Introduction to Quantum

Mechanics
Duong Quang Ha, Ph.D
Postulates of Quantum
Mechanics
 Basic Postulate in Quantum Mechanics
❑ The formalism of quantum mechanics is based on a
number of postulates. These postulates are in turn
based on a wide range of experimental observations.
• These postulates cannot be derived; they result from
experiment. They represent the minimal set of
assumptions needed to develop the theory of quantum
mechanics.
 Basic Postulate in Quantum Mechanics
❑ According to classical mechanics, the state of a
particle is specified, at any time t, by two fundamental
dynamical variables: the position 𝑟(𝑡) and the
momentum 𝑝(𝑡).
• Any other physical quantity, relevant to the system,
can be calculated in terms of these two dynamical
variables.
 Basic Postulate in Quantum Mechanics
❑ In quantum mechanics, these ideas are specified by
postulates :
▪ How a quantum state is described mathematically at a
given time t
▪ How to calculate the various physical quantities from
this quantum state
▪ Knowing the system’s state at a time t, how to find the
state at any later time t’ ; that is, how to describe the
time evolution of a system.
 Basic Postulate in Quantum Mechanics
❖ Postulate 1 : State of a system
▪ The state of any physical system is specified, at each time t,
by a state vector |ψ(t)> in a Hilbert space H; |ψ(t)> contains
(and serves as the basis to extract) all the needed information
about the system. Any superposition of state vectors is also a
state vector.
❖Postulate 2 : Observables and operators
▪ To every physically measurable quantity A, called an
observable or dynamical variable, there corresponds a linear
Hermitian operator A whose eigenvectors form a complete
basis.
 Basic Postulate in Quantum Mechanics
❖ Postulate 3 : Measurements and eigenvalues of operators
▪ The measurement of an observable A may be represented
formally by the action of A on a state vector |ψ(t)>. The only
possible result of such a measurement is one of the
eigenvalues an (which are real) of the operator A. If the result
of a measurement of A on a state |ψ(t)> is an, the state of the
system immediately after the measurement changes to
|ψn(t)>:
 Basic Postulate in Quantum Mechanics
❖ Postulate 4 : Probabilistic outcome of measurements
▪ Discrete spectra: When measuring an observable A of a
system in a state an, the probability of obtaining one of the
nondegenerate eigenvalues an of the corresponding operator A
is given by :

▪ If the eigenvalue is m-degenerate, Pn becomes :

 Basic Postulate in Quantum Mechanics
❖ Postulate 4 : Probabilistic outcome of measurements
▪ Continuous spectra: The equations for discrete spectra can be
extended to determine the probability density that a
measurement of A yields a value between a and a + da on a
system which is initially in a state |ψ>:

▪ For instance, the probability density for finding a particle

between x and x + dx :
 Basic Postulate in Quantum Mechanics
❖ Postulate 4 : Probabilistic outcome of measurements
▪ In consistent with the probability definition, the real positive
number an must obey the sum rule :
 an = 1   Pn = 1
2
n n
▪ The mean value <A> of the measurement results in the state
|ψ> is :
2
A  =  an Pn   A  =  an  n 
n n
 Basic Postulate in Quantum Mechanics
❖ Postulate 5 : Time evolution of a system
▪ The time evolution of the state vector |ψ(t)> of a system is
governed by the time-dependent Schrödinger equation :

where H is the Hamiltonian operator corresponding to the total

energy of the system.
 The State of A System
❑ In quantum mechanics, the state vector |ψ(t)> can be
represented in two ways :
▪ The wavefunction ψ(r,t) in position space :
 (r , t ) = r  (t )
▪ The wavefunction Ψ(p,t) in momentum space :
 ( p, t ) = p  ( t )
▪ The wavefunction of a particle is physically acceptable if it
along with its derivatives are finite, continuous and single-
valued everywhere.
 Probability Density
• According to Born’s probabilistic interpretation, the position
probability density is represented:
2
P (r , t ) =  (r , t )
• The total probability of finding the system somewhere in
space is equal to 1 :
 Superposition Principle
• The state of a system does not have to be represented by a
single wave function; it can be represented by a superposition
of two or more wave functions.
 Superposition Principle
• In general, the linear superposition of many wave functions
gives a new wave function which represents a possible
physical state of the system :
2
 =  i  i → P =  i  i
i i

• If the states |ψi> are mutually orthonormal :

P=  i
2
i
Example
 Observables and Operators
❑ An observable is a dynamical variable that can be measured
(the position, linear momentum, angular momentum, and
energy).
• According to the second postulate, a Hermitian operator is
associated with every physical observable.
• In general, any function, f( 𝑟Ԧ , 𝑝)
Ԧ which depends on the
position and momentum variables can be made into a
function of operators :
f ( r , p ) → F ( R, P )
 Observables and Operators
• For example :

f ( x , p ) → F ( X , −i )
x
• The Hamiltonian operator in position representation :
1 2
H= ( p) + V ( r , t )
2
H =−  + V ( R, t )
2
2m 2m
• Due to P operator is Hermitian, if the potential function
V(R,t) is a real function, the Hamiltonian is Hermitian.
Observables and Operators
 Example
❑ Find the operator representing the classical orbital angular
momentum.
y 𝑖Ԧ 𝑗Ԧ 𝑘 𝑦 𝑧 𝑥 𝑧 𝑥 𝑦
𝐿= 𝑥 𝑦 𝑧 = 𝑖Ԧ. 𝑝 𝑝𝑧 − 𝑗
Ԧ 𝑝𝑥 𝑝𝑧 + 𝑘 𝑝𝑥 𝑝𝑦
𝑥
x 𝑝𝑥 𝑝𝑦 𝑝𝑧

z 𝐿 = 𝑦𝑝𝑧 − 𝑝𝑦 𝑧 𝑖Ԧ + 𝑧𝑝𝑥 − 𝑥𝑝𝑧 𝑗Ԧ + (𝑥𝑝𝑦 − 𝑦𝑝𝑥 )𝑘

𝜕 𝜕
𝐿𝑥 = 𝑦𝑝𝑧 − 𝑝𝑦 𝑧 → 𝐿෢𝑥 = 𝑌.
෠ 𝑃෡𝑧 − 𝑃
෢ መ ෠
𝑦 . 𝑍 = −𝑖ℏ. 𝑌.
መ
+ 𝑖ℏ. 𝑍.
𝜕𝑧 𝜕𝑦

𝐿 = 𝑟Ԧ × 𝑝Ԧ
 Measurement in Quantum Mechanics
• In classical physics, it is possible to perform measurements
on a system without disturbing it significantly because the
disturbance is small enough to neglect.
• However, in quantum mechanics, the measurement process
perturbs the system significantly because in atomic and
subatomic systems, the act of measurement induces
nonnegligible or significant disturbances.
• In general, the act of measurement generally changes the state
of the system.
 Measurement in Quantum Mechanics
• Consider the quantum system in the state |ψ>. Before
measuring an observable A, the state |ψ> is the linear
superposition of the eigenstates |ψn> of the corresponding
operator A :

• According to Postulate 4, the act of measuring A changes the

state of the system from |ψ> to one of the eigenstates |ψn> of
the operator A, and the result obtained is the eigenvalue an.
• The only exception to this rule is when the system is already
in one of the eigenstates of the observable being measured.
 Measurement in Quantum Mechanics
• Before a measurement, we do not know in advance with
certainty in which eigenstate, among the various states
|ψn>, a system will be after the measurement; only a
probabilistic outcome is possible.
• Postulate 4 states the probability of finding the system in a
nondegenerate eigenstate |ψn> :

• In conclusion, in quantum mechanics, it is the effects of the

interference by the equipment on the system.
 Expectation Values
• In essence, the expectation value <A> represents the average
result of measuring A on the state |ψ>.

• This relation can be extended to continuous distribution :

• The key difference in quantum mechanics is that measuring

the same observable may obtain different results.
Example
H n = an n , n n = 1 → n H n = n an n = an n n = an
→ an = n H n
a1 = 1 H 1 = 1  0 1 =  0 1 1 =  0
a2 = 2 H 2 = 2 0
a3 = 3 0 , a4 = 4 0 , a5 = 5 0
2
1  1
P1 (a1 ) = =
 15
1 5 2 3 5 15
 = 1 1 + 2 2 + 3 3 + 4 4 + 5 5 =
19 19 19 19 19 19
2 1 1
1  =( 1 1 ) 2 =
19 19
2 2 2 2
2  4 3  2 4  3 5  5
P2 (a2 ) = = , P3 (a3 ) = = , P4 (a4 ) = = , P5 (a5 ) = =
 15  15  15  15

5
1 4 2 3 5 52
E =  Pa
i i =  0 +  2 0 +  3 0 +  4 0 +  5 0 =  0
1 15 15 15 15 15 15
 Commuting Operators
• Two observables A and B are said to be compatible if :
 A, B  = 0
• If A and B do not commute, they cannot be measured
simultaneously; the order in which they are measured
matters.
❑ Theorem : If two observables are compatible, their
corresponding operators possess a set of common (or
simultaneous) eigenstates (both degenerate and
nondegenerate).
→ A and B are simultaneously measurable.
 Measurement and the Uncertainty Relations
• The uncertainty condition pertaining to the measurement of
any two observables A and B :
1 
A.B  A, B 
2  
• Consider the joint measurement of the position and
momentum observables. Since these observables are not
compatible, their simultaneous measurement with infinite
accuracy is not possible.
 Measurement and the Uncertainty Relations
• Since :
X,P = i
 
• Applying the uncertainty condition for position and
momentum operators :

x .p 
2
• This is the interference between two measurements.
 Time Evolution Operator
❑ Physical systems are dynamic and evolve in time.
❑ In quantum mechanics, the time evolution from time t0 to t of
a quantum system is described by a linear operator U(t, t0) :

• U(t, t0) is the time evolution operator or propagator.

▪ The time evolution operator should do nothing when t=t0
lim U ( t , t0 ) = U ( t0 , t0 ) = I
t →t0
 Time Evolution Operator
❑ The propagator should preserve the normalization of state
kets. That is, if |ψ> is normalized at t0, it should also be
normalized at later times t.

  =  ( t )  ( t ) =  U ( t , t0 )U ( t , t0 ) 

→ U ( t , t0 )U ( t , t0 ) = I
▪ The propagator U(t,t0) is a unitary operator. A unitary
operator preserves the norm of the states.
 Time Evolution Operator
❑ The propagator should satisfy the composition property :
U ( t 2 , t0 ) = U ( t 2 , t1 )U ( t1 , t0 )
• From time-dependent Schrodinger equation (postulate 5) :
 Stationary States
❑ The idea of ‘stationary states’ was first introduced by Bohr
as a name given to those states of a hydrogen atom for which
the orbits that the electron occupied were stable. This term is
now used to identify those states of a quantum system that do
not change in time.
▪ In quantum mechanics, a stationary state turns out to be one
for which the probabilities of outcomes of a measurement of
any property of the system is the same no matter at what time
the measurement is made.
 Stationary States
• In the position representation, the time-dependent
Schrödinger equation for a particle :

• In case of time-independent potentials :

• The solution of this equation can be separable as :

 Stationary States
• Breaking this equation into 2 separate differential equations,
one depending on time and one depending on space variable :

Time-independent Schrodinger
equation

Stationary state
 Stationary States
❖ In summary, stationary states exist only for time-
independent potentials.
❖ The set of energy levels (the solutions of the Schrodinger
equation) are called energy spectrum.
❖ The states corresponding to discrete and continuous spectra
are called bound and unbound states, respectively.
❖The most general solution to the time-dependent Schrödinger
equation :
 Wave Packet
• The wave packet representing a particle of energy E and
momentum p moving in a potential V :
 Wave Packet
• Obviously, wave packet is one of the solutions of time-
dependent Schrodinger’s equation :

• This equation is valid for spatially varying potentials V =

V(x).
• Such wave packets are the physical “position” states of a
quantum system.
 The Conservation of Probability
• Since the Hamiltonian operator is Hermitian, the probability
density

is time-independent. It means that if |ψ(t)> is normalized, it

stays normalized for all subsequent times.
• To calculate the probability density in the position
representation :
 d  (t )  (t )
 (t )  (t ) = constt → =0
dt
d  (t )  (t ) d (t ) d (t )
=  (t ) +  (t )
dt dt dt
d  (t ) d (t ) i d (t ) i
i = H  (t ) → = − H  (t ) →  (t ) = −  (t ) H  (t )
dt dt dt

d (t ) i d (t ) i d (t ) i
= −( H  (t ) ) → =  (t ) H →  (t ) =  (t ) H  (t )
dt dt dt
 The Conservation of Probability
• Find the complex conjugate :

Conservation law of probability

Probability density Probability current density

 2
 (r , t )  (r , t ) P 2
i = H  (r , t ) → i =( + V (r , t )) (r , t ) = −  2 (r , t ) + V (r , t ) (r , t )
t t 2m 2m
 (r , t ) * 2
→i  (r , t ) = −  2 (r , t ) * (r , t ) + V (r , t ) (r , t ) * (r , t )(1)
t 2m
*
 (r , t ) *  * (r , t )  2 2  2
(i ) = −i = −   (r , t ) + V (r , t ) (r , t )  = −  2 * (r , t ) + V (r , t ) * (r , t )
t t  2m  2m
 * (r , t ) 2
→ −i  (r , t ) = −  2 * (r , t ) (r , t ) + V (r , t ) * (r , t ) (r , t )(2)
t 2m
  (r , t ) *  * (r , t )  2
⎯⎯⎯(1) − (2)
→i   (r , t ) +  (r , t )  = −  2 (r , t ) * (r , t ) −  2 * (r , t ) (r , t )  + V (r , t )  (r , t ) * (r , t ) − * (r , t ) (r , t ) 
 t t  2m
 2
→i  (r , t ) (r , t )  =
*
 2 * (r , t ) (r , t ) −  2 (r , t ) * (r , t ) 
t 2m
 2
i  (r , t ) (r , t )  = −
*
 2 * (r , t ) (r , t ) −  2 (r , t ) * (r , t ) 
t 2m
 (r , t ) =  (r , t ) * (r , t )
2
J (r , t ) =  (r , t ) * (r , t ) − * (r , t ) (r , t ) 
2m
 (r , t )  (r , t )
i = −J (r , t ) → i + J ( r , t ) = 0
t t
 Density Operator
• In quantum mechanics, the state of a quantum system (an
ensemble of objects) is represented by a state vector. A
quantum system with a state vector |ψ> is called pure state.
However, it is also possible for a system to be in a statistical
ensemble of different state vectors : they would be mixed
state.
• The density matrix (density operator) is especially useful for
mixed states, because any state, pure or mixed, can be
characterized by a single density matrix.
 Density Operator
❑ Example : Light polarization
The incandescent light
bulb (1) emits completely
random polarized photons
(2) with mixed state
density matrix
After passing through
vertical plane polarizer (3),
the remaining photons are
all vertically polarized (4)
and have pure state density
matrix

0.5 0  1 0 
 0 0.5 0 0 
   
 Density Operator
• For a finite-dimensional function space, the most general
density operator is of the form :
 =  pj  j  j
j

• This represents a mixed state, with probability pj that the

system is in the pure state |ψj>.
• Time evolution of density operator :

 ( t0 ) = U ( t , t0 )  ( t )U ( t , t0 )
 Density Operator
❑ Time evolution of density operator : Von Neumann equation
 Density Operator
❑ The density matrix ρ for the pure state |ψ> is given by :

❑ The density matrix has some properties :

 Time Evolution of Expectation Value
❑ If the state |Ψ(t)> is normalized, the expectation value is :

• The observable A is a constant of the motion if the

expectation value of an operator does not depend on time and
commutes with the Hamiltonian is constant in time.
 Poisson Bracket and Commutators
❑ To establish a connection between quantum mechanics and
classical mechanics, we may look at the time evolution of
observables.
▪ The Poisson bracket between two dynamical variables A and
B is defined in terms of the generalized coordinates qi and the
momenta pi of the system:

• The Poisson brackets of the canonical coordinates are :

qi , q j  = 0, pi , p j  = 0,qi , p j  = ij
 Poisson Bracket and Commutators
❑ Properties of Poisson Bracket :
▪ Anti-symmetry :

▪ Linearity :

▪ Complex conjugate :

▪ Distributivity:

▪ Jacobi identity:
 Poisson Bracket and Commutators
❑ The total time derivative of a dynamical variable A is :

❑ Hamiltonian equations of classical mechanics :

❑The total time evolution of a dynamical variable A :

❑ If dA/dt=0 or {A,H}=0, A is a constant of motion

(conserved through motion).
 Poisson Bracket and Commutators
❑ Comparing with the classical relation :

❑ We can infer the general rule:

▪ Note : the expressions of classical mechanics can be derived

from quantum mechanics but the opposite is not possible.
 Constant of Motion
• An observable quantity Q will be a constant of motion if it
commutes with the Hamiltonian H, and it does not itself
depend explicitly on time.

• For arbitrary state of quantum mechanics, if :

 H ,Q = 0
and Q is not dependent on time :
d Q
=0
dt
Example
 Ehrenfest Theorem
• If quantum mechanics is to be more general than classical
mechanics, it must contain classical mechanics as a limiting
case.

• For classical mechanics :

Quantum Mechanics vs. Classical Mechanics
❑ Question :
▪ How does one decide on when to use classical or quantum
mechanics to describe the motion of a given system?
▪ How do we know when a classical description is good
enough or when a quantum description becomes a must?
Quantum Mechanics vs. Classical Mechanics
❑ Answer :
▪ If the value of the action of a system is too large compared to
h, this system can be accurately described by means of
classical physics. Otherwise, the use of a quantal description
becomes unavoidable.
Exercise
Exercise
THE END!!!