Chapter 2

Quantum theory

This chapter introduces some of the terminology of

quantum mechanics and stating the postulates of
quantum mechanics and showing some of their
applications
 Postulate 1
• For any possible state of a system composing of N particles, there is a
function, Ψ (psi) wavefunction (state function) , of the coordinates of
the particles of the system and time that completely describes the
system.

• It contains information about all the properties of the system.

• it has no physical meaning (can’t be directly measured by

experiment) .
• The quantity 𝜓 𝑟 2 𝑑𝜏 is the probability that the particle lies in the
volume element dτ located at the point r.
• For a single particle described by Cartesian coordinates, the wavefunction is:
•
• Ψ = Ψ (x, y, z, t)
•
• For two particles, the coordinates of each particle must be specified so that:
•
• Ψ = Ψ (x1, y1, z1, x2, y2, z2, t)
•
• For a general system, we can use generalized coordinates ri:
•
• Ψ = Ψ (r1, r2, r3, …, t) = Ψ (ri, t)
• Where, r1 is x1, y1, z1 and so on.

• Ψ the time-dependent wavefunction.

• .𝝍 is the time-independent wavefunction.
• 𝝍 𝒓 𝟐 = 𝝍∗ 𝒓 𝝍 𝒓 if 𝝍(𝒓) is complex;
• 𝝍∗(r) is the complex conjugate of 𝝍(𝒓).

𝟐
• 𝝍 𝒓 = 𝝍∗ 𝒓 𝝍 𝒓 = 𝝍𝟐 𝒓 if 𝝍(𝒓) is real, 𝝍∗ = 𝝍.

• The probability of a particle being in a certain region between points a

and b in space
𝒃 𝟐 𝒅𝝉 𝒃 ∗
• 𝐩𝐫𝐨𝐛𝐚𝐛𝐢𝐥𝐢𝐭𝐲 𝒂 ≤ 𝛕 ≤ 𝒃 = ‫𝒂׬‬ 𝝍 = ‫𝝉𝒅 𝝍 𝝍 𝒂׬‬
 The probability varies from 0 to unity
• Normalization: • Orthogonality:
• The probability for a particle • If two functions 𝜓1 and 𝜓2 are said
to be orthogonal if having the
evaluated over the entire space property:
•
• ‫= 𝜏𝑑 𝜓 ∗ 𝜓 𝑒𝑐𝑎𝑝𝑠 𝑙𝑙𝑎׬‬ ∗

• ‫𝟎 = 𝝉𝒅 𝟐𝝍 𝟏𝝍 ׬‬
∞
‫׬‬−∞ 𝜓 ∗ 𝜓 𝑑𝜏 = 1 • or ∗

• ‫𝟎 = 𝝉𝒅 𝟐𝝍 𝟏𝝍 ׬‬
•
• 𝝍 normalized wavefunction.
• Sets of functions that are normalized
• Therefore wavefunction 𝝍 ≠∞ and mutually orthogonal are called
orthonormal.
over a finite region of space
 Normalization Constant
• : if 𝜓 is not normalized:
∞ ∗
• ‫׬‬−∞ 𝝍
𝝍 𝒅𝝉 ≠ 𝟏
•
• To convert it to be normalized, multiply it by a suitable constant A
(Normalization Constant) :
•
∞ ∞
• ‫׬‬−∞(𝑨𝝍∗ ) 𝑨𝝍 𝒅𝝉 = 𝑨 𝟐
‫׬‬−∞ 𝝍∗ 𝝍 𝒅𝝉 = 𝟏
Well-behaved or physically acceptable wavefunction
• The normalized wavefunction must be finite, single valued, and
continuous WHY

( Acceptable infinite. not single discontinuous

• Finite
• The implication of the normalization condition is that the
wavefunction cannot become infinite over a finite region of space. If it
∞
‫׬‬−∞ 𝜓 ∗ 𝜓
is infinite, the integral dτ would be infinite.
• Single valued
• Have one value at each point of space. Because in a given region of
space, there is only one probability of finding a particle.
• Continuous
• If there is a certain probability of finding an electron at a given
distance from the nucleus, there will be a slightly different probability
if the distance is changed slightly. Therefore, the probability function
does not have discontinuities and so the wavefunction must be
continuous (so there are no kinks in the function).
 • Example: Determine whether each of the following functions is
acceptable or not as a state function over the indicated intervals:
𝟏
a) 𝟒−𝒙
, 𝟎≤𝒙≤𝟑
b)Acceptable; because it meets all criteria for acceptable wavefunctions
within that stated range of the variable x.

𝟏
a) 𝟒−𝒙
, 𝟎 ≤ 𝒙 ≤ 𝟏𝟎
b)Not acceptable, because the function approaches infinity for x = 4,
which is part of the range
•
a) ± 𝒙, 𝒙≥𝟎
b)Not acceptable, because the function is not single-valued.
 Postulate 2
• For every observable in classical mechanics there is a corresponding
operator in quantum mechanics.

• An observable is any dynamical variable that can be measured (such

as energy, momentum, angular momentum, and position coordinates).
•
• An operator is a symbol to carry out some mathematical operation on
𝒅
a function e.g., multiplication x, differentiation ,
𝒅𝒙
• SQR (square) ()2 SQRT (square root).

• The operators in quantum mechanics are linear and Hermitian

 ෡ 𝒇 𝒙 = 𝒈(𝒙) Operator 𝑨
•𝑨 ෡ operates on f(x) to give a function g(x)
• Observable Operator form Operator symbol

Momentum
Px 𝑑 𝑃෠ x
−𝑖ħ
𝑑𝑥
Py 𝑑 𝑃෠ y
−𝑖ħ
𝑑𝑦
Pz 𝑑 𝑃෠ z
−𝑖ħ
𝑑𝑧

Positions (coordinates) Multiply by x, y, z, r ෠ 𝑌,

𝑋, ෠ 𝑍,
መ 𝑅෠
x, y, z, r
ħ2 𝑑 2 𝑑2 𝑑2
Kinetic energy T − ( 2+ 2
+ 2 𝑇෠
2𝑚 𝑑𝑥 𝑑𝑦 𝑑𝑧

Potential energy V(r) Multiply by V(r) ෠

𝑉(𝑟)
 • An operator is said to be linear if:
෡ 𝒄𝟏 𝒇𝟏 𝒙 + 𝒄𝟐 𝒇𝟐 𝒙
•𝑨 ෡ 𝒇𝟏 𝒙 + 𝒄𝟐 𝑨
= 𝒄𝟏 𝑨 ෡ 𝒇𝟐 𝒙
•
• where 𝑐1 and 𝑐2 are constants and 𝑓1 𝑥 and 𝑓2 𝑥 are functions.
𝑑 𝑑𝑓1 (𝑥)
መ
• 𝐴 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑐1 +
𝑑𝑥 𝑑𝑥
𝑑𝑓2 (𝑥)
𝑐2
𝑑𝑥
𝑑𝑓1 (𝑥) 𝑑𝑓2 (𝑥)
መ መ
• 𝑐1 𝐴𝑓1 𝑥 + 𝑐2 𝐴𝑓2 𝑥 = 𝑐1 + 𝑐2
𝑑𝑥 𝑑𝑥
• Thus:
𝑑 𝑑𝑓1 (𝑥) 𝑑𝑓2 (𝑥)
• 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑐1 + 𝑐2
𝑑𝑥 𝑑𝑥 𝑑𝑥
𝐴መ 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = න 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 𝑑𝑥

= 𝑐1 න 𝑓1 𝑥 𝑑𝑥 + 𝑐2 න 𝑓2 𝑥 𝑑𝑥

መ 1 𝑥 + 𝑐2 𝐴𝑓
𝑐1 𝐴𝑓 መ 2 𝑥 = 𝑐1 න 𝑓1 𝑥 𝑑𝑥 + 𝑐2 න 𝑓2 𝑥 𝑑𝑥

Thus:
• ‫𝑐 ׬‬1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 𝑑𝑥 = 𝑐1 ‫𝑓 ׬‬1 𝑥 𝑑𝑥 + 𝑐2 ‫𝑓 ׬‬2 𝑥 𝑑𝑥
 • 𝐴መ 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑆𝑄𝑅 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥
•
• = 𝑐12 𝑓12 𝑥 + 𝑐22 𝑓22 𝑥 + 2𝑐1 𝑐2 𝑓1 𝑥 𝑓2 𝑥
•
መ 1 𝑥 + 𝑐2 𝐴𝑓
• 𝑐1 𝐴𝑓 መ 2 𝑥 = 𝑐1 𝑆𝑄𝑅𝑓1 𝑥 + 𝑐2 𝑆𝑄𝑅𝑓2 𝑥 = 𝑐1 𝑓12 𝑥 +
𝑐2 𝑓22 𝑥
• Thus:
• 𝑆𝑄𝑅 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 ≠ 𝑐1 𝑆𝑄𝑅𝑓1 𝑥 + 𝑐2 𝑆𝑄𝑅𝑓2 𝑥
•
• The "square" operator, SQR, on the other hand, is nonlinear
• Example
• Perform the following operations:
𝑑2
• a 𝐴መ 2𝑥 , 𝐴መ =
𝑑𝑥 2
𝑑2 𝑑
• b 𝐴መ (𝑥 2 ), 𝐴መ = +2 +3
𝑑𝑥 2 𝑑𝑥
•
• Answer:
𝑑2
• a 𝐴መ 2𝑥 = 2𝑥 =0
𝑑𝑥 2
𝑑2 2 𝑑 2
• b 𝐴መ 𝑥 2 = 𝑥 + 2 𝑥 + 3𝑥 2 = 2 + 4𝑥 + 3𝑥 2
𝑑𝑥 2 𝑑𝑥
• Example 2.3
• Determine whether the following operators are linear or nonlinear:
• a 𝐴መ = SQRT (take the square root)
• b 𝐴መ = 𝑥 2 (multiply by x2)
•
• Answer:
• a 𝐴መ 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = SQRT 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = ሾ𝑐1 𝑓1 𝑥
1
+ 𝑐2 𝑓2 𝑥 ሿ2

•
1 1
• መ 1 𝑥 + 𝑐2 𝐴𝑓
𝑐1 𝐴𝑓 መ 2 𝑥 = 𝑐1 𝑆𝑄𝑅𝑇𝑓1 𝑥 + 𝑐2 𝑆𝑄𝑅𝑇𝑓2 𝑥 = 𝑐1 𝑓 𝑥 + 𝑐2 𝑓 (𝑥)
2 2
1 2
• Thus:
• SQRT 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 ≠ 𝑐1 𝑆𝑄𝑅𝑇𝑓1 𝑥 + 𝑐2 𝑆𝑄𝑅𝑇𝑓2 𝑥
•
• and so SQRT is a nonlinear operator.
 • 𝑏 𝐴መ 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑥 2 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 =
𝑐1 𝑥 2 𝑓1 𝑥 + 𝑐2 𝑥 2 𝑓2 𝑥
•
መ 1 𝑥 + 𝑐2 𝐴𝑓
• 𝑐1 𝐴𝑓 መ 2 𝑥 = 𝑐1 𝑥 2 𝑓1 𝑥 + 𝑐2 𝑥 2 𝑓2 𝑥

• Thus:

• 𝑥 2 𝑐1 𝑓1 𝑥 + 𝑐2 𝑓2 𝑥 = 𝑐1 𝑥 2 𝑓1 𝑥 + 𝑐2 𝑥 2 𝑓2 𝑥
•
• and so x2 (multiply by x2) is a linear operator
• Hermitian operator:
• Consider two functions ϕ1 and ϕ2, the operator 𝐴መ is Hermitian if:
∗ ∗
෡ 𝝓𝟐 𝐝𝛕 = ‫𝑨 𝟐𝝓 ׬‬
• ‫𝑨 𝟏𝝓 ׬‬ ෡ ∗ 𝝓𝟏 𝐝𝛕

• Because the value of an observable is a real quantity,

• the eigenvalues of any operator that corresponds to an observable
must themselves be real.
• The reality of eigenvalues is guaranteed if the operator is Hermitian
operator.
 Postulate 3
• In any measurement of the observable associated with the operator
መ the only values that will ever be observed are the eigenvalues 𝑎𝑛 ,
𝐴,
which satisfy the eigenvalue equation:
•𝑨෡ 𝝍 = 𝒂𝒏 𝝍 eigenvalue equation
𝒏 𝒏

• 𝝍 is an ‘eigenfunction’ 𝒂 constant is eigenvalue

• In this case, the observable has a sharp quantity (only one value).
• For example, the only found values for the energy of a system are the
eigenvalues of the energy operator 𝐻෡ (Hamiltonian operator) and no
others.
 • Example
• Show that 𝑒 𝑎𝑥 is an eigenfunction of the operator d/dx. What is the eigenvalue?
•
• Answer:
𝒅 𝒂𝒙
• 𝒆 = 𝒂 𝒆𝒂𝒙
𝒅𝒙
• And so the eigenvalue is a.
•
• Example
𝑑
• Show that 𝑒 𝑖𝑘𝑥 is an eigenfunction of the operator 𝑃෠𝑥 = −𝑖ħ . What is the
𝑑𝑥
eigenvalue?
• Answer:
𝒅 𝒊𝒌𝒙
• ෡
𝑷𝒙 𝒆 = −𝒊ħ 𝒆 = 𝒌ħ𝒆𝒊𝒌𝒙
𝒊𝒌𝒙
𝒅𝒙
•
• kħ is the eigenvalue of the operator 𝑃෠𝑥 .
 Commutation and non-commutation:
• the outcome of successive operations (A followed by B, [BA],
or B followed by A, [AB]) depends on the order in which the operations are
carried out.

That is, if: ෡𝑩

𝑨 ෡ 𝒇(𝒙) = 𝑩
෡𝑨෡ 𝒇(𝒙)

• The two operators 𝐴መ and 𝐵෠ commute.

• Their observable quantities have simultaneously well-defined values.

• And if: ෡𝑩
𝑨 ෡ 𝒇(𝒙) ≠ 𝑩
෡𝑨෡ 𝒇(𝒙)

•
• The two operators 𝐴መ and 𝐵෠ do not commute.
 Example : Consider the operators 𝑋෠ and 𝑃෠𝑥 and a specific
function x2. Determine whether the operators 𝑃෠𝑥 and 𝑋෠
commute or do not commute

• Answer:
𝑑 2
መ ෠ ෠ ෠
• 𝐴𝐵𝑓 𝑥 = 𝑋𝑃𝑥 𝑥 = 𝑥 (−𝑖ħ 𝑥 ) = 𝑥 −2ħ𝑖 𝑥 = −2ħ𝑖𝑥 2
2
𝑑𝑥
•
𝑑 𝑑 3
෠ መ ෠ ෠
• 𝐵𝐴𝑓(𝑥) = (𝑃𝑥 𝑋) x = −𝑖ħ
2 2
𝑥 𝑥 = −𝑖ħ 𝑥 = -3ħi x2
𝑑𝑥 𝑑𝑥
• Thus, the operators 𝑋෠ and 𝑃෠𝑥 do not commute.
 መ 𝐵෠ , is defined as:
• The commutator of the two operators, 𝐴,
•
• ෡, 𝑩
𝑨 ෡ = 𝑨
෡𝑩෡ −𝑩
෡𝑨෡

෡, 𝑩
• If 𝑨 ෡ f(x) = 𝑨
෡, 𝑩
෡ = 0 for f(x) then 𝑨
෡ 𝒂𝒏𝒅 𝑩
෡ commute.

෡, 𝑩
• If 𝑨 ෡ f(x) = 𝑨
෡, 𝑩
෡ ≠0 ෡ 𝒂𝒏𝒅 𝑩
for f(x) then 𝑨 ෡
do not commute.
 ෡ 𝒙, 𝑿
Example: Evaluate the commutator 𝑷 ෡ .

• We let 𝑃෠𝑥 , 𝑋෠ act upon an arbitrary function f (x):

•
• 𝑃෠𝑥 , 𝑋෠ 𝑓 𝑥 = 𝑃෠𝑥 𝑋෠ 𝑓 𝑥 − 𝑋෠ 𝑃෠𝑥 𝑓 𝑥
•
𝑑 𝑑
෠ ෠
• 𝑃𝑥 𝑋 𝑓 𝑥 = −𝑖ħ 𝑥𝑓 𝑥 = −𝑖ħ𝑓 𝑥 − 𝑥𝑖ħ 𝑓 𝑥
𝑑𝑥 𝑑𝑥
𝑑
• 𝑋෠ 𝑃෠𝑥 𝑓 𝑥 = −𝑥𝑖ħ 𝑓 𝑥
𝑑𝑥
•
• 𝑃෠𝑥 𝑋෠ 𝑓 𝑥 − 𝑋෠ 𝑃෠𝑥 𝑓 𝑥 = −𝑖ħ𝑓 𝑥
•
• we get: 𝑃෠𝑥 , 𝑋෠ = −𝑖ħ
•

• Thus, the two operators do not commute and therefore, their corresponding
observable quantities “𝑥 and 𝑃𝑥 ” do not have simultaneously well-defined
values,
• Example
• Evaluate the commutator 𝑇෠𝑥 , 𝑃෠𝑥 ; kinetic energy and momentum in x
direction.
•
• Answer:
• 𝑇෠𝑥 , 𝑃෠𝑥 𝑓 𝑥 = 𝑇෠𝑥 𝑃෠𝑥 𝑓 𝑥 − 𝑃෠𝑥 𝑇෠𝑥 𝑓 𝑥
•
ħ2 𝑑 2 𝑑 𝑖ħ3 𝑑 3
• 𝑇෠𝑥 𝑃෠𝑥 𝑓 𝑥 = (− )(−𝑖ħ )𝑓 𝑥 = 𝑓 𝑥
2𝑚 𝑑𝑥 2 𝑑𝑥 2𝑚 𝑑𝑥 3
•
𝑑 ħ2 𝑑 2 𝑖ħ3 𝑑 3
• 𝑃෠𝑥 𝑇෠𝑥 𝑓 𝑥 = (−𝑖ħ )(− )𝑓 𝑥 = 𝑓 𝑥
𝑑𝑥 2𝑚 𝑑𝑥 2 2𝑚 𝑑𝑥 3
•
• Therefore,
• 𝑇෠𝑥 𝑃෠𝑥 𝑓 𝑥 − 𝑃෠𝑥 𝑇෠𝑥 𝑓 𝑥 = 𝑇෠𝑥 , 𝑃෠𝑥 = 0 Thus, they commute
Postulate 4.
• When a system is described by a wavefunction 𝜓, then the average value of the
observable corresponding to 𝐴መ in a series of measurements is equal to the
expectation value of 𝐴መ , which is given by:

∞
‫׬‬−∞ 𝝍∗ 𝑨
෡ 𝝍𝒅𝝉
• 𝒂 = ∞
‫׬‬−∞ 𝝍∗ 𝝍𝒅𝝉
•
• If the wavefunction is chosen to be normalized to 1, then the expectation value is
simply:
•
∞
• 𝒂 = ෡ 𝝍𝒅𝝉
‫׬‬−∞ 𝝍∗ 𝑨
• The observable in this case has not a sharp quantity (i.e. has more than
one value).