Dirac Equation and Hydrogen Atom

I. RADIAL KLEIN-GORDON EQUATION AND SPINLESS HYDROGEN ATOM

Now we consider the situation where the scalar potential is spherical symmetric: V (r) = V (r). As in non-relativistic
case, the solution to the Klein Gordon equation can be decomposed to a radial part and a angular part, with the
latter given by the spherical harmonics: ψ(r) = Rl (r)Ylm (θ, φ). The radial Klein-Gordon equation takes the form:
µ ¶ · ¸
1 d 2 dRl l(l + 1) (W − V )2 − m2 c4
− 2 r + − Rl = 0 (1)
r dr dr r2 ~2 c2
This can be compared to the radial Schrödinger equation in non-relativistic QM:
µ ¶ · ¸
1 d 2 dRl l(l + 1) 2m
− 2 r + − 2 (E − V ) Rl = 0
r dr dr r2 ~
We apply this to the specific case of Coulomb potential where
e2
V (r) = −
r
The radial Klein-Gordon equation become:
µ ¶ · ¸
1 d 2 dRl l(l + 1) − α2 W 2 − m2 c4 2(W/c2 ) e2
− 2 r + − − Rl = 0
r dr dr r2 ~2 c2 ~2 r
where α = e2 /(~c) is the fine-structure constant. If we define W/c2 = m0 ,
W2
l0 (l0 + 1) = l(l + 1) − α2 , − m2 c2 = 2m0 W 0
c2
then the above equation can be rewritten as
µ ¶ · 0 0 ¸
1 d dRl l (l + 1) 2m0 W 0 2m0 e2
− 2 r2 + − − Rl = 0
r dr dr r2 ~2 ~2 r
which can be compared to the radial Schrödinger equation for non-relativistic Coulomb potential:
µ ¶ · ¸
1 d dRl l(l + 1) 2mE 2m e2
− 2 r2 + − − Rl = 0
r dr dr r2 ~2 ~2 r
If we make the following correspondence:
l0 ↔ l , W0 ↔ E , m0 ↔ m
then the two equations look identical.
Hence the solution to the radial Klein-Gordon equation is
m0 e4
W0 = − , n 0 = nr + l 0 + 1
2~2 n02
where nr = 0, 1, 2, 3, ... is the radial quantum number.
Converting to non-primed quantities, we have:
mc2
W =r
1+ √α2
nr +1/2+ (l+1/2)2 −α2

Taylor expanding this in powers of α2 , we have

µ ¶
2 Ry Ry α2 1 3
Wnl = mc − 2 − 2 − + ···
n n n l + 1/2 4n
Here n = nr + l + 1 = 1, 2, 3, ... is the principal quantum number. We recognize that the last term is the fine-structure
correction due to the relativistic kinetic energy term.
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II. DIRAC EQUATION FOR SPIN-1/2 PARTICLES

The Klein-Gordon equation does not take spin degrees of freedom into account, hence is valid for spinless particles.
To take care of spin, we have to use the Dirac equation.
The motivation for Dirac is to construct a equation which is first order in both temporal and spatial variables. So
it is conjectured that
p
W = p2 c2 + m2 c4 = c α · p + βmc2
where α and β are dimensionless quantities to be determined. The conditions must satisfied by α and β are obtained
by square the above equation, and can be written as
αx2 = αy2 = αz2 = β 2 = 1 , αi β + βαi = 0 , αi αj + αj αi = 0 (i 6= j)
A consequence of these relation is that Tr(αi )=Tr(β)=0, and eigenvalues of them must be ±1. This means αi and β
must be matrices of even rank. The smallest rank can be shown to be 4. A standard (not unique) representation of
the 4 × 4 Dirac matrices are:
µ ¶ µ ¶
I 0 0 σi
β= , αi =
0 −I σi 0
where I is the 2 × 2 identity matrix and σi are Pauli matrices.
The Dirac equation for free particle can then be written down as
∂ ¡ ¢
i~ψ(r, t) = c α · p + βmc2 ψ(r, t) (2)
∂t
In the presence of scalar and vector potentials, we have
µ ¶
∂ qA ¡ ¢
i~ ψ(r, t) = c α · p − ψ(r, t) + βmc2 + V ψ(r, t) (3)
∂t c

A. Non-Relativistic Limit

Write the wavefunction

µ ¶
φ
ψ=
ϕ
Then Eq. (3) becomes
µ ¶
∂ qA
i~ φ = cσ · p − ϕ + (V + mc2 )φ (4)
∂t c
µ ¶
∂ qA
i~ ϕ = c σ · p − φ + (V − mc2 )ϕ (5)
∂t c
Under the NR limit, i~∂ϕ/∂t ≈ mc2 ϕ, hence
µ ¶
1 qA
ϕ≈ σ· p− φ
2mc c
Inserting this into (4), we have
· µ ¶¸2
∂ 1 qA
i~ φ = σ· p− φ + (V + mc2 )φ
∂t 2m c
µ ¶2
1 qA q~
= p− φ− σ · B φ + (V + mc2 )φ
2m c 2mc
For electron, q = e, then second term at the r.h.s. can be written as −µ · B where
ge
µ = µB S
~
where ge = 2 is the electron g-factor from Dirac theory, S = ~σ/2 is the internal degree of freedom now called spin.
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III. DIRAC EQUATION WITH COULOMB POTENTIAL

To study the hydrogen using Dirac theory, let us consider the time-independent Dirac equation in the presence of
the Coulomb potential:
£ ¤
W − c α · p − βmc2 − V (r) ψ(r) = 0

or
µ ¶µ ¶
W − mc2 − V −c σ · p φ
=0
−c σ · p W + mc2 − V ϕ

A. Non-Relativistic Limit

Again, let us consider the NR limit first. We shall keep terms up to second order in 1/c. Define the kinetic energy
Ek = W − mc2 . In terms of φ,
µ ¶
c 1 Ek − V
ϕ= σ · pφ ≈ 1− σ·p
2mc2 + Ek − V 2mc 2mc2
Eliminating ϕ, we have
µ ¶ µ 2 ¶
σ·p Ek − V p p2 σ · pV σ · p
(Ek − V ) φ = c σ · p ϕ = 1− σ · pφ = − Ek + φ
2m 2mc2 2m 4m2 c2 4m2 c2
or
µ ¶ µ ¶
p2 p2 σ · pV σ · p
Ek 1 + φ= +V + φ (6)
4m2 c2 2m 4m2 c2
Now we should consider how φ is normalized. The normalization condition is
Z Z Z µ ¶
† 2 2 p2
1 = dr ψ ψ = dr (|φ| + |ϕ| ) ≈ dr 1 + |φ|2
4m2 c2
which motivates us to define
r µ ¶
p2 p2
φ̃ = 1+ φ= 1+ φ
4m2 c2 8m2 c2
or
µ ¶
p2
φ= 1− φ̃
8m2 c2
Inserting this into (6), we have
µ ¶µ ¶ µ ¶
p2 p2 p2
Ek 1 + 1 − φ̃ = Ek 1 + φ̃
4m2 c2 8m2 c2 8m2 c2
µ 2 ¶µ ¶
p σ · pV σ · p p2
= +V + 1 − φ̃
2m 4m2 c2 8m2 c2
or
µ ¶µ 2 ¶µ ¶
p2 p σ · pV σ · p p2
Ek φ̃ = 1− + V + 1 − φ̃
8m2 c2 2m 4m2 c2 8m2 c2
· 2 ¸
p p4 1 2 2 σ · pV σ · p
= +V − − (V p + p V ) + φ̃
2m 8m3 c2 8m2 c2 4m2 c2
Using

σ · p V σ · p = V p2 − i~σ · (∇V ) σ · p , p2 V − V p2 = −~2 (∇2 V ) + i2~(∇V ) · p

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and
σ · (∇V ) σ · p = (∇V ) · p + iσ · (∇V × p)
we have
· ¸
p2 p4 ~2 2 ~σ · (∇V × p)
Ek φ̃ = +V − + ∇ V + φ̃
2m 8m3 c2 8m2 c2 4m2 c2

Using V = −e2 /r, hence ∇V = e2 r/r3 and ∇2 V = 4πe2 δ(r), we may identify the last three terms in the square
bracket as the relativistic kinetic energy, Darwin term and the spin-orbit coupling term during the discussion of the
fine-structure of hydrogen atom.

IV. SYMMETRIES OF DIRAC EQUATION

• Charge Conjugation — Like Klein-Gordon equation, Dirac equation also supports negative-energy solutions.
Negative-energy solutions for particle correspond to positive-energy solution for anti-particle. The charge con-
jugation operator Cˆ is defined as
ˆ = U ψ∗
Cψ
where
 
0 0 0 1
0 0 −1 0
U = U −1 = = iβαy
0 −1 0 0
1 0 0 0

Using U α∗ U −1 = α and U βU −1 = −β, one can show that if ψ satisfies

∂ψ £ ¤
i~ = cα · (−i~∇ − qA/c) + βmc2 + qΦ ψ
∂t
ˆ satisfies
then ψc = Cψ
∂ψc £ ¤
i~ = cα · (−i~∇ + qA/c) + βmc2 − qΦ ψc
∂t
• Time Reversal Invariance — Dirac equation is time-reversal invariant, meaning under the time reversal operation
t −→ −t , A −→ −A
the form of the Dirac equation remain unchanged. Define the time reversal operator T̂ as
T̂ ψ = T ψ ∗
where
 
0 i 0 0
 −i 0 0 0
T = T −1 = = −iαx αz
0 0 0 i
0 0 −i 0

Using T α∗ T −1 = −α and T βT −1 = β, one can show that if ψ satisfies

∂ψ £ ¤
i~ = cα · (−i~∇ − qA/c) + βmc2 + qΦ ψ
∂t
then ψT = T̂ ψ satisfies
∂ψT £ ¤
i~ 0
= cα · (−i~∇ − qA/c) + βmc2 + qΦ ψT
∂t
where t0 = −t.
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V. DIRAC HYDROGEN ATOM

Before we solve the Dirac equation with the Coulomb potential, let us first study the angular momentum operators.
One can easily show that neither orbital angular momentum operator L = r × p nor spin angular momentum operator
S = ~σ/2 commutes with Dirac Hamiltonian. However, the total angular momentum operator J = L + S does
commute with H if V = V (r) is a central force potential. Define an operator K̂ 2 as

K̂ 2 = J 2 + ~2 /4 = L2 + ~σ · L + ~2

Obviously, K̂ 2 share the same eigenstates with J 2 and its eigenvalues are

j(j + 1)~2 + ~2 /4 = (j + 1/2)2 ~2

Thus eigenvalues of K̂ must be ±(j + 1/2)~ = −~κ where κ = ±1, ±2, ±3, .... To obtain an expression for K̂ without
the square root, we use

(σ · L)2 = L2 + iσ · (L × L) = L2 − ~σ · L

then

K̂ 2 = (σ · L)2 + 2~σ · L + ~2 = (σ · L + ~)2

or

K̂ = β (σ · L + ~)

One can show that

[K̂, H] = [K̂, J 2 ] = [K̂, Jz ] = 0

Therefore, to solve for the Dirac hydrogen atom, we may seek common eigenstates of H, J 2 , Jz and K̂ which satisfy
the Dirac equation
£ ¤
cα · p + βmc2 + V (r) ψ = W ψ

We shall write the above equation in radial coordinates. Using the identity
∂ i r̂
∇ = r̂(r̂ · ∇) − r̂ × (r̂ × ∇) = r̂ − ×L
∂r ~ r
where r̂ = r/r, we have
∂ 1
α · p = −i~α · r̂ − α · r̂ × L
∂r r
Using (α · A)(α · B) = A · B + iσ · (A × B) and
µ ¶ µ ¶
0 1 0 1
α = σ, σ =α
1 0 1 0

we have
∂ i ∂ i
α · p = −i~α · r̂ + (α · r̂)(σ · L̂) = −i~α · r̂ + (α · r̂)(β K̂ − ~)
∂r r ∂r r
Now we write the wavefunction as
µ m ¶
gκ (r)χκ j
ψ= m
ifκ (r)χ−κj
m
where χκ j are common eigenstates of Jz , K̂ and J 2 with

Jz χm mj
κ = ~mj χκ ,
j
K̂χm mj
κ = −~κχκ
j
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There is no need to specify the value of j since j = |κ| − 1/2. Inserting ψ into the Dirac equation, two coupled
differential equations for gκ and fκ can be found:
µ ¶
∂ 1 κ m m
−c~ + + gκ χ−κj + (W − V + mc2 )fκ χ−κj = 0
∂r r r
µ ¶
∂ 1 κ
c~ + − fκ χm 2
κ + (W − V − mc )gκ χκ
j mj
= 0
∂r r r

The χ’s can now be eliminated. The remaining equation can be solved exactly to give the eigenenergies
" #−1/2
2 α2
W = mc 1+ p
[n − (j + 1/2) + (j + 1/2)2 − α2 ]2

Performing Taylor expansion to order α2 , we have

µ ¶
Ry Ry α2
2 1 3
W = mc − 2 − 2 − + ···
n n n j + 1/2 4n

where the last term is the same as obtained from perturbation approach.