The Hydrogen Atom

1 Application of the Schrödinger

Equation to the Hydrogen Atom
2 Solution of the Schrödinger
Equation for Hydrogen
3 Quantum Numbers
4 Magnetic Effects on Atomic
Spectra–The Zeeman Effect
5 Intrinsic Spin
Erwin Schrödinger (1887-1961)
6 Energy Levels and Electron
Probabilities
The atom of modern physics can be symbolized only through a partial differential
equation in an abstract space of many dimensions. All its qualities are inferential; no
material properties can be directly attributed to it. An understanding of the atomic world
in that primary sensuous fashion…is impossible.
- Werner Heisenberg
1: Application of the Schrödinger
Equation to the Hydrogen Atom
The potential energy of the electron-proton system is electrostatic:

Use the three-dimensional time-independent Schrödinger Equation.

For Hydrogen-like atoms (He+ or Li++), replace e2 with Ze2 (Z is the

atomic number).
In all cases, for better accuracy, replace m with the reduced mass, m.
Spherical Coordinates
The potential (central force)
V(r) depends on the distance r
between the proton and
electron.
Transform to spherical polar
coordinates because of the
radial symmetry.
The
Schrödinger
Equation in
Spherical
Coordinates

Transformed into
spherical coordinates,
the Schrödinger
equation becomes:
Separable Solution

The wave function y is a function of r, q, f. This is a potentially

complicated function.

Assume instead that y is separable, that is, a product of three

functions, each of one variable only:

This would make life much simpler, and it turns out to work.
Solution of the Schrödinger Equation for H

azimuthal equation It is convenient to choose the

solution to be .
mℓ integer

Radial equation

Angular equation

We’ve separated the Schrödinger equation into three ordinary second-

order differential equations, each containing only one variable.
Principal
Quantum
Number n

There are many solutions to the radial wave equation, one for
each positive integer, n. n = 1, 2, 3, …

The result for the quantized energy is:

A negative energy means that the electron (u.a. mint a Bohr-

and proton are bound together. modellben)
Kvantumszámok
A négy atomi kvantumszám:
n: fő kvantumszám
ℓ: mellék (pálya-impulzusmomentum) kvantumszám
mℓ: mágneses (azimutális) kvantumszám

A kvantumszámok lehetséges értékei:

n = 1, 2, 3, 4, . . .
ℓ = 0, 1, 2, 3, . . . , n − 1
mℓ = −ℓ, −ℓ + 1, . . . , 0, 1, . . . , ℓ − 1, ℓ

Equivalently:
n>0 The energy levels are:
ℓ<n
|mℓ| ≤ ℓ
Kvantumszámok értékeinek jelölése

Az n fő kvantumszám értékeire:
n= 1 2 3 4 5...
Jelölés: K L M N O...

Az ℓ mellék kvantumszám értékeire:

ℓ= 0 1 2 3 4 5...
Jelölés: s p d f g h...

Energy levels are degenerate with respect to ℓ (the energy is

independent of ℓ).

Atomic states are usualy referred to by their values of n and ℓ.

A state with n = 2 and ℓ = 1 is called a 2p state.

Hydrogen Atom Radial Wave Functions

First few (associated Laguerre functions)

radial
wave
functions
Rnℓ

Sub-
scripts
on R
specify
the
values of
n and ℓ.
Normalized
Spherical
Harmonics
Solution of the Schrödinger Equation for H

The radial wave function R and the spherical harmonics Y determine

the probability density for the various quantum states. The total wave
function depends on n, ℓ, and mℓ. The wave function
becomes
Probability Distribution Functions

We use the wave functions to calculate the probability

distributions of the electrons.

The “position” of the electron is spread over space and is not

well defined.

We may use the radial wave function R(r) to calculate radial

probability distributions of the electron.

The probability of finding the electron in a differential volume

element dt is:
Probability Distribution Functions
The differential volume element in spherical polar coordinates is

Therefore,

At the moment, we’re only interested in the radial dependence.

The radial probability density is P(r) = r2|R(r)|2 and it depends only on n

and ℓ.
Probability
Distribution
Functions

R(r) and P(r)

for the lowest-
lying states of
the hydrogen
atom.
Probability Distribution Functions
The probability density for the hydrogen atom for three different
electron states.
Orbital Angular Momentum Quantum
Number ℓ
It’s associated with the R(r) and f(θ) parts of the wave function.

Classically, the orbital angular momentum with L = mvorbitalr.

L is related to ℓ by

In an ℓ = 0 state,

This disagrees with Bohr’s

semi-classical “planetary”
model of electrons orbiting Classical orbits—which do not
a nucleus L = nħ. exist in quantum mechanics
 Magnetic Quantum
The solution for g(f) specifies that Number mℓ
mℓ is an integer and is related to
the z component of L:

Example: ℓ = 2:

Only certain orientations of are

possible. This is called space
quantization.

And (except when ℓ = 0) we just

don’t know Lx and Ly!
Rough derivation of ‹L2› = ℓ(ℓ+1)ħ2
We expect the average of the angular momentum components
squared to be the same due to spherical symmetry:

But

Averaging over all mℓ values (assuming each is equally likely):

because: 
n
m2  (  1)(2  1) / 3
Magnetic Effects on Atomic
Spectra—The Zeeman Effect
In 1896, the Dutch physicist Pieter Zeeman
showed that spectral lines emitted by atoms
in a magnetic field split into multiple energy
levels. It is called the Zeeman effect.
Consider the atom to behave like a small magnet.
Think of an electron as an orbiting circular current loop of I = dq / dt
around the nucleus. If the period is T = 2p r / v,

then I = -e/T = -e/(2p r / v) = -e v /(2p r).

The current loop has a magnetic moment m = IA = [-e v /(2p r)] p r2 =

[-e/2m] mrv:
e
m L
2m
where L = mvr is the magnitude of the orbital angular momentum.
 e
The Zeeman Effect m L
2m

The potential energy due to the

magnetic field is:

If the magnetic field is in the z-direction, we only care about the z-

component of m:

e e
mz   Lz   (m )   m B m
2m 2m

where mB = eħ / 2m is called the Bohr magneton.

The Zeeman Effect
A magnetic field splits the mℓ levels. The potential energy is quantized
and now also depends on the magnetic quantum number mℓ.

When a magnetic field is applied, the 2p level of atomic hydrogen is

split into three different energy states with energy difference of ΔE =
mBB Δmℓ.

mℓ Energy
1 E0 + μBB
0 E0
−1 E0 − μBB
The
Zeeman
Effect

The transition
from 2p to 1s,
split by a
magnetic field.

Magyarázat az
eddigiek alapján:
iránykvantálással
Stern-Gerlach kísérlet
An atomic beam of particles in the ℓ = 1 state pass through a
magnetic field along the z direction.

Az iránykvan-
tálás közvetlen
kísérleti
bizonyítéka.
(1921.)

 mB m (dB / dz)

The mℓ = +1 state will be deflected down, the mℓ = −1 state up, and

the mℓ = 0 state will be undeflected.
Energy Levels
and Electron
Probabilities

For hydrogen, the energy

level depends on the prin-
cipal quantum number n.

In the ground state, an atom

cannot emit radiation. It can
absorb electromagnetic
radiation, or gain energy
through inelastic
bombardment by particles.

Selection Rules
The probability is proportional to
the mag square of the
We can use the wave functions
to calculate transition probabilities
for the electron to change from
one state to another.
where i and f


dipole moment:
d  *f er  i are the initial and
final states of the
transition.
Allowed transitions:
Electrons absorbing or emitting photons can change states
when Δℓ = ±1 and Δmℓ = 0, ±1.

Forbidden transitions:
Other transitions are possible
but occur with much smaller
probabilities.
Saját impulzusmomentum (spin)

Stern–Gerlach-kísérlet alapállapotban lévő Ag atomokkal

 Ag-nyaláb két részre bomlik

 spektoszkópiai mérésekből: alapállapot s-állapot (ℓ = 0)

 pálya-impulzusmomentummal (L) nem magyarázható

Magyarázat: elektron saját impulzusmomentuma (spin, S) alapján

Samuel A. Goudsmit (1902–1978.), George E. Uhlenbeck (1900–1988.)
Saját impulzusmomentum (spin)
Atomi elektronok teljes impulzusmomentuma: J  LS

pálya impulzusmomentum spin

L  L     1 S  S   ss  1
: mellék-kvantumszám s: spin-kvantumszám

Lz  m S z  m s
m  ,,  mágneses kvsz. ms  s , , s spin mágneses kvsz.
giromágneses hányadosok
μ     L μ s   s S
μ e μs
   s  ?
L 2m S
Saját impulzusmomentum (spin)
Iránykvantálás

1 1
Stern–Gerlach-kísérlet → s  , ms  
2 2

S  S   ss  1
11 
   1 
22 
3

2
1
szokásos jelölés: ↑ ms   2

↓ m 1
s
2
Saját impulzusmomentum (spin)
Giromágneses hányados spinre

Einstein–de Haas-effektus

μs
e
→ s    2 
S m vas: vezetési
sáv „szabad”
pálya impulzusmomentum spin elektronjaira:
μ s   s S L0
μ     L
L S
μ    g mB μ s   gs mB
 
g  1 Landé-faktorok gs  2

Dirac-egyenlet → g s  2 ,0023
Spin-pálya kölcsönhatás
Szemiklasszikus modell: elektron mozgása pályán, de
impulzusmomentuma kvantált

Elektron koordinátarendszerében: atommagtól eredő köráram

→ elektron mágneses térben
m 0 Ze m 0 Ze
B v   r   L (Biot–Savart-törvényből)
4pr 3
4pr me
3

m0 Ze m0 Ze 2
E  μ s  B  g s m B S  L  S  L
4pr me 
3
4pme r
2 3
Teljes impulzusmomentum
Atomi elektronok teljes impulzusmomentuma: J  LS

J  J   j  j  1 kvantálás

j  j  , s  telj. impulzusmomentum kvatumszám

(belső kvantumszám)

1 1
j  vagy j , ha   0
2 2 1
j 
1 2
j , ha   0
2

J z  mj

mj   j , j  1,, j
Spin-pálya kölcsönhatás
Szemiklasszikus modell: elektron mozgása pályán, de
impulzusmomentuma kvantált

Elektron koordinátarendszerében: atommagtól eredő köráram

→ elektron mágneses térben
m 0 Ze m 0 Ze
B v   r   L (Biot–Savart-törvényből)
4pr 3
4pr me
3

m0 Ze m0 Ze 2
E  μ s  B  g s m B S  L  S  L
4pr me 
3
4pme r
2 3

 Z 2 2  1 3 
 En 1    m0ce2 e2 1
En , j
n  j  1 2  4n    
    4p 4p 0c 137