Introduction to Quantum

Mechanics

Course Instructor
Dr. M. Tahir
 Why Quantum Mechanics?
Classical Physics is unable to offer a satisfactory explanation of
phenomena in microworld, of the structure of even the simplest
atom, Hydrogen. It makes no sense on atomic phenomena:
potoelectronic effect, thermal radiation, optical spectra of
atoms, Compton scattering, etc.

Bohr-Sommerfeld theory can partially explain hydrogen atom,

but it is not satisfied in theory, does not work for atoms with
two or more electrons.

Solution: Quantum mechanics

First introduced by Schrödinger in 1926
 Wave-particle duality

Matter wave

Correspond to a wave function  r , t 
Of the system, to describe particle behaviors at
space r and changing with time t.
2
 dV Means the probability to find the
particles in volume dV =
dxdydz.
 Wave Function
• Max Born’s best known contribution to quantum
mechanics was his proposal that the wave
function, or rather its square modulus, should be
interpreted as the probability density for finding
the system in a given state at a given time.
However, he also proposed four conditions on the
wave function which are used in finding many
solutions of the Schrödinger equation.
 Wave Function
• The wave function must be single valued. This
means that for any given values of and , must have
a unique value. This is a way of guaranteeing that
there is only a single value for the probability of
the system being in a given state. Actually, if is a
proper mathematical function, it will satisfy this
requirement automatically, since one condition all
functions must satisfy is that they are single-
valued.
 Wave Function
• The wave function must be square-integrable. In
other words, the integral of over all space must be
finite. This is another way of saying that it must be
possible to use as a probability density, since any
probability density must integrate over all space to
give a value of 1, which is clearly not possible if
the integral of is infinite. One consequence of this
proposal is that must tend to 0 for infinite
distances.
 Wave Function
• The wave function must be continuous
everywhere. That is, there are no sudden jumps in
the probability density when moving through
space. In the limit of a step function, this would
imply an infinite derivative. Since the momentum
of the system is found using the momentum
operator, which is a first order derivative, this
would imply an infinite momentum, which is not
possible in a physically realistic system.
• All first-order derivatives of the wave function
must be continuous. Following the same reasoning
as in condition 3, a discontinuous first derivative
would imply an infinite second derivative, and
since the energy of the system is found using the
second derivative, a discontinuous first derivative
would imply an infinite energy, which again is not
physically realistic.
Wavefunction properties
 Schrödinger equation
The Schrödinger equation plays the role of Newton's
laws and conservation of energy in classical mechanics
- i.e., it predicts the future behavior of a dynamic
system. It is a wave equation in terms of the
wavefunction which predicts analytically and precisely
the probability of events or outcome. The detailed
outcome is not strictly determined, but given a large
number of events, the schrödinger equation will predict
the distribution of results.
Schrödinger equation is a fundamental assumption in
Quantum Mechanics, which can not be derived from
other theories.
 Schrödinger equation
—a harmonic oscillator example
 For a 1D(x) free particle
Wavefunction:
i
 ( Et  Px )
Ψ ( x, t )  Ψ o e 

i
Ψ i  ( E t P x) i
  EΨ o e 
  EΨ
t  
 Ψ
2 2
Ψ
Ψ
2
P 2
  2 Ψ oe
i
 ( E t P x)

P2
 2Ψ
  i
x 2
  2m x 2
t
P2
E  Ek 
2m schrödinger equation
 For a particle with 1D(x) potential field U(x,t)
2
P
E  Ek  U  U
2m Ψ i P 2
 [  U ( x, t )]Ψ
Ψ i t  2m
  EΨ
t    2Ψ P2
  Ψ
2m x 2
2m
 2Ψ P2
 2 Ψ
x 2


 Ψ
2 2
Ψ
  U ( x, t )Ψ  i
2m x 2
t
schrödinger equation
 1D → 3D
schrödinger equation:

 
2
2
 2 2
Ψ
 [ 2  2  2 ]Ψ  U ( x, y, z , t )Ψ  i
2m x y z t
 2
 2
 2
Lapalace operator ： 2   
x 2
y 2
z 2

schrödinger equation in general case:


 2
   Ψ (r , t )
  Ψ (r , t )  U (r , t )Ψ (r , t )  i
2

2m t
Schrödinger equation is a fundamental dynamic equation of
nonrelativistic quantum mechanics, which plays the role of
Newton’s law in classical mechanics.
 
  2
   Ψ (r , t )
   U (r , t )Ψ (r , t )  i
2

 2m  t

H, Hamilatonian
The kinetic and potential energies are
transformed into the Hamiltonian which acts
upon the wavefunction to generate the
evolution of the wavefunction in time and
space. The Schrödinger equation gives the
quantized energies of the system and gives
the form of the wavefunction so that other
properties may be calculated.
 Steady Schrödinger equation
i

Steady wavefunction ： Ψ ( r , t )  Φ ( r )e
  Et


2 2 Ψ
  Ψ  UΨ  i
2m t
2 2 i
       Et
[   U (r )]Ψ (r , t )  {[ 
2
  U ( r )] ( r )}e
2 
2m 2m
i
Ψ   Et

i  EΦ (r )e
t

2 2 2m
  Φ  UΦ  EΦ or  Φ  2 ( E  U )Φ  0
2

2m 
 The structure of hydrogen atom
The hydrogen atom consists of a single proton surrounded by a single electron. It
is thus the simplest of all atoms. The proton may be thought to be approximately
at rest at the origin of the coordinate (the center of the hydrogen atom) because
proton is about 1836 times heavier than electron. The Coulomb attractive force
works between the proton and the electron. Its potential is written:

1 e2
V (r )   
4 0 r
where r is the distance between the proton and the electron. The
(nonrelativistic) Schrödinger equation describing the motion of
the electron takes the form:

 2 2 1 e2 
       E
 2m 4 0 r 
 The Schrödinger equation and its solution
The polar coordinate (r,,) shown in the following is more
convenient than the Cartesian coordinate (x,y,z).
 The Schrödinger equation and its solution

We solve the Schrödinger equation by setting the boundary

condition that the wave function should be smoothly continuous
at every point of the coordinate space and should converge to 0
at the infinitely long distance. Then we have a set of discrete
energy eigenvalues and the corresponding eigenstates. The
details of the method to solve it is omitted here. If you want to
study them, please refer to some other textbooks of quantum
mechanics.

The wave functions of the eigenstates is expressed as

 (r , ,  )  Rnl (r )Ylm ( ,  )
  (r , ,  )  Rnl (r )Ylm ( ,  )

the part Rnl(r) is the radial wave function which is

specified by a set of integers, n and l. n and l are
quantum numbers, which characterize the eigenstates.

n = 1,2,3,…; l = 0,1,2,…; l  n-1

The part Ylm(,) denotes the angular wave function. It

describes the revolving state of the electron around the
coordinate origin (proton), which is specified by a set of
quantum numbers (integers), l and m:

m l, i.e., m = -l, -l +1, …, l - 1, l

 Quantum numbers

n: principal quantum number,

n = 1, 2, 3, …;

l: orbital quantum number,

l = 0, 1, 2, …, n-1;

m: magnetic quantum number,

m = -l, -1+1, …, l-1, l.
The energy eigenvalues of hydrogen atom are determined
only by the quantum number n

The ground state:

The abscissa denotes the position coordinate of the

electron (the distance between the proton and electron),
r , in units of the Bohr radius , where

4 0  2 10
a0  2
 0 . 529  10 m
me
The energy is quantised; En is continues when n  
The orbital quantum number l expresses the speed of the
revolution of the electron, i.e. the magnitude of the
angular momentum of the electron; and the magnetic
quantum number m represents the orientation (direction)
of angular momentum vector.
The angular momentum of the electron is quantised:
 h
L  l (l  1)  l (l  1) 
2

The orientation of the angular momentum is also

quantised, i.e., the component in z direction is quantised:
h
LZ  m  m
2
For example ： l  2

B(z)
L  l (l  1)   2(2  1)   6  L z  2 m=2
 m=1
LZ  m 0 m=0

L 6  m = -1
m  0 ,  1,  2 ,    ,  l
 2 m = -2
LZ  0,  ,  2
 These result implies that not only energy but also
angular momentum and its orientation are
quantized in quantum mechanics. This was
confirmed by the Stern-Gerlach experiment
(1922). Needless to say, this also originates from
the particle-wave duality of electrons. And this can
never understood by the classical theory.
 The probability to find an electron
at the position r from the center—
the probability density in the space:

r Rnl r 
2 2


 r Rnl r  dr  1
2 2
0
 The atomic models

Plum-pudding model Planet model by Rutherford

by Thomson

Electron cloud model Bohr’s model

 Atomic orbitals

n=1,l=0 n=2,l=0 n=2,l=1 n=3,l=0 n=3,l=1 n=3,l=2

m=0

m=1

m=2
 Atomic orbitals

n=4,l=0 n=4,l=1 n=4,l=2 n=4,l=3

m=0

m=1

m=2

m=3
The probability density of the electrons of H atom

n=1 l=0 m=0

l=0 m=0
n=2 m=0
l=1
& m = ±1
l=0 m=0
m=0
n=3 l=1
& m = ±1
m=0
l=2
& m = ±1 & m = ±2
n=6 l=3 m=0

n = 11 l = 6 m = ±3
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 1, l = 0, m = 0,
spherically symmetrical distributions
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 2, l = 0, m = 0,
spherically symmetrical distributions
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 2, l = 1, m = 0,
Dumbbell shaped distribution
along one axis
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 2, l = 1, m = ±1,
Dumbbell shaped distribution
along one axis
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 0, m = 0,
spherically symmetrical distributions
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 1, m = 0,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 1, m = ±1,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 2, m = 0,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 2, m = ±1,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 3, l = 2, m = ±2,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 6, l = 3, m = 0,
 The colors in the plots of the probability
distributions vary from blue to red
corresponding to the increase of the
probability from small (zero) to large
values.

n = 11, l = 6, m = ±3,