Quantum Mechanics and the hydrogen atom

Since we cannot say exactly where an electron is, the Bohr picture
of the atom, with electrons in neat orbits, cannot be correct.

Quantum theory describes

electron probability distributions:

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 Hydrogen Atom:
Schrödinger Equation and Quantum Numbers

Potential energy for the hydrogen atom:

The time-independent Schrödinger equation in three

dimensions is then:
Equation 39-1 goes here.

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 Where does the quantisation in QM come from ?

The atomic problem is spherical so rewrite the equation in (r,θ,φ)

x = r sin θ cos φ y = r sin θ sin φ z = r cosθ

Rewrite all derivatives in (r,θ,φ), gives Schrödinger equation;

h2 ⎛ ∂ 2 ∂ ⎞ h 2 ⎛⎜ 1 ∂ ∂ 1 ∂ 2 ⎞⎟
− ⎜ r ⎟Ψ − sin θ + Ψ + V ( r ) Ψ = EΨ
2m ⎝ ∂r ∂r ⎠ 2m ⎜⎝ sin θ ∂θ ∂θ sin 2 θ ∂φ 2 ⎟⎠

This is a partial differential equation, with 3 coordinates (derivatives);

Use again the method of separation of variables:
Ψ (r ,θ ,φ ) = R(r )Y (θ ,φ )

Bring r-dependence to left and angular dependence to right (divide by Ψ):

1 ⎡ d 2 dR 2mr 2 ⎤
QM
Oθφ Y (θ ,φ )
⎢ r + ( E − V (r ))R ⎥ = − =λ
R ⎣ dr dr h 2
⎦ Y (θ ,φ ) Separation of variables
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 Where does the quantisation in QM come from ?

1 ⎡ d 2 dR 2mr 2 ⎤
Radial equation ⎢ r + 2
( E − V (r ))R ⎥=λ
R ⎣ dr dr h ⎦
⎛ 1 ∂ ∂ 1 ∂ 2 ⎞
− ⎜⎜ sin θ + 2 ⎟Y (θ ,φ )
QM
Oθφ Y (θ ,φ ) sin θ ∂θ ∂θ sin θ ∂φ ⎠2⎟
Angular equation − = ⎝ =λ
Y (θ ,φ ) Y (θ ,φ )

∂ 2Y ∂ ∂Y
− = sin θ sin θ + λ sin 2 θY
∂φ 2 ∂θ ∂θ

Once more separation of variables: Y (θ ,φ ) = Θ(θ )Φ(φ )

1 ∂ 2Φ 1 ⎛ ∂ ∂Θ ⎞
Derive: − = ⎜ sin θ sin θ + λ sin 2
θΘ ⎟ = m 2
(again arbitrary constant)
Φ ∂φ 2 Θ ⎝ ∂θ ∂θ ⎠

Simplest of the three: the azimuthal angle;

∂ 2Φ(φ )
+ m 2Φ(φ ) = 0
∂φ 2
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 Where does the quantisation in QM come from ?

A differential equation with a boundary condition

∂ 2Φ(φ ) Φ(φ + 2π ) = Φ (φ )
+ m 2Φ(φ ) = 0 and
∂φ 2

Solutions:

Φ(φ ) = eimφ

Boundary condition; Φ(φ + 2π ) = eim(φ +2π ) = Φ(φ ) = eimφ

e 2πim = 1

m is a positive or negative integer

this is a quantisation condition

General: differential equation plus a boundary condition gives a quantisation

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 Where does the quantisation in QM come from ?

with integer m
First coordinate Φ(φ ) = e imφ
(positive and negative)

angular
1 ∂ ∂Θ ⎛⎜ m 2 ⎞⎟ part
Second coordinate sin θ + λ − 2 ⎟Θ = 0
sin θ ∂θ ∂θ ⎜⎝ sin θ ⎠
angular
Results in λl = l(l + 1) with l = 0,1,2,K momentum

and m = −l,−l + 1,K, l − 1, l

1 ⎡ d 2 dR 2mr 2 ⎤
Third coordinate ⎢ r + 2
( E − V (r ))R ⎥ = l(l + 1)
R ⎣ dr dr h ⎦

Differential
equation Results in quantisation of energy radial
part
2
Z2 Z 2 ⎛⎜ e 2 ⎞⎟ me
En = − 2 R∞ = − 2 ⎜
n n ⎝ 4πε 0 ⎟⎠ 2h 2
with integer n (n>0)
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 Angular wave functions

h⎡ 1 ∂ ∂ 1 ∂2 ⎤
Operators: L = ⎢
2
sin θ + 2 ⎥ Angular momentum
i ⎣ sin θ ∂θ ∂θ sin θ ∂φ 2 ⎦
r
h ∂ L = ( Lx , L y , Lz )
Lz =
i ∂φ

There is a class of functions that are simultaneous eigenfunctions

L2Ylm (θ ,φ ) = l(l + 1)h 2Ylm (θ ,φ ) LzYlm (θ ,φ ) = mhYlm (θ ,φ )

with l = 0,1,2,K and m = −l,−l + 1,K, l − 1, l

Spherical harmonics (Bolfuncties) Ylm (θ ,φ ) Vector space of solutions

∫ Ylm (θ ,φ ) dΩ = 1
1 3 2
Y00 = Y11 = − sin θeiφ
4π 8π Ω
∫ YlmYl 'm'dΩ = δ ll 'δ mm'
*
3
Y10 = − cosθ Ω
4π
Parity
3
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8π
sin θe −iφ Pop Υlm (θ , φ ) = Υ (π − θ , φ + π ) = (− )l Υlm (θ , φ )
 The radial part: finding the ground state

1 ⎡ d 2 dR 2mr 2 ⎤
⎢ r + 2 (E − V (r ))R ⎥ = λ h2 Ze 2
R ⎣ dr dr h ⎦ Prefactor for 1/r: − =0
ma 4πε 0

Find a solution for l = 0, m = 0 Solution for the

length scale paramater
h2 ⎛ 2 ⎞ Ze 2
− ⎜ R"+ R ' ⎟ − R = ER
2m ⎝ r ⎠ 4πε 0 r 4πε 0 h 2
a0 = Bohr radius
Physical intuition; no density for r → ∞ Ze 2 m

trial: R (r ) = Ae −r / a
A R
R ' = − e −r / a = − Solutions for the energy
a a
A R
R" = 2 e −r / a = 2
2
2⎛
2 ⎞
h2 e ⎟ me
a a E=− = − Z ⎜⎜ ⎟
⎝ 4πε 0 ⎠ 2h
2ma 2

h2 ⎛ 1 2 ⎞ Ze 2
− ⎜ 2 − ⎟− =E
2m ⎝ a ar ⎠ 4πε 0 r
Ground state in the
Bohr model (n=1)
must hold for all values of r
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 Hydrogen Atom:
Schrödinger Equation and Quantum Numbers
There are four different quantum numbers needed to
specify the state of an electron in an atom.
1. The principal quantum number n gives the total energy.
2. The orbital quantum number l gives the angular
momentum; l can take on integer values from 0 to n - 1.

3. The magnetic quantum number, m , gives the l

direction of the electron’s angular momentum, and can
take on integer values from –l to +l.

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 Hydrogen Atom Wave Functions

The wave function of the ground state of hydrogen has

the form:

The probability of finding the electron in a volume dV

around a given point is then |ψ|2 dV.

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 Radial Probability Distributions

Spherical shell of thickness dr, inner radius r

and outer radius r+dr.

Its volume is dV=4πr2dr

Density: |ψ|2dV = |ψ|24πr2dr

The radial probablity distribution is then:

Pr =4πr2|ψ|2

Ground state

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 Hydrogen Atom Wave Functions
This figure shows the three probability distributions for n = 2 and l
= 1 (the distributions for m = +1 and m = -1 are the same), as well
as the radial distribution for all n = 2 states.

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 Hydrogen “Orbitals” (electron clouds)

Represents the probability to find a particle

r 2
Ψ (r ,t )
At a location r at a time t

The probability density

The probability distribution

Max Born

The Nobel Prize in Physics 1954

"for his fundamental research in
quantum mechanics, especially for his
statistical interpretation of the wavefunction"

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 Atomic Hydrogen Radial part

Analysis of radial equation yields:

Z2
Enlm = − 2
R∞
n

me e 4
with R∞ =
8ε 0 h 3c

Wave functions:
r
Ψnlm (r , t ) = Rnl (r )Υlm (θ , φ )e −iEn t / h

For numerical use:

u (r ) (n − l − 1)!e − Zρ / n ⎛ 2Zρ ⎞l +1 L2l +1 ⎛ 2Zρ ⎞

unl (ρ ) =
2Z
R = nl ⎜ ⎟ n − l −1⎜ ⎟
r na0 2n(n + 1)! ⎝ n ⎠ ⎝ n ⎠
ρ / r = 2 Z / na a = 4πε 0h 2 / μe 2
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 Quantum analog of electromagnetic radiation

Classical electric dipole radiation Transition dipole moment

Classical oscillator Quantum jump

r& 2
& * r 2
I rad ∝ er I rad ∝ ∫ψ 1 erψ 2 dτ
The atom does not radiate when it is in a stationary state !
The atom has no dipole moment

*r
μii = ∫ ψ 1 r ψ 1dτ =0
2
Intensity of spectral lines linked μ fi
Bif =
to Einstein coefficient for absorption: 6ε 0h 2

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 Selection rules

Mathematical background: function of odd parity gives 0 when integrated over space
∞ ∞
In one dimension: Ψ f x Ψi = ∫ Ψ *f xΨi dx = ∫ f ( x)dx with f ( x) = Ψ *f xΨi
−∞ −∞

∞ 0 ∞ 0 ∞ ∞ ∞

∫ f ( x)dx = ∫ f ( x)dx + ∫ f ( x)dx = ∫ f (− x)d (− x ) + ∫ f ( x)dx = ∫ f (− x)dx + ∫ f ( x)dx

−∞ −∞ 0 ∞ 0 0 0

∞
= 2 ∫ f ( x)dx ≠ 0 if f ( − x) = f ( x) Ψi and Ψ f opposite parity
0

=0 if f (− x) = − f ( x) Ψi and Ψ f same parity

Electric dipole radiation connects states of opposite parity !

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 Selection rules
depend on angular behavior of the wave functions

Parity operator
r All quantum mechanical wave functions
r have a definite parity
r r
θ Ψ (− r ) = ± Ψ (r )

φ r
Ψ f r Ψi ≠ 0

r
−r If Ψf and Ψi have opposite parity

r r
Pr = −r Rule about the Ylm functions
( x , y , z ) → ( − x, − y , − z )
PYlm (θ , φ ) = (− )l Ylm (θ , φ )
(r ,θ , φ ) → (r , π − θ , φ + π )
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 Hydrogen Atom:
Schrödinger Equation and Quantum Numbers

“Allowed” transitions between energy levels occur between states

whose value of l differ by one:

Other, “forbidden,” transitions also occur but with much lower

probability.

“selection rules, related to symmetry”

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 Selection rules in Hydrogen atom

Intensity of spectral lines given by

r r
μ fi = ∫ Ψ*f μΨi = Ψ f − er Ψi

1) Quantum number n
no restrictions Balmer series

2) Parity rule for l

Δl = odd

3) Laporte rule for l

Angular momentum rule: Lyman series
r r r
l f = li + 1 so Δl ≤ 1
From 2. and 3. Δl = ±1

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