V.

THE HYDROGEN ATOM IN THE

ELECTRIC FIELD – VARIATIONAL
APPROACH

Polarization of an atom or molecule can be calculated by using the finite field

method described on p. 639. Let us apply this method to the hydrogen atom. Its
polarizability was already calculated using a simple version of perturbation theory
(p. 636). This time we will use the variational method.
The Hamiltonian for the isolated hydrogen atom (within the Born–Oppenhei-
mer approximation) reads as

1 1
Ĥ (0) = − e − 
2 r

where the first term is the electronic kinetic energy operator, and the second its
Coulomb interaction energy with the nucleus (proton–electron distance is denoted
by r). The atom is in a homogeneous electric field E = (0 0 E) with E > 0 and as
in perturbation theory (p. 636), the total Hamiltonian has the form

Ĥ = Ĥ (0) + V

with V = zE, where z denotes the coordinate of the electron and the proton is at
the origin (the derivation of the formula is given on p. 636, the exchange of z to x
does not matter).
The variational wave function ψ is proposed in the form

ψ = χ1 + cχ2  (V.1)

where χ1 = √1
π
exp(−r) is the 1s orbital of the hydrogen atom (ground state) and
χ2 is the normalized1 p-type orbital

χ2 = Nz exp(−ζr)
1 N can be easily calculated from the normalization condition
  ∞  π  2π
 2
1 = N2 z exp(−ζr) dV = N 2 dr r 4 exp(−2ζr) dθ sin θ cos2 θ dφ
0 0 0
2 π
= N 2 4! (2ζ)−5 2π = N 2 
3 ζ5
!
5
This gives N = ζπ .

1029
1030 V. THE HYDROGEN ATOM IN THE ELECTRIC FIELD – VARIATIONAL APPROACH

There are two variational parameters c and ζ. Let us assume for a while that
we have fixed the value of ζ, so the only variational parameter is c. The wave
function ψ is a linear combination of two expansion functions (“two-state model”):
χ1 and χ2 . Therefore, optimal energy follows from the Ritz method, according to
case III of Appendix D on p. 948:

E = Ear ± 2 + h2  (V.2)

where arithmetic mean energy Ear ≡ H11 +H

2
22
, while ≡ H11 −H
2
22
and h ≡ H12 =
H21 with
     
Hij ≡ χi Ĥχj = χi Ĥ (0) χj + χi |V χj 

Let us calculate all the ingredients of the energy given by (V.2).

First, let us note that H11 ≡ χ1 |Ĥ (0) χ1  = − 12 a.u., since χ1 is the ground state
of the isolated hydrogen atom (p. 178), and V11 = χ1 |V χ1  = 0, because the inte-
grand is antisymmetric with respect to z → −z.
(0)
Now let us calculate H22 = H22 + V22 . Note that V22 = 0, for the same reason
as V11 . We have
  
1 1
(0)
H22 = − χ2 | e χ2  − χ2  χ2 
2 r
The second integral is
    ∞  π  2π
1

χ 2  χ2 = N 2 3
dr r exp(−2ζr) 2
dθ sin θ cos θ dφ
r 0 0 0

ζ5 2 1
= · 3!(2ζ)−4 · · 2π = ζ
π 3 2
where the dots separate the values of the corresponding integrals.2 In Appendix R,
the reader will find the main ingredients needed to calculate the first integral of
(0)
H22 :
 
 1 ∂ ∂ 1 ∂ ∂
χ2 | e χ2  = N r cos θ exp(−ζr) 2 r 2 + 2
2
sin θ
r ∂r ∂r r sin θ ∂θ ∂θ
2  
1 ∂
+ 2 ∂φ2
r cos θ exp(−ζr)
2
r sin θ
$    %
r cos θ exp(−ζr) cos θ r12 ∂r ∂ 2
r exp(−ζr) − ζr 3 exp(−ζr) +
=N 2
  
r cos θ exp(−ζr) (−2rcos2
θ)
r exp(−ζr) + 0
    
 2
2 
= N r cos θ exp(−ζr) cos θ − ζ − 3ζ + ζ r exp(−ζr) 2
r
2 Note that, in spherical coordinates, the volume element dV = r 2 sin θ dr dθ dφ. In derivations of this

Appendix (and not only) we often use the equality 0∞ dx xn exp(−αr) = n!α−(n+1) .
V. THE HYDROGEN ATOM IN THE ELECTRIC FIELD – VARIATIONAL APPROACH 1031
  
 (−2 cos θ)
+ r cos θ exp(−ζr) exp(−ζr)
r
  
ζ5 2 2·2 4ζ · 3! ζ 2 · 4! 2 · 2!
= · 2π − + −
π 3 (2ζ)3 (2ζ)4 (2ζ)5 (2ζ)3
= −ζ 2 

Thus, we obtain H22 = 12 ζ 2 − 12 ζ. This formula looks good, since for χ2 = 2pz ,
i.e. for ζ = 12 we get correctly (see p. 178) H22 = E2p = − 18 a.u., the energy of
orbital 2p.
Let us turn to the non-diagonal matrix element of the Hamiltonian: H12 =
(0) (0)
H12 + V12 . Note, that H12 = 0, because χ1 is an eigenfunction of Ĥ (0) and
χ1 |χ2  = 0. Thus,
  
 1
h = NE r cos θ exp(−ζ)r cos θ √ exp(−r)
π
 ∞   2π
1   π
= NE √ dr r 4 exp −(ζ + 1)r dθ sin θ cos2 θ dφ
π 0 0 0

ζ5 2 ζ5
=E · 4!(ζ + 1)−5 · · 2π = 32 E
π 3 (ζ + 1)5
Now we can write eq. (V.2) as a function of ζ:
&
 10
1 2  1 2 2 2
E = ζ −ζ −1 − ζ − ζ + 1 + ζ5 E 2 (V.3)
4 16 ζ+1
We would like to expand this expression in a power series of E to highlight
the coefficient at E 2 , because this coefficient is related to the polarizability. The
expansion gives (in a.u.)
1 2  1  1 1 1
E≈ ζ − ζ − 1 − ζ 2 − ζ + 1 − αzz E 2 + · · · = − − αzz E 2 + · · · 
4 4 2 2 2
where, according to eq. (12.24), the polarizability (in a.u.) reads as
 10
ζ5 2
αzz = 4 · 2  (V.4)
|ζ − ζ + 1| ζ + 1
Several numerical values of αzz calculated using (V.3) and (V.4), are given on
p. 639. They may be compared with the exact result αzz = 45 a.u.