Introduction to Quantum

Mechanics
Duong Quang Ha, Ph.D
Angular Momentum
 Angular Momentum
❑ Classical angular momentum :
𝐿 = 𝑟Ԧ × 𝑝Ԧ
❑ In Cartesian coordinate system :
𝐿𝑥 = 𝑦𝑝𝑧 − 𝑧𝑝𝑦
𝐿𝑦 = 𝑧𝑝𝑥 − 𝑥𝑝𝑧
𝐿𝑧 = 𝑥𝑝𝑦 − 𝑦𝑝𝑥
❑ Under the influence of spherically symmetric or central
potential, the orbital angular momentum is conserved.
 Angular Momentum
❑ In quantum mechanics, angular
momentum plays a critical role in the
description of molecular rotations,
the motion of electrons in atoms, and
the motion of nucleons in nuclei.
❑The quantum theory of angular
momentum is a prerequisite for
studying molecular, atomic, and
nuclear systems.
 Angular Momentum
❑ In quantum mechanics, the classical vector 𝑟,
Ԧ 𝑝,
Ԧ 𝐿 become
operators.
𝑟Ԧ → (𝑥,
ො 𝑦,
ො 𝑧)Ƹ
𝑝Ԧ → (ෞ
𝑝𝑥 , 𝑝
ෞ𝑦 , 𝑝
ෞ𝑧 )
𝐿 → (𝐿෢𝑥 , 𝐿෢𝑦 , 𝐿
෢𝑧 )
❑ The corresponding principle :
𝐿෠ = 𝑅෠ × 𝑃෠ = −𝑖ħ𝑅෠ × 𝛻
 i j k
y z x z x y
L = r p = x y z = i− j+ k
py pz px pz px py
px py pz
Lx = ypz − zp y
Ly = zpx − xpz
Lz = xp y − ypx

Lx = Y Pz − Z Py X,px
Ly = Z Px − X Pz
Lz = X Py − Y Px

( )

Lx = (Y Pz − Z Py ) = (Y Pz ) − ( Z Py ) = ( Pz ) (Y ) − ( Py ) ( Z ) = Pz Y − Py Z = Lx

(L ) ( )
 
y,py z,pz
y = Ly , Lz = Lz
 Angular Momentum
❑ The Cartesian component of 𝐿෠ in position space :

and the relationship between all components of 𝐿෠ :

 Angular Momentum
❑ The commutation relations :

❑ Note : 𝐿෢𝑥 , 𝐿෢𝑦 , 𝐿

෢𝑧 do not commute → they can not be measured
simultaneously to arbitrary precision.
 A + B, C  =  A, C  +  B, C 
 AB, C  =  A, C  B + A  B, C 
 A, BC  =  A, B  C + B  A, C 
 Lx , Ly  = [Y Pz − Z Py , Z Px − X Pz ]= Y Pz , Z Px − X Pz  −  Z Py , Z Px − X Pz 
     
= Y Pz , Z Px  − Y Pz , X Pz  −  Z Py , Z Px  +  Z Py , X Pz 
       
= Y Pz , Z Px  − Y , X  Pz − Z  Py , Px  +  Z Py , X Pz  = Y Pz , Z Px  +  Z Py , X Pz 
           
= Y , Z Px  Pz + Y  Pz , Z Px  +  Z , X Pz  Py + Z  Py , X Pz 
       
= ( Y , Z  Px + Z Y , Px  ) Pz + Y (  Pz , Z  Px + Z  Pz , Px  ) + (  Z , X  Pz + X  Z , Pz  ) Py + Z (  Py , X  Pz + X  Py , Pz  )
               
= Y  Pz , Z  Px + X  Z , Pz  Py = −i Y Px + i X Py = i ( X Py − Y Px ) = i Lz
   

 Ly , Lz  = i Lx ,  Lz , Lx  = i Ly
   
 1
A.B   A, B 
2
1
Lx .Ly   Lx , Ly  = Lz
2 2
1
Ly .Lz   Ly , Lz  = Lx
2 2
1
Lz .Lx   Lz , Lx  = Ly
2 2

Lz = Lx = Ly = 0
2 2 2 2
L = Lx + Ly + Lz
 L2 , L  =  L 2 + L 2 + L 2 , L  =  L 2 + L 2 , L  =  L 2 , L  +  L 2 , L  =
 x
  x y z x
  y z x
  y x   z x 
=  Ly , Lx  Ly + Ly  Ly , Lx  +  Lz , Lx  Lz + Lz  Lz , Lx  = −i Lz Ly − i Ly Lz + i Ly Lz + i Lz Ly = 0
       
 L2 , L  =  L2 , L  = 0
 y
  z

 Angular Momentum
❑ In a more general representation, angular momentum 𝐽መ that
is defined by 3 components : 𝐽෡𝑥 , 𝐽෡𝑦 , 𝐽෡𝑧

❑ Since 𝐽෡𝑥 , 𝐽෡𝑦 , 𝐽෡𝑧 do not mutually commute, they do not

possess common eigenstates.

❑ 𝐽෡2 is a scalar operator :

𝐽෡2 , 𝐽෡𝑥 = 𝐽෡2 , 𝐽෡𝑦 = 𝐽෡2 , 𝐽෡𝑧 =0
 (J )

J 2, J  = 0 + = ( J x + iJ y ) = ( J x ) + (iJ y ) = J x + J y .(−i ) = J −
 z

(J )

2 = J+
,  → J ,  =  ,  , J z ,  =  ,  −

J + = J x + iJ y , J − = J x − iJ y
1 1
J x = ( J + + J − ), J y = ( J + − J − )
2 2i
− i J x , J y  = J x + J y + J z
2 2 2 2 2 2
J + J − = ( J x + iJ y )( J x − iJ y ) = J x + J y + iJ y J x − iJ x J y = J x + J y
 
+ i J x , J y  = J x + J y − J z
2 2 2 2 2 2
J − J + = ( J x − iJ y )( J x + iJ y ) = J x + J y + iJ x J y − iJ y J x = J x + J y
 
2 1 2
J = (J+ J− + J− J+ ) + J z
2
J+ , J− 
(J+ J− − J− J+ ) =   → J , J  = 2 J
1
Jz =
2 2  + − z
 2  2
,  J ,  =  ,  ,  =  = ,  ( J J ) ,  = J ,  J ,  = J ,  → 0

,  J z ,  =  ,  ,  = 
2 2 2 2  
,  (J x + J y ) ,  = ,  J x ,  + ,  J y ,  = ,  J x J x ,  + ,  J y J y , 
2 2 2 2 2 2 2 
= J x ,  + J y ,  = ,  (J − J z ) ,  = ,  J ,  − ,  J z ,  = ,  J ,  − ,  J z J z , 

=  − 2  0 → −     

 J 2 , J  =  J 2 + J 2 + J 2 , J + iJ  =  J 2 + J 2 , J  + i  J 2 + J 2 , J  =
 +
  x y z x y
  y z x
  x z y


= J y , Jx + Jz , Jx + i Jx , J y + i Jz , J y  =
      
2 2 2 2

       
=  J y , J x  J y + J y  J y , J x  +  J z , J x  J z + J z  J z , J x  + i ( J x , J y  J x + J x  J x , J y  ) + i(  J z , J y  J z + J z  J z , J y )
               
= −i J z J y − i J y J z + i J y J z + i J z J y + i (i J z J x + i J x J z − i J x J z − i J z J x ) = 0
J 2, J  = 0
 −

 J + , J z  =  J x + iJ y , J z  =  J x , J z  + i  J y , J z  = −i J y + i.(i ) J x = − J x − i J y = − ( J x + iJ y ) = − J +
       
 J − , J z  =  J x − iJ y , J z  =  J x , J z  − i  J y , J z  = −i J y − i.(i ) J x = J x − i J y = ( J x − iJ y ) = J −
       

J +  ,  =  ',  '
J z (  ',  ' ) = J z J +  ,  = ( J + J z −  J + , J z )  ,  = ( J + J z + J + )  ,  = J + J z  ,  + J +  , 
 
= J + (   ,  ) + J +  ,  = (  + )(  ',  ' ) → J +  ,  =  ',  +
J 2 (  ',  ' ) = J 2 J +  ,  = J + J 2  ,  = J + (  ,  ) =  ( J +  ,  ) =  (  ',  ' ) → J +  ,  =  ,  +
J −  ,  =  ',  '
J z (  ',  ' ) = J z J −  ,  = ( J + J z −  J − , J z  )  ,  = ( J + J z − J + )  ,  = J + J z  ,  − J +  , 
 
= J + (   ,  ) − J +  ,  = (  − )(  ',  ' ) → J −  ,  =  ',  −
J 2 (  ',  ' ) = J 2 J −  ,  = J − J 2  ,  = J − (  ,  ) =  ( J −  ,  ) =  (  ',  ' ) → J −  ,  =  ,  −
 μmin μmax
J- J+ J+ μ

μ μ+ℏ μ+2ℏ
−  
2 2
J +  , max = 0 → J − J +  , max = 0 → ( J − J z − J z )  , max = 0 → ( −  max 2 −  max )  ,  max = 0
→  − max 2 − max = 0 → max 2 + max = 
2 2
J −  , min = 0 → J + J −  , min = 0 → ( J − J z + J z )  , min = 0 → ( −  min 2 +  min )  ,  min = 0
→  − min 2 + min = 0 → min 2 − min = 
max 2 + max = min 2 − min → max 2 − min 2 + ( max + min ) = 0 → max + min = 0 → max = − min

Applying n step from μmin to μmax : n n n

max − min = n. → max = →  = ( + 1) 2

2 2 2
n
= j →  = ( j + 1) j 2 ( j = 0,1, 2,...)
2
 = m. ( m  j )
 Angular Momentum
❑෢𝐽2 and 𝐽෡𝑧 commute → they share the same eigenstates |α,β>
with the corresponding eigenvalues :

❑ For simplicity, we can assume that these eigenstates are

orthonormal.

❑ Introducing lowering and raising operators :

 Angular Momentum
❑ We can obtain the relationship :
 Angular Momentum
❑ Consider 𝐽෡± operate on |α,β>. Since 𝐽෡± do not commute with
𝐽෡𝑧 → the kets |α,β> are not eigenstates of 𝐽෡± .

❑ Thus, the ket ( 𝐽෡± |α,β>) is an eigenstate of 𝐽෡𝑧 with

eigenvalues ħ(β+1). Since 𝐽෡𝑧 and ෢
𝐽2 commute → (𝐽෡± |α,β>)
is also the eigenstate of ෢
𝐽2 .

❑ When 𝐽෡± acts on |α,β>, it does not affect the first quatum
number α but it raises or lowers the second quantum number
β by ±1.
 Angular Momentum
❑ We have :

❑ For a given eigenvalue α of ෢

𝐽2 , there exists an upper limit
for quantum number β.

❑ Since β has an upper limit :

 Angular Momentum
❑ There exists the lower limit of quantum number β :

❑ Since βmin was reached by n applications of 𝐽෡− on |α,βmax> :

n
= (0,1, 2,3,...)
2
n n
 = ( + 1) 2
❑ Introduce the notation j and m to denote βmax and β : 2 2
 Angular Momentum
❑ To determine the eigenvalues of 𝐽෡± within the |j,m> basis :

❑ Since |j,m> is normalized :

 Angular Momentum
❑ The eigenvalue equations for 𝐽෡+ and 𝐽෡− :
 Angular Momentum
❑ The expectation values of 𝐽෡𝑥 and 𝐽෡𝑦 :
 Angular Momentum
❑ Matrix Representation of Angular Momentum :
▪ Since ෢ 𝐽2 and 𝐽෡𝑧 commute, the set of their common
eigenstates {|j,m>} can be chosen as a basis; this basis is
discrete, orthonormal and complete.

❑ The matrices representing ෢ 𝐽2 and 𝐽෡𝑧 in the |j,m> basis are

diagonal, their diagonal elements being equal to ħ2j(j+1) and
ħm.
 Angular Momentum
❑ Since the operators 𝐽෡± do not commute with 𝐽෡𝑧 :
Example
 j, m , j = 1
m  j → m = −1, 0,1 → 1, −1 , 1, 0 , 1,1
 1, −1 J 2 1, −1 1, −1 J 2 1, 0 1, −1 J 2 1,1 
 
J 2 =  1, 0 J 2 1, −1 1, 0 J 2 1, 0 1, 0 J 2 1,1 
 
 1,1 J 2 1, −1 1,1 J 2 1, 0 1,1 J 2 1,1 
 
2 2 0 0  1 0 0
   
= 0 2 2 0  = 2 2 0 1 0
 0 2 0 0 1
 0 2   
 1, −1 J z 1, −1 1, −1 J z 1, 0 1, −1 J z 1,1 
 
Jz =  1, 0 J z 1, −1 1, 0 J z 1, 0 1, 0 J z 1,1  =
 
 1,1 J z 1, −1 1,1 J z 1, 0 1,1 J z 1,1 
 
− 0 0
 
= 0 0 0
 0 
 0 
 Angular Momentum
❑ Geometrical Representation of angular momentum :

j=2, state |2,m>

m = -2, -1, 0 ,1, 2

❑ For a fixed value of j, the total angular momentum 𝐽መ is

represented by a vector whose length is ħ 𝑗(𝑗 + 1).
 Angular Momentum
❑ Geometrical Representation of angular momentum :

❑ The z-component is < 𝐽෡𝑧 >=ħm. The x,y-components lie

within x-y plane.
 Spin Angular Momentum
❑ Stern–Gerlach experiment :
 Spin Angular Momentum
▪ Silver has 47 electron and the 47th electron occupies in 5s
orbital. If the silver atom is in ground state, its total angular
momentum l = 0.
▪ According to Schrödinger’s wave theory, if the atoms had an
orbital angular momentum l, we would expect the beam to
split into an odd (discrete) number of 2l + 1 components →
with l =0, there exists only one spot on the screen.
▪ However, the beam splits into 2 distinct components ???
 Spin Angular Momentum
❑ Sodium D-line doublet :
▪ Grotrian diagram for doublet states of
neutral sodium showing permitted
transitions, including Na D-line
transition at 589 nm.
▪ D-line is split into a doublet: D1 =
589.59 nm, D2 = 588.96 nm.
▪ Many lines of alkali atoms are
Na “D-line”
doublets. Occur because terms (bar s-
term) are split in two.
 Spin Angular Momentum
❑ Both experimental situations are consistent with the
possession of an intrinsic angular momentum and a magnetic
moment by individual electrons.
❑ Quantization of angular momentum had already arisen for
orbital angular momentum, and if this electron spin behaved
the same way, an spin angular momentum with quantum
number s was required to give just two states.
❑ The spin angular momentum of a particle does not depend
on its spatial degrees of freedom.
 Spin Angular Momentum
❑ Goudsmit and Uhlenbeck postulation :

Earth’s rotation Electron spin

 Spin Angular Momentum
❑ From the classical theory of electromagnetism, an orbital
magnetic dipole moment is generated with the orbital motion
of a particle of charge q:
𝑞
𝜇𝐿 = 𝐿
2𝑚
❑ For electron with charge –e :
−𝑒
𝜇𝐿 = 𝐿
2𝑚𝑒
 Spin Angular Momentum
❑ The spin magnetic dipole moment of an electron is :
𝑒
𝜇𝑠 = −𝑔𝑠 . 𝑆Ԧ
2𝑚𝑒
where gs is Landé factor (gyromagnetic
ratio of the electron). In practice , gs ≈ 2.
❑ Under the effect of external magnetic
field, the force will be exerted on
electron’s intrinsic dipole.
The direction and magnitude of the force is related to the
relative orientation of the field and the dipole.
 Spin Angular Momentum
❑ By analogy with orbital angular momentum, the
spin angular momentum is characterized by 2
numbers : the spin s and its projection ms on z-
axis, where ms = -s, -s+1, …, 0,1, …, s-1, s.
❑ From Stern–Gerlach experiment :
1 1
2𝑠 + 1 = 2 → 𝑠 = → 𝑚𝑠 = ±
2 2

❑ In nature it turns out that every fundamental particle has a

specific spin. Some particles have integer spin s (bosons) and
others have half-odd-integer (fermions).
 Spin Angular Momentum
❑ The theory of spin is identical to the general theory of
angular momentum. In particular, the spin is also represented
መ whose components 𝑆
by a vector operator 𝑆; ෢𝑥 , 𝑆෢𝑦 , 𝑆෡𝑧 :

❑ Since 𝑆෢2 and 𝑆෡𝑧 commute, they have the common

eigenvector |s, ms>:

❑ Similarly, we introduce :
 Spin Angular Momentum
❑ The spin states form an orthonormal and complete basis :

❑ For a particle with spin ½ :

1 1 1 1
|𝑠, 𝑚𝑠 >= | , >, | ,− >
2 2 2 2
❑ The eigenvalues of 𝑆෢2 and 𝑆෡𝑧 :
θ
 Spin Angular Momentum
❑ The matrix representation of the operator 𝑆෢2 and 𝑆෡𝑧 on the
basis |s, ms> :
 Pauli Matrices
❑ For s = ½, it is convenient to introduce Pauli matrices σx, σy,
σz related to spin vectors :

❑ The properties of Pauli matrices :

Exercise
Eigenfunctions of Orbital Angular Momentum
❑ The eigenstates of orbital angular momentum :

❑ The operators 𝐿෠ in spherical coordinates :

Eigenfunctions of Orbital Angular Momentum
❑ Since the operators 𝐿෠ and 𝐿 ෢𝑧 depend only on the angles θ
and φ, their eigenstates will only depend on θ and φ.

෢𝑧 depend only on φ :
❑ Since 𝐿
Eigenfunctions of Orbital Angular Momentum
෢𝑧 :
❑ The eigenfunctions and eigenvalues of 𝐿

❑ Φm must be single-value :

෢𝑧 :
❑ The expectation value of 𝐿
Eigenfunctions of Orbital Angular Momentum
❑ The eigenfunctions and eigenvalues of 𝐿෡2 :
Eigenfunctions of Orbital Angular Momentum
❑ The properties of Legendre functions :

❑ The normalization condition :

Eigenfunctions of Orbital Angular Momentum
❑ We can deduce the eigenfunctions :
THE END!!!