258 Chapter 7 The Hydrogen Atom

Phipps and Taylor found only two distinct lines, as did Stern we just calculated! The total separation of the two lines (one
and Gerlach for silver atoms, and the separation of the lines deected up and one down) was 0.38 mm. The mystery re-
from the central ray with no magnetic eld was 0.19 mm as mained as to why there were only two lines.

7.5 Intrinsic Spin

It was clear by the early 1920s that there was a problem with space quantization
and the number of lines observed in the Stern-Gerlach experiment. Wolfgang
Pauli was the rst to suggest that a fourth quantum number (after n, /, m /) as-
signed to the electron might explain the anomalous optical spectra discussed in
Section 7.4. His reasoning for four quantum numbers was based on relativity, in
which there are four coordinatesthree space and one time. The physical
signicance of this fourth quantum number was not made clear.
In 1925 Samuel Goudsmit and George Uhlenbeck, two young physics gradu-
ate students in Holland, proposed that the electron must have an intrinsic angular
momentum and therefore a magnetic moment (because the electron is charged).
Classically, this corresponds in the planetary model to the fact that the Earth
rotates on its own axis as it orbits the sun. However, this simple classical picture
runs into serious difculties when applied to the spinning charged electron. In
order to achieve the angular momentum needed, Paul Ehrenfest showed that
the surface of the spinning electron (or electron cloud) would have to be mov-
ing at a velocity greater than the speed of light! If such an intrinsic angular
momentum exists, we must regard it as a purely quantum-mechanical result (see
Problems 44 and 45).
To explain experimental data, Goudsmit and Uhlenbeck proposed that the
Intrinsic spin electron must have an intrinsic spin quantum number s 1/2. The spinning
quantum number electron reacts similarly to the orbiting electron in a magnetic eld. Therefore,
we should try to nd quantities analogous to the angular momentum variable L,
Lz , /, and m /. By analogy, there will be 2s 1 2(1/2) 1 2 components of
Magnetic spin the spin angular momentum vector S . Thus the magnetic spin quantum number
quantum number ms has only two values, ms 1/2. The electrons spin will be oriented either
up or down in a magnetic eld (see Figure 7.9), and the electron can never
be spinning with its magnetic moment ms exactly along the z axis (the direction of
the external magnetic eld B ).
For each atomic state described by the three quantum numbers (n, /, m /)
discussed previously, there are now two distinct states, one with ms 1/2 and one
with ms 1/2. These states are degenerate in energy unless the atom is in an
external magnetic eld. In a magnetic eld these states will have different energies
due to an energy separation like that of Equation (7.33). We say the splitting of
these energy levels by the magnetic eld has removed the energy degeneracy.
z

1
ms
2
Figure 7.9 (a) A purely classical 3
schematic of the intrinsic spin S
w4
angular momentum, S , of a spin-
ning electron. (b) The quantiza-
S
tion of S , which can have only two
positions in space relative to z 1
m
s 2
(direction of external magnetic
eld). The z component of S is
Sz U/2. (a) (b)
 7.5 Intrinsic Spin 259

The intrinsic spin angular momentum vector S has a magnitude of S Intrinsic spin angular
2s 1s 12 U 23 /4 U . The magnetic moment is ms 1e/m 2 S , or 2mBS/ U . momentum vector
The fact that the coefcient of S/ U is 2mB rather than mB as with the orbital
angular momentum L is a consequence of the theory of relativity (Dirac equa-
tion), and we will not pursue the matter further here. This numerical factor re-
lating the magnetic moment to each angular momentum vector is called the
gyromagnetic ratio. It is designated by the letter g with the appropriate subscript
(/ or s), so that g / 1 and gs 2. In terms of the gyromagnetic ratios, then,

g /mBL mB L
m/ (7.34a)
U U
Gyromagnetic ratios
gs mBS mB S
ms 2 (7.34b)
U U

The z component of S is Sz ms U U /2.

We can now understand why the experiment of Stern and Gerlach produced
only two distinct lines. If the atoms were in a state with / 0, there would be no B
splitting due to m /. However, there is still space quantization due to the intrinsic
spin that would be affected by the inhomogeneous magnetic eld. The same ar-
guments used previously for m / (we now use the subscript / to indicate the mag-
netic moment due to the orbiting electron and the subscript s to indicate the e
magnetic moment due to intrinsic spin) can now be applied to m s , and the poten-
p
tial energy, Equation (7.27), becomes
e
B Vs# m BS # B (7.35)
m

If we look at the hydrogen atom in the frame of the orbiting electron, we have
the classical result shown in Figure 7.10. This classical picture indicates that the
B
orbiting proton creates a magnetic eld at the position of the electron. There-
fore, even without an external magnetic eld, the electron will feel the effects of
an internal magnetic eld, and Equation (7.35) predicts an energy difference Figure 7.10 The hydrogen
depending on whether the electrons spin is up or down. Many levels are effec- atom in the frame of reference of
tively split into two different states called doublets. the electron. In this case, the or-
The relativistic quantum theory proposed by P. A. M. Dirac in 1928 showed biting proton creates a magnetic
that the intrinsic spin of the electron required a fourth quantum number as a eld at the position of the
consequence of the theory of relativity. electron.

EXAMPLE 7.9
How many distinctly different states (and therefore wave Solution For the 4d level (n 4, / 2) there are 2/ 1
functions) exist for the 4d level of atomic hydrogen? 5 different values of m /. For each of these values of m / ( 2,
1, 0, 1, 2), there are two ms states ( 1/2). Therefore there
Strategy As shown in Example 7.4, the degeneracy of are 10 different states for a 4d level of atomic hydrogen.
each level is n2, before spin is taken into account. In the
absence of an applied magnetic eld, the fourth quantum
number for intrinsic spin makes the degeneracy of the nth
quantum level 2n 2. The number of states has increased
signicantly.