QUANTUM

MECHANICS
FORMALISM OF QUANTUM MECHANICS
• Consider the wavefunction
Ψ = 𝑐1 Ψ1 + 𝑐2 Ψ2 + 𝑐3 Ψ3

• Note that the coefficients 𝑐𝑛 are in general complex. If we represent Ψ as a column matrix
𝑐1
Ψ = 𝑐2 ,
𝑐3
• then normalization can be written as
𝑐1 3

Ψ Ψ = 𝑐1∗ 𝑐2∗ 𝑐3∗ 𝑐2 = ෍ 𝑐𝑛 2 =1

𝑐3 𝑛=1
𝑐1
• The column matrix is the ket Ψ = 𝑐2 and the row matrix is a bra Ψ = 𝑐1∗ 𝑐2∗ 𝑐3∗ .
𝑐3
 FORMALISM OF QUANTUM MECHANICS
𝑐1 1 0 0
Ψ = 𝑐2 = 𝑐1 0 + 𝑐2 1 + 𝑐3 0
𝑐3 0 0 1
where the basis vectors are now
1 0 0
• 𝜓1 = 0 , 𝜓2 = 1 , 𝜓3 = 0 .
0 0 1
𝑐1 𝑑1
For two wavefunctions 𝜓 = 𝑐2 and 𝜙 = 𝑑2 ,
𝑐3 𝑑3
𝑐1
𝜙 𝜓 = 𝑑1∗ 𝑑2∗ 𝑑3∗ 𝑐2 = 𝑑1∗ 𝑐1 + 𝑑2∗ 𝑐2 + 𝑑3∗ 𝑐3 .
𝑐3
∞
In terms of functions, we saw this when looking at orthonormality: ‫׬‬−∞ 𝜓𝑛∗ 𝜓𝑚 𝑑𝑥 = 𝛿𝑛𝑚 is written as 𝜓𝑛 𝜓𝑚 = 𝛿𝑛𝑚
EXAMPLES
2 1 + 3𝑖 1 0 0
1. Let 𝐴 = −7𝑖 and 𝐵 = 4 , with basis vectors 0 , 1 , 0 .
1 8 0 0 1
(a) Calculate 𝑎 𝐴 and 𝑎 𝐵 .
2 2𝑎 1 + 3𝑖 𝑎 + 3𝑖𝑎
𝑎 𝐴 = 𝑎 −7𝑖 = −7𝑎𝑖 , 𝑎𝐵 =𝑎 4 = 4𝑎
1 𝑎 8 8𝑎
(b) Find 𝐴 𝐵 and 𝐵 𝐴 .
⟨𝐴| = 2 7𝑖 1 , ⟨𝐵| = 1 − 3𝑖 4 8
EXAMPLES
1 + 3𝑖
⇒ 𝐴𝐵 = 2 7𝑖 1 4 = 2 1 + 3𝑖 + 7𝑖 4 + 1 8 = 2 + 6𝑖 + 28𝑖 + 8
8
= 10 + 34𝑖
2
⇒ 𝐵 𝐴 = 1 − 3𝑖 4 8 −7𝑖 = 1 − 3𝑖 2 + 4 −7𝑖 + 8 1 = 2 − 6𝑖 − 28𝑖 + 8
1
= 10 − 34𝑖

• Note: In general, 𝐵 𝐴 = 𝐴 𝐵 ∗ .
EXAMPLES
1
2. Let 𝜓 = 𝑎 3 . Find 𝑎 such that 𝜓 is normalized.
−2
1 𝑎
𝜓 = 𝑎 3 = 3𝑎 ⇒ ⟨𝜓| = 𝑎∗ 3𝑎∗ −2𝑎∗
−2 −2𝑎
The normalization condition is
𝑎 1
2 2 2 2
𝜓𝜓 =1⇒ 𝑎∗ 3𝑎∗ −2𝑎∗ 3𝑎 = 1 ⇒ 𝑎 +9 𝑎 +4 𝑎 =1⇒ 𝑎 =
−2𝑎 14

1 1 1
𝑒 𝑖𝜙
→ 𝑎 = ⇒𝑎= 𝑒 𝑖𝜙 ⇒ 𝜓 = 3
14 14 14 −2
SUMMARY: BRACKET NOTATION
1. The state of a particle is represented by a normalized vector Ψ in the Hilbert space 𝐿2 .
∞
I. The normalization of the wavefunction ‫׬‬−∞ Ψ 2 𝑑𝑥 = 1 is written as Ψ Ψ = 1.
∞
II. The orthonormality condition ‫׬‬−∞ Ψ𝑖∗ Ψ𝑗 𝑑𝑥 = 𝛿𝑖𝑗 is written as Ψ𝑖 Ψ𝑗 = 𝛿𝑖𝑗

2. The general solution is a linear combination of the stationary states. The TISE yields an infinite
set of stationary states 𝜓1 𝑥 , 𝜓2 𝑥 , … each with its associated energy 𝐸1 , 𝐸2 , … The time-
dependent stationary states are
Ψ𝑛 𝑥, 𝑡 = 𝜓𝑛 𝑥 𝑒 −𝑖𝐸𝑛 𝑡/ℏ .

3. The general time-dependent wave function

Ψ 𝑥, 𝑡 = σ∞
𝑛=1 𝑐𝑛 𝜓𝑛 𝑥 𝑒
−𝑖𝐸𝑛 𝑡/ℏ

is written using the braket notation as:

𝑛=1 𝑐𝑛 Ψ𝑛 .
Ψ = σ∞
DIRAC BRACKET NOTATION
4. The coefficients are expressed in the braket notation as:
∞
𝑐𝑛 = ‫׬‬−∞ ψ∗𝑛 Ψ(𝑥, 0) 𝑑𝑥 = ψ𝑛 Ψ(𝑥, 0)
∞ ∞ ∞ ∞ ∞

Ψ(𝑥, 0) = ෍ 𝑐𝑛 𝜓𝑛 = ෍ න ψ𝑛∗ 𝑥 ′ Ψ(𝑥 ′ , 0) 𝑑𝑥 ′ ψ𝑛 = න ෍ ψ∗𝑛 𝑥 ′ ψ𝑛 𝑥 Ψ 𝑥 ′ , 0 𝑑𝑥 ′

𝑛=1 𝑛=1 −∞ −∞ 𝑛=1

∞ ∞
⇒ ෍ ψ∗𝑛 𝑥 ′ ψ𝑛 𝑥 = 𝛿 𝑥 − 𝑥 ′ ⇒ Ψ 𝑥, 0 = න 𝛿 𝑥 − 𝑥 ′ Ψ 𝑥 ′ , 0 𝑑𝑥 ′
𝑛=1 −∞

The function 𝛿 𝑥 − 𝑥 ′ is called the Dirac delta function and has properties
∞
𝑓 𝑥 = ‫׬‬−∞ 𝑓 𝑥 ′ 𝛿 𝑥 − 𝑥 ′ 𝑑𝑥 ′
∞
𝛿 𝑥 − 𝑥 ′ = 2𝜋 −1
‫׬‬−∞ exp 𝑖𝑘 𝑥 − 𝑥 ′ 𝑑𝑘.
COMPARISON WITH VECTORS
Vectors Wave functions
• In a vector space, all vectors Normalization 𝑨 2 =1 ΨΨ =1
can be represented using the Projection ෝ⋅𝑨
𝐴1 = 𝒙 𝑐1 = Ψ1 Ψ
basis 𝒙 ෝ, 𝒛ො .
ෝ, 𝒚 ෝ⋅𝑨
𝐴2 = 𝒚 𝑐2 = Ψ2 Ψ
𝐴3 = 𝒛ො ⋅ 𝑨 𝑐3 = Ψ3 Ψ
• In a Hilbert space, wave
Orthonormal basis ෝ⋅𝒚
𝒙 ෝ=0 Ψ1 Ψ2 = 0
functions can be represented
ෝ⋅𝒙
𝒙 ෝ=1 Ψ1 Ψ1 = 1
using the basis Ψ1 , Ψ2 , Ψ3 .
The Hilbert space is limited to Components 1 1
ෝ= 0
𝒙 Ψ1 = 0
all wavefunctions satisfying 0 0
Ψ Ψ = 1. 0 0
ෝ= 1
𝒚 Ψ2 = 1
• We say that Ψ is square 0 0
integrable, or that the Hilbert 0
𝒛ො = 0 Ψ3
0
= 0
space is 𝐿2 . 1 1
 FORMALISM OF QUANTUM MECHANICS
• In the braket notation, operators are written as 𝑛 × 𝑛 matrices which transform one vector into another. For example,

1 2 0 2
= .
3 4 1 3
• An example of an operator is the Hamiltonian in the Schrodinger equation:

෡ 𝜓𝑛 = 𝐸𝑛 𝜓 .
𝐻

• Operators are written to the left of kets 𝐴መ 𝑈 and to the right of bras 𝑈 𝐴.
መ

• The identity operator 𝐼መ is

1 0
𝐼መ =
0 1

and 𝐼መ 𝑈 = 𝑈 .

• The identity operator is also written in terms of the basis vectors as

1 ⋮
መ𝐼 = σ∞
𝑛=1 ψ𝑛 ψ𝑛 = 0 1 0 ⋯ + ⋯+ 0 ⋯ 0 1
⋮ 1
 FORMALISM OF QUANTUM MECHANICS
• An operator 𝐴መ acting on Ψ gives the new wave function 𝑋 = 𝐴መ Ψ .

• The wavefunction 𝑋 can also be expanded in terms of the basis 𝜓𝑚 as

𝑋 = σ𝑚 𝑑𝑚 𝜓𝑚

where 𝑑𝑚 = 𝜓𝑚 𝑋 in the usual way. The wavefunction Ψ can also be expanded in terms of the basis 𝜓𝑚 as

Ψ = ෍ 𝑐𝑚 𝜓𝑚 ,
𝑚

𝑑𝑚 = 𝜓𝑚 𝑋 = 𝜓𝑚 𝐴መ Ψ = ෍ 𝜓𝑚 𝐴መ 𝜓𝑛 𝑐𝑛
𝑛

• The quantities 𝐴𝑚𝑛 = 𝜓𝑚 𝐴 𝜓𝑛 are called matrix elements of the operator 𝐴 in the basis 𝜓𝑚 .

𝑑𝑚 = σ𝑛 𝐴𝑚𝑛 𝑐𝑛 .

This can be written as a matrix equation:

𝑑1 𝐴11 𝐴12 … 𝑐1
𝑋 = 𝐴 𝜓 = 𝑑2 = 𝐴21 𝐴22 … 𝑐2
⋮ ⋮ ⋮ ⋱ ⋮
FORMALISM OF QUANTUM MECHANICS
• The average, or expectation value, of position 𝑥 is

𝑥 = නΨ ∗ 𝑥Ψ 𝑑𝑥 = න ෍ 𝑐𝑖∗ Ψ𝑖∗ 𝑥 ෍ 𝑐𝑛 Ψ𝑛 𝑑𝑥
𝑖 𝑛

= ෍ 𝑐𝑖∗ නΨ𝑖∗ 𝑥Ψ𝑛 𝑑𝑥 𝑐𝑛 = ෍ 𝑐𝑖∗ 𝑥𝑖𝑛 𝑐𝑛 = Ψ 𝑥ො Ψ

𝑖,𝑛 𝑖,𝑛

• Similarly, the expectation value of momentum 𝑝 is

ℏ 𝜕
𝑝 = න Ψ∗ Ψ 𝑑𝑥 = Ψ 𝑝Ƹ Ψ
𝑖 𝜕𝑥
FORMALISM OF QUANTUM MECHANICS
• The entry in the 𝑖th row and 𝑗th column of the operator matrix is 𝑇𝑖𝑗 = 𝑢𝑖 𝑇෠ 𝑢𝑗 .

𝑇11 𝑇12 ⋯ 𝑢1 𝑇෠ 𝑢1 𝑢1 𝑇෠ 𝑢2 ⋯
𝑇෠ = 𝑇21 𝑇22 ⋯ = 𝑢2 𝑇෠ 𝑢1 𝑢2 𝑇෠ 𝑢2 ⋯
⋮ ⋮ ⋱ ⋮ ⋮ ⋱
• Example: Suppose that in some orthonormal basis 𝑢1 , 𝑢2 , 𝑢3 an operator 𝐴መ
acts as follows: 𝐴 𝑢1 = 2 𝑢1 , 𝐴 𝑢2 = 3 𝑢1 − 𝑖 𝑢3 , 𝐴 𝑢3 = − 𝑢2 . The matrix is

𝑢1 𝐴መ 𝑢1 𝑢1 𝐴መ 𝑢2 𝑢1 𝐴መ 𝑢3
𝐴መ = 𝑢2 𝐴መ 𝑢1 𝑢2 𝐴መ 𝑢2 𝑢2 𝐴መ 𝑢3
𝑢3 𝐴መ 𝑢1 𝑢3 𝐴መ 𝑢2 𝑢3 𝐴መ 𝑢3
FORMALISM OF QUANTUM MECHANICS

𝑢1 (2 𝑢1 ) 𝑢1 3 𝑢1 − 𝑖 𝑢3 ) 𝑢1 − 𝑢2 )
⇒ 𝐴መ = 𝑢2 (2 𝑢1 ) 𝑢2 3 𝑢1 − 𝑖 𝑢3 ) 𝑢1 − 𝑢2 )
𝑢3 (2 𝑢1 ) 𝑢3 3 𝑢1 − 𝑖 𝑢3 ) 𝑢1 − 𝑢2 )

2 𝑢1 |𝑢1 3 𝑢1 𝑢1 − 𝑖 𝑢1 𝑢3 − 𝑢1 𝑢2 2 3 0
⇒ 𝐴መ = 2 𝑢2 |𝑢1 3 𝑢2 𝑢1 − 𝑖 𝑢2 𝑢3 − 𝑢2 𝑢2 = 0 0 −1
2 𝑢3 |𝑢1 3 𝑢3 𝑢1 − 𝑖 𝑢3 𝑢3 − 𝑢3 𝑢2 0 −𝑖 0

(since 𝑢𝑖 𝑢𝑗 = 𝛿𝑖𝑗