Introductory Atomic and Molecular Physics

Chapter 4: One-electron atoms

L. F. Errea, L. Méndez, I. Rabadán

October 26, 2023

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 1 / 24

Outline

1 Central potentials

2 One-electron atoms

The Schrödinger equation for one-electron atoms

Energy levels

Radial wavefunctions

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 2 / 24

Central forces

We consider a spherically symmetric potential V (r ). In polar coordinates:

~2 2
H = − ∇ + V (r )
2m 
~2 1 ∂ ∂2
    
2 ∂ 1 ∂ ∂ 1
= − r + sin θ + + V (r )
2m r 2 ∂r ∂r r 2 sin θ ∂θ ∂θ r 2 sin2 θ ∂φ2
" #
~2 1 ∂ L2
 
2 ∂
= − r − 2 2 + V (r )
2m r 2 ∂r ∂r ~ r

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 3 / 24

Schrödinger equation

The Schrödinger equation reads as

~2 1 ∂ L2
     
2 ∂
− r − 2 2 + V (r ) Ψ(r) = E Ψ(r)
2m r 2 ∂r ∂r ~ r

Since

[H, L2 ] = [L2 , Lz ] = [H, Lz ] = 0,

we may look for solutions of the Schrödinger equation which are

simultaneous eigenfunctions of the operators H, L2 and Lz .

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 4 / 24

Solutions of the Schrödinger equation

We may propose solutions separable intro products:

ψE ,l,m (r , θ, φ) = RE ,l (r )Ylm (θ, φ)

Here, Ylm (θ, φ), the spherical harmonics, are the simultaneous

eigenfunctions of the operators L2 and Lz , and RE ,l (r ) fulfills:

~2 1 d
     
2 d l(l + 1)
− r − + V (r ) RE ,l (r ) = E RE ,l (r )
2m r 2 dr dr r2

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 5 / 24

The effective potential

The equation for the radial wavefunction can be written as:

~2 1 d
     
2 d l(l + 1)
− r − + V (r ) RE ,l (r ) = ERE ,l (r )
2m r 2 dr dr r2
~2 1 d
    
2 d
− r + Veff (r ) RE ,l (r ) = ERE ,l (r )
2m r 2 dr dr

where the effective potential has the form:

l(l + 1)~2
Veff (r ) = V (r ) +
2mr 2

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 6 / 24

The Hamiltonian for the relative motion

Working on the center of mass, we must solve the (fictitious)

one-particle time-independent Schrödinger equation:

~2 Ze 2
 
− ∇2 − ψ(r) = E ψ(r)
2µ (4π0 )r

with µ the reduced mass of the system:

mM
µ=
(m + M)

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 7 / 24

The effective potential
Ze 2 l(l + 1)~2
Veff (r ) = − + ≡ Vl (r )
(4π0 )r 2µr 2
3

l=2
1
l=1
Veff

-1 l=0

-2

-3
0 1 2 3 4 5
r (a.u.)
L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 8 / 24
The radial equation

To simplify the resolution, we introduce the reduced radial function

uE ,l (r ) = rRE ,l (r )

that satisfies the equation

d 2 uE ,l 2µ
2
+ 2 [E − Veff (r )]uE ,l (r ) = 0
dr ~

where the effective potential is:

Ze 2 l(l + 1)~2
Veff (r ) = − + ≡ Vl (r )
(4π0 )r 2µr 2

(depends on the angular momentum quantum number l).

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 9 / 24
Solution of the radial equation

Now, we look for the bound states of the hydrogen atom: E < 0.

We look for regular solutions: finite at r = 0 ⇒ uE ,l (0) = 0.

Consider the dimensionless quantities

8µE 1/2 Ze 2  µ 1/2

 
ρ= − 2 r ; λ= −
~ (4π0 )~ 2E

then, the radial equation is:

d2
 
l(l + 1) λ 1
uE ,l (ρ) = − + uE ,l (ρ)
dρ2 ρ2 ρ 4

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 10 / 24

Asymptotic solution
d2
 
l(l + 1) λ 1
uE ,l (ρ) = − + uE ,l (ρ)
dρ2 ρ2 ρ 4
In the limit ρ → 0, it can be proved that

uE ,l (ρ) ∼ ρl+1
ρ→0

In the limit ρ → ∞, the constant term in the brackets dominates:

d2 1
uE ,l (ρ) = uE ,l (ρ)
dρ2 4

”Acceptable” solutions are only exponentially decreasing functions

−ρ/2
uE ,l (ρ)ρ→∞
∼ e ⇒ uE ,l (ρ) = ρl+1 e −ρ/2 f (ρ)
L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 11 / 24
Quantum numbers

We look for a solution of

d2
 
l(l + 1) λ 1
− + − uE ,l (ρ) = 0
dρ2 ρ2 ρ 4

of the form

uE ,l (ρ) = ρl+1 e −ρ/2 f (ρ)

We assume the solution f (ρ) can be express as a power series:

∞
X
f (ρ) = ck ρk ; c0 6= 0
k=0

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 12 / 24

Energy levels

Substitution into the differential equation leads to

k +l +1−λ
ck+1 = ck
(k + 1)(k + 2l + 2)

that for large k behaves as

ck+1 1
∼
ck k

which is the same as the series for ρp exp(ρ). The series must therefore

terminate. If the highest power of ρ is nr , we obtain:

λ = nr + l + 1 ≡ n = 1, 2, 3, ...
L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 13 / 24
Energy levels

We had
Ze 2  µ 1/2
λ= −
4π0 ~ 2E

Therefore the energy eigenvalues are

2
Ze 2

1 µ
En = − 2
2n 4π0 ~2

or, in atomic units

Z 2µ
En = − (µ in a.u., me =1)
2n2

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 14 / 24

Energy levels
Z 2µ
En = − (µ in a.u., me =1)
2n2
The energy agrees with the Bohr model.

Since n = 1, 2, ..., ∞: there is an infinite number of bound states.

The energy depends only on the principal quantum number n

Degeneracy:

l = 0, 1, . . . , n − 1

m = −l, −l + 1, . . . , l
Pn−1
l=0 (2l + 1) = n2
L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 15 / 24
Energy levels

Spectroscopic notation

Value of l 0 1 2 3

Letter used s p d f

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 16 / 24

The radial wavefunctions of the bound states

Remember that we were looking for a solution of

d2
 
l(l + 1) λ 1
− + − uE ,l (ρ) = 0
dρ2 ρ2 ρ 4

of the form

uE ,l (ρ) = ρl+1 e −ρ/2 f (ρ)

f (ρ) the radial equation

d2
 
d
ρ 2 + (2l + 2 − ρ) + (λ − l − 1) f (ρ) = 0
dρ dρ

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 17 / 24

The radial wavefunctions of the bound states

f (ρ) the radial equation

d2
 
d
ρ 2 + (2l + 2 − ρ) + (λ − l − 1) f (ρ) = 0
dρ dρ

The solutions of this equation are:

f (ρ) = Nnl L2l+1

n+l (ρ)

where
dp d q q −ρ
Lpq (ρ) = Lq (ρ) ; Lq (ρ) = e ρ (ρ e )
dρp dρq

Lpq (ρ): the Associated Laguerre polynomials; and Lq (ρ) the Laguerre polynomials.

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 18 / 24

The radial wavefunctions of the bound states

The normalized bound state radial functions are:

( 3 )1/2
2Z (n − l − 1)!
Rnl (r ) = − e −ρ/2 ρl Ln+l
2l+1
(ρ)
naµ [2n(n + l)!]3

with
2Z 4π0 ~2
ρ= r , aµ =
naµ µe 2

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 19 / 24

The radial wavefunctions of the bound states

For infinitely heavy nucleus, the first radial eigenfunctions are , in a.u., by:

R10 (r ) = 2Z 3/2 e −Zr

R20 (r ) = 2(Z /2)3/2 (1 − Zr /2)e −Zr /2

1
R21 (r ) = √ (Z /2)3/2 Zre −Zr /2
3
R30 (r ) = 2(Z /3)3/2 (1 − 2Zr /3 + 2Z 2 r 2 /27)e −Zr /3
√
4 2
R31 (r ) = (Z /3)3/2 (1 − Zr /6)(Zr )e −Zr /3
9
4
R32 (r ) = √ (Z /3)3/2 (Zr )2 (Zr )e −Zr /3
27 10
L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 20 / 24
Radial distribution functions

Probability density

1
|ψnlm (r , θ, φ)|2 = |Rnl (r )|2 |Ylm (θ, φ)|2 = |Rnl (r )|2 |Θlm (θ)|2
2π

Radial distribution function

Z π Z 2π
2 2
Dnl (r )dr = r |Rnl (r )| dr dθ sin θ dφ|Ylm (θ, φ)|2
0 0
2 2
= r |Rnl (r )| dr

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 21 / 24

Radial wavefunctions

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 22 / 24

Radial distributions

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 23 / 24

Probability density plots

L. F. Errea, L. Méndez, I. Rabadán Chapter 4: One-electron atoms October 26, 2023 24 / 24