 | \left | 0, -\frac\right\rangle | -\mu\rmBz | |
\left | -1, \frac\right\rangle | 0 | \left | 0, \frac\right\rangle | +\mu\rmBz | |
\left | 0, -\frac\right\rangle | -\mu\rmBz | \left | 0, -\frac\right\rangle | -\mu\rmBz | |
\left | -1, -\frac\right\rangle | -2\mu\rmBz | \left | 0, -\frac\right\rangle | -\mu\rmBz |
In the magnetic dipole approximation, the Hamiltonian which includes both the hyperfine and Zeeman interactions is
H=hA\vecI ⋅ \vecJ-\vec\mu ⋅ \vecB
H=hA\vecI ⋅ \vecJ+(\mu\rmgJ\vecJ+\mu\rmgI\vecI) ⋅ \vec{\rmB}
A
\mu\rm
\mu\rm
\vecJ
\vecI
gJ
In the case of weak magnetic fields, the Zeeman interaction can be treated as a perturbation to the
|F,mf\rangle
|I,J,mI,mJ\rangle
|mI,mJ\rangle
I
J
|F,mF\rangle
|mI,mJ\rangle
J=1/2
L=0
J=1/2
We now utilize quantum mechanical ladder operators, which are defined for a general angular momentum operator
L
L\pm\equivLx\pmiLy
These ladder operators have the property
L\pm|L,mL\rangle=\sqrt{(L\mpmL)(L\pmmL+1)}|L,mL\pm1\rangle
as long as
mL
{-L,......,L}
J\pm
I\pm
H=hAIzJz+
hA | |
2 |
(J+I-+J-I+)+\mu\rmBgJJz+\mu\rmBgIIz
We can now see that at all times, the total angular momentum projection
mF=mJ+mI
Jz
Iz
mJ
mI
J+I-
J-I+
mJ
mI
J=1/2
mJ
\pm1/2
mF
|\pm\rangle\equiv|mJ=\pm1/2,mI=mF\mp1/2\rangle
This pair of states is a two-level quantum mechanical system. Now we can determine the matrix elements of the Hamiltonian:
\langle\pm|H|\pm\rangle=-
1 | |
4 |
hA+\mu\rmBgImF\pm
1 | |
2 |
(hAmF+\mu\rmBgJ-\mu\rmBgI))
\langle\pm|H|\mp\rangle=
1 | |
2 |
hA\sqrt{(I+1/2)2-
2} | |
m | |
F |
Solving for the eigenvalues of this matrix – as can be done by hand (see two-level quantum mechanical system), or more easily, with a computer algebra system – we arrive at the energy shifts:
\DeltaEF=I\pm1/2=-
h\DeltaW | |
2(2I+1) |
+\mu\rmgImFB\pm
h\DeltaW | |
2 |
\sqrt{1+
2mFx | |
I+1/2 |
+x2}
x\equiv
B(\mu\rmgJ-\mu\rmgI) | |
h\DeltaW |
\DeltaW=A\left(I+
1 | |
2 |
\right)
where
\DeltaW
B
x
mF=\pm(I+1/2)
+ | h\DeltaW |
2 |
(1\pmx)
s
J=1/2
Note that index
F
\DeltaEF=I\pm1/2
B=0
F
mF
|F=I+1/2,mF=\pmF\rangle
George Ellery Hale was the first to notice the Zeeman effect in the solar spectra, indicating the existence of strong magnetic fields in sunspots. Such fields can be quite high, on the order of 0.1 tesla or higher. Today, the Zeeman effect is used to produce magnetograms showing the variation of magnetic field on the Sun.
The Zeeman effect is utilized in many laser cooling applications such as a magneto-optical trap and the Zeeman slower.
Zeeman-energy mediated coupling of spin and orbital motionsis used in spintronics for controlling electron spins in quantum dots through electric dipole spin resonance.[11]
Old high-precision frequency standards, i.e. hyperfine structure transition-based atomic clocks, may require periodic fine-tuning due to exposure to magnetic fields. This is carried out by measuring the Zeeman effect on specific hyperfine structure transition levels of the source element (cesium) and applying a uniformly precise, low-strength magnetic field to said source, in a process known as degaussing.[12]
The Zeeman effect may also be utilized to improve accuracy in atomic absorption spectroscopy.
A theory about the magnetic sense of birds assumes that a protein in the retina is changed due to the Zeeman effect.[13]
The nuclear Zeeman effect is important in such applications as nuclear magnetic resonance spectroscopy, magnetic resonance imaging (MRI), and Mössbauer spectroscopy.
The electron spin resonance spectroscopy is based on the Zeeman effect.
The Zeeman effect can be demonstrated by placing a sodium vapor source in a powerful electromagnet and viewing a sodium vapor lamp through the magnet opening (see diagram). With magnet off, the sodium vapor source will block the lamp light; when the magnet is turned on the lamp light will be visible through the vapor.
The sodium vapor can be created by sealing sodium metal in an evacuated glass tube and heating it while the tube is in the magnet.
Alternatively, salt (sodium chloride) on a ceramic stick can be placed in the flame of Bunsen burner as the sodium vapor source. When the magnetic field is energized, the lamp image will be brighter. However, the magnetic field also affects the flame, making the observation depend upon more than just the Zeeman effect. These issues also plagued Zeeman's original work; he devoted considerable effort to ensure his observations were truly an effect of magnetism on light emission.[14]
When salt is added to the Bunsen burner, it dissociates to give sodium and chloride. The sodium atoms get excited due to photons from the sodium vapour lamp, with electrons excited from 3s to 3p states, absorbing light in the process. The sodium vapour lamp emits light at 589nm, which has precisely the energy to excite an electron of a sodium atom. If it was an atom of another element, like chlorine, shadow will not be formed.[15] When a magnetic field is applied, due to the Zeeman effect the spectral line of sodium gets split into several components. This means the energy difference between the 3s and 3p atomic orbitals will change. As the sodium vapour lamp don't precisely deliver the right frequency any more, light doesn't get absorbed and passes through, resulting in the shadow dimming. As the magnetic field strength is increased, the shift in the spectral lines increases and lamp light is transmitted.