A deeper look 3   Separation of variables

A number of physical systems can be regarded intuitively 1 d 2Φ sinθ d dΘ

as combinations of motion of different kinds, such as + sinθ = −ε sin 2θ
Φ dφ 2 Θ dθ dθ
motion through space and an internal motion. These intu-
itive notions can be justified mathematically and typically and, after minor rearrangement,
result in the separate, but sometimes linked, equations for
each type of motion. 1 d 2Φ sinθ d dΘ
+ sinθ + ε sin 2θ = 0 (2)
Φ dφ 2 Θ dθ dθ

(a) Particle on a sphere Step 2  Verify that the expression is separable

This section shows how to separate the Schrödinger The first term on the left depends only on ϕ and the
equation for a particle able to move on the surface of a remaining two terms depend only on θ. Each term is
sphere into separate equations for the azimuth ϕ and the therefore equal to a constant. Thus, if the first term is set
colatitude θ. equal to the constant −ml2 , the separated equations are
The Schrödinger equation for the motion of a particle of
1 d 2Φ sinθ d dΘ
mass m on the surface of a sphere is = −ml2 sinθ + ε sin 2θ = ml2
Φ dφ 2 Θ dθ dθ
2 2
− ∇ ψ = Eψ
2m (b) Hydrogenic atoms
The laplacian is The goal of this calculation is to show that the full
1 ∂2
1 Schrödinger equation for a hydrogenic atom separates into
∇2 = r + Λ2  (1a) two equations, one for the motion of the atom as a whole
r ∂r 2 r 2
through space and the other for the motion of the electron
and the legendrian is relative to the nucleus.
1 ∂2 1 ∂ ∂ Step 1 Separate the internal motion from the external
Λ2 = 2 + sinθ
sin θ ∂φ
2
sin θ ∂θ ∂θ motion
Consider a one-dimensional system (which is easily gener-
Because r is constant, the part of the laplacian that
alized to three dimensions) in which the potential energy
involves differentiation with respect to r can be discarded,
depends only on the separation of the two particles. The
and the equation then becomes
total energy is
2
− Λ2ψ = Eψ  (1b) p12 p2
2mr 2 E= + 2 + V ( x1 − x 2 ) (3)
2m1 2m2
In terms of the moment of inertia, I = mr2, this expression where p1 = m1 (dx1 /dt ) and p2 = m2 (dx 2 /dt ). The centre of
becomes mass (Fig. 1) is located at
2 IE m1 m
Λ2ψ = −εψ ε=  (1c) X= x + 2x m = m1 + m2  (4a)
2 m 1 m 2
and the separation of the particles is x = x1 − x2. It follows
Step 1  Insert the factorized possible solution
that
Insert ψ = ΘΦ and obtain
m2 m1
x1 = X + x x2 = X − x (4b)
1 ∂ 2 (ΘΦ ) 1 ∂ ∂(ΘΦ ) m m
Λ ΘΦ = 2
2
+ sinθ = −εΘΦ
sin θ ∂φ 2 sinθ ∂θ ∂θ
m1 m2
Now use the fact that Θ and Φ are each functions of
one variable, so the partial derivatives become complete
derivatives:
Θ d 2Φ Φ d dΘ x
+ sinθ = −εΘΦ x1 X x2
sin 2θ dφ 2 sinθ dθ dθ
Figure 1  The coordinates used for discussing the separation
Division through by ΘΦ and multiplication by sin 2θ of the relative motion of two particles from the motion of
gives their centre of mass (the black dot).
2 A deeper look 3  Separation of variables

The linear momenta of the particles can now be expressed where the partial derivatives with respect to r have been
in terms of the rates of change of x and X: replaced by complete derivatives because R depends only
on r. Multiply through by r2/RY and obtain
dx1 dX m1m2 dx
p1 = m1 = m1 +
dt dt m dt 2  2 d2R dR  2 2
2
− r + 2r + Vr − Λ Y = Er 2  (9d)
 (5) 2 µ R  dr 2 dr  2 µY
dx 2 dX m1m2 dx
p2 = m2 = m2 −
dt dt m dt
The functions Y satisfy the equation
Then, with
Λ2Y = −l ( l +1)Y  (10)
1 1 1 mm mm
= + , or µ = 1 2 = 1 2  (6)
µ m1 m2 m1 + m2 m so eqn 9d becomes
Independent of θ, ϕ
it follows that because the Ys cancel

2  2 d2R dR  2  2l(l +1)
p12 p2
2
 dX  1  dx 
2
−  r 2 + 2r  + Vr + Y = Er 2  (9e)
+ 2 = 12 m  + µ  (7) 2 µ R  dr dr  2 µY
2m1 2m2  dt  2  dt 

By writing P = m(d X /dt ) for the linear momentum of the Step 3  Write an expression for the radial contribution
system as a whole and p = µ(d x /dt ), it follows that
Continuing the argument from step 2, rewrite eqn 9e
P p2 2 by dividing both sides by r2 and multiplying by R. The
E= + + V ( x ) (8a) result is
2m 2 µ

The corresponding hamiltonian (generalized to three  2  d 2 R 2 dR   2l(l +1)

−  2 +  + VR + R = ER  (11a)
dimensions) is therefore 2 µ  dr r dr  2 µr 2
2 2 2
Hˆ = − ∇ c.m. − ∇ 2 + V (r )  (8b) Because for a hydrogenic atom V = − Ze 2 /4π ε 0r , write
2m 2µ
Ze 2 l ( l +1)  2
where the first term differentiates with respect to the Veff = − +  (11b)
4π ε 0 r 2 µr 2
centre of mass coordinates and the second with respect to
the relative coordinates.
and the equation becomes
Now write the overall wavefunction as the product
ψtotal(X,x) = ψc.m.(X)ψ(x), where the first factor is a func-  2  d 2 R 2 dR 
− + + V R = ER  (12)
tion of only the centre of mass coordinates and the second 2 µ  dr 2 r dr  eff
is a function of only the relative coordinates. The overall
Schrödinger equation, Ĥ ψtotal = Etotalψtotal, then separates, This expression, the radial wave equation, has the form
with Etotal = Ec.m. + E. of a Schrödinger equation. It describes the motion of a
Step 2 Write the Schrödinger equation associated with particle of mass µ in the region 0 ≤ r < ∞ where the poten-
internal motion tial energy is Veff. Solving this equation gives the radial
wavefunctions R.
The Schrödinger equation for the internal motion of a
hydrogenic atom is
(c) Harmonic oscillator
2
 2   ∂
2 2
2 ∂ 1 2 The goal of this calculation is to show that the full
− ∇ ψ + Vψ = − + + Λ ψ + Vψ = Eψ
2µ 2 µ  ∂r 2 r ∂r r 2  Schrödinger equation for the vibration of a diatomic mol-
 (9a) ecule (with a harmonic potential) separates into two equa-
tions, one for the motion of the molecule through space
Attempt a solution of the form ψ = RY , where R depends and the other for the relative motion of the atoms.
only on the radius and Y depends only on the angular
coordinates. Then Step 1  Write the Schrödinger equation for the molecule
The total energy of a two atoms of masses m1 and m2 free to
 2  ∂2 2 ∂ 1 2  move in one dimension and subject to a potential energy
− + + Λ RY + VRY = ERY  (9b)
2 µ  ∂r 2 r ∂r r 2  that depends on their separation is
and therefore
p12 p2
Etotal = + 2 + V ( x1 − x 2 ) (13)
2m1 2m2
 2  d 2 R 2Y dR R 2 
− Y + + Λ Y  + VRY = ERY  (9c)
2 µ  dr 2 r dr r 2 
3 A deeper look 3  Separation of variables

As in Part (b), the linear momenta of the particles are Step 2  Show that the equation separates
expressed in terms of the rates of change of the separation Write the overall wavefunction as the product ψtotal(X,x) =
x and the location of the centre of mass X: ψc.m.(X)ψ(x), where ψc.m.(X) is a function of only the
centre of mass coordinate and ψ(x) is a function of only
dx1 dX m1m2 dx
p1 = m1 = m1 + the separation of the atoms. The overall Schrödinger equa-
dt dt m dt
(14) tion then becomes
dx dX m1m2 dx
p2 = m2 2 = m2 − 
dt dt m dt  2 ∂ 2ψ c.m. ( X )ψ ( x )  2 ∂ 2ψ c.m. ( X )ψ ( x )
− − 
2m ∂X 2 2µ ∂x 2 (19a)
Then, with
+ kf x ψ c.m. ( X )ψ ( x ) = Etotalψ c.m. ( X )ψ ( x )
1
2
2

1 1 1 mm mm
= + , or µ = 1 2 = 1 2  (15)
µ m1 m2 m1 + m2 m and therefore
it follows that 2 d 2ψ c.m. ( X )  2 d 2ψ ( x )
− ψ (x ) − ψ ( X )
2 2
2m dX 2 2 µ c.m. dx 2  (19b)
p12 p2  dX  1  dx  
+ 2 = 12 m  + µ (16) + 12 kf x 2ψ c.m. ( X )ψ ( x ) = Etotalψ c.m. ( X )ψ (x )
2m1 2m2  dt  2  dt 

By writing P = m(dX /dt ) for the linear momentum of the After division by ψtotal(X,x) = ψc.m.( X )ψ ( x ), this equation
molecule as a whole and p = µ(dx /dt ), the total energy becomes
becomes
Depends on X Depends on x
2 2  
P p 2 d 2ψ c.m. ( X )  2 d 2ψ ( x ) 1
Etotal = + + V ( x ) (17a) − − + 2 kf x 2 = Etotal
2m 2 µ 2mψ c.m. ( X ) 2 µψ ( x ) dx 2
dX 2
For a harmonic oscillator  (19c)

V ( x ) = 12 kf x 2  (17b) Therefore, by the usual separation of variables argument, each

term under the braces is equal to a constant, and their sum,
Ec.m. + E, is the total energy Etotal. The contribution that depends
At this stage, therefore, the hamiltonian is
only on the separation x, after minor rearrangement, is
 2 ∂2  2 ∂2 1
Hˆ = − − + k x2  (18a)  2 d 2ψ ( x ) 1
2m ∂X 2 2 µ ∂x 2 2 f − + 2 kf x 2ψ ( x ) = Eψ ( x )  (20)
2 µ dx 2
and the Schrödinger equation is
which is the equation for a particle of effective mass μ in a
 ∂ ψ total ( X , x )  ∂ ψ total ( X , x ) 1
2 2 2 2
parabolic potential energy. The separation is independent
− − + 2 kf x 2ψ total ( X , x ) of whether the potential energy is parabolic: the argument
2m ∂X 2 2µ ∂x 2
 = Etotalψ total ( X , x ) (18b) depends only on whether the potential energy depends on
the separation of the two atoms; it therefore also applies to
anharmonic oscillation.