4: THE 7 POSTULATES

OF QUANTUM
MECHANICS
CHAPTER OVERVIEW
4: THE 7 POSTULATES OF QUANTUM MECHANICS
The following summary of the mathematical framework of quantum mechanics.

POSTULATE 1: QUANTUM MECHANICS

POSTULATE 2: QUANTUM MECHANICS
POSTULATE 3: QUANTUM MECHANICS
POSTULATE 4: QUANTUM MECHANICS
POSTULATE 5: QUANTUM MECHANICS
POSTULATE 6: QUANTUM MECHANICS
POSTULATE 7: QUANTUM MECHANICS

1 9/15/2020
Postulate 1: Quantum Mechanics
Every physically-realizable state of the system is described in quantum mechanics by a state function ψ that contains all
accessible physical information about the system in that state.

Discussion
The properties of a quantum mechanical system are determined by a wavefunction Ψ(r,t) that depends upon the spatial
coordinates of the system and time, r and t . For a single particle system, r is the set of coordinates of that particle
r = (x , y , z ) .
1 1 1 For more than one particle, r is used to represent the complete set of coordinates
r = (x , y , z , x , y , z , … x , y , z ). Since the state of a system is defined by its properties, Ψ specifies or identifies the
1 1 1 2 2 2 n n n

state and sometimes is called the state function rather than the wavefunction.

9/15/2020 Postulate 1.1 https://chem.libretexts.org/@go/page/20836

Postulate 2: Quantum Mechanics
If a system is in a quantum state represented by a wavefunction ψ , then

2
P =∫ Ψ dV (Postulate 2.1)

is the probability that in a position measurement at time t the particle will be detected in the infinitesimal volume dV .

Discussion
The wavefunction is interpreted to be the probability amplitude and the absolute square of the wavefunction, Ψ (r, t)Ψ(r, t), ∗

is interpreted to be the probability density at time t. A probability density times a volume is a probability, so for one particle
∗
Ψ (x1 , y1 , z1 , t)Ψ(x1 , y1 , z1 , t)dx1 dy1 dz1 (Postulate 2.2)

is the probability that the particle is in the volume dx dy dz located at x , y , z at time t . For a many particle system, we write
l l l

the volume element as dτ = dx dy dz … dx dy dz ; and Ψ (r, t)Ψ(r, t)dτ is the probability that particle 1 is in the
1 1 1 n n n
∗

volume dx dy dz at x y z and particle 2 is in the volume dx dy dz at x y z , etc. Because of this probabilistic

l l 1 l l l 2 2 2 2 2 2

interpretation, the wavefunction must be normalized.

∗
∫ Ψ (r, t)ψ(r, t)dτ = 1 (3-38)

allspace

The integral sign here represents a multi-dimensional integral involving all coordinates: x l … zn .
.

9/15/2020 Postulate 2.1 https://chem.libretexts.org/@go/page/20837

Postulate 3: Quantum Mechanics
Every observable in quantum mechanics is represented by an operator which is used to obtain physical information about the
observable from the state function. For an observable that is represented in classical physics by a function Q(x, p), the
corresponding operator is Q(x ^).
^, p

Discussion
For every observable property of a system there is a quantum mechanical operator. The operator for position of a particle in
three dimensions is just the set of coordinates x, y, and z, which is written as a vector
r = (x, y, z) = x x⃗ + y y ⃗ + zz ⃗ (3.1)

The operator for a component of momentum is

∂
^
P x = −iℏ (3.2)
∂x

and the operator for kinetic energy in one dimension is

2 2
ℏ ∂
^
T x = (− ) (3.3)
2
2m ∂x

and in three dimensions

^ = −iℏ∇
p (3.4)

and
2
ℏ
^ 2
T = (− )∇ (3.5)
2m

The Hamiltonian operator H ^

is the operator for the total energy. In many cases only the kinetic energy of the particles and the
electrostatic or Coulomb potential energy due to their charges are considered, but in general all terms that contribute to the
energy appear in the Hamiltonian. These additional terms account for such things as external electric and magnetic fields and
magnetic interactions due to magnetic moments of the particles and their motion.

9/15/2020 Postulate 3.1 https://chem.libretexts.org/@go/page/20838

Postulate 4: Quantum Mechanics
The time development of the state functions of an isolated quantum system is governed by the time-dependent Schrödinger
equation
∂
^
H (r, t)ψ(r, t) = iℏ Ψ(r, t) (4.1)
∂t

where H = T + V is the Hamiltonian of the system.

Discussion
The time evolution or time dependence of a state is found by solving the time-dependent Schrödinger equation (Eq. 4.1). For
the case where H^
is independent of time, the time dependent part of the wavefunction is e −iωt
where ω = E

ħ
or equivalently
ν =
E

h
, which shows that the energy-frequency relation used by Planck, Einstein, and Bohr results from the time-dependent
Schrödinger equation. This oscillatory time dependence of the probability amplitude does not affect the probability density or
the observable properties because in the calculation of these quantities, the imaginary part cancels in multiplication by the
complex conjugate.

9/15/2020 Postulate 4.1 https://chem.libretexts.org/@go/page/20839

Postulate 5: Quantum Mechanics
If a system is in a state described by a wave function ψ , then the average value of the observable corresponding to the ^
A

operator is given by
∞
∗ ^
∫ ψ Aψ dτ
∞
⟨A⟩ = (5.1)
∞
∗
∫ ψ ψ dτ
∞

If the wavefunction is normalizedt, then this expression simplifies to

∞
∗ ^
⟨A⟩ = ∫ ψ Aψ dτ (5.2)
∞

since
∞
∗
∫ ψ ψ dτ = 1 (5.3)
∞

9/15/2020 Postulate 5.1 https://chem.libretexts.org/@go/page/20840

Postulate 6: Quantum Mechanics
If a system is described by the eigenfunction Ψ of an operator A ^
then the value measured for the observable property
corresponding to A
^
will always be the eigenvalue a , which can be calculated from the eigenvalue equation.
^
AΨ = aΨ (6.1)

9/15/2020 Postulate 6.1 https://chem.libretexts.org/@go/page/20892

Postulate 7: Quantum Mechanics
If a system is described by a wavefunction Ψ, which is not an eigenfunction of an operator A ^
, then a distribution of measured
values will be obtained, and the average value of the observable property is given by the expectation value integral:
∗ ^
∫ Ψ AΨdτ
⟨A⟩ = (7.1)
∗
∫ Ψ Ψdτ

where the integration is over all coordinates involved in the problem. The average value ⟨A⟩, also called the expectation value,
is the average of many measurements. If the wavefunction is normalized, then the normalization integral in the denominator of
Eq. 4.1 equals 1, which then converts to

∗ ^
⟨A⟩ = ∫ Ψ AΨdτ (7.2)

9/15/2020 Postulate 7.1 https://chem.libretexts.org/@go/page/20901