Report

The Schrodinger . . .
Probability and . . .
The Harmonic . . . Wolkite University
Angular . . .
College of Natural and
Computational sciences
Home Page Department of Physics

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December 26, 2022
JJ II
J I
Page 1 of 71
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1. Preminaries
Probability and . . . • Quantum mechanics was formulated in two different ways by Schrodinger
The Harmonic . . . and Heisenberg.
Angular . . .
• Schrodingers wave mechanics and Heisenbergs matrix mechanics
are the representations of the general formalism of quantum me-
chanics in continuous and discrete basis systems, respectively.
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• What is observable?
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• An observable is a dynamical variable(physical quantities) that can
be measured.
JJ II
• In classical mechanics observables such as position, momentum ,
J I energy etc are represented by ordinary variables, while in quantum
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mechanics observables are represented by operators.
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• What is operator?
Full Screen • An operator is a mathematical rule that transforms a given function

into another function.
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• Or a mathematical rule that when applied to a ket |Ψi transforms it
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into another ket |Ψ0 i of the same space and when it acts on a brahΨ|
transforms it into another hΨ0 |.
• A hatˆover a symbol in the language of quantum theory indicates
The Schrodinger . . . that the symbol is mathematically an operator.
The Harmonic . . .
Angular . . .
1.1. Dirac Notation(Bra, Ket)
• The physical state of a system is represented in quantum mechan-
ics by elements of a Hilbert space; these elements are called state
vectors(wave function).
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• To manipulate the formalism of quantum mechanics with ease and
Title Page clarity, Dirac introduced the concepts of kets, bras, and bra-kets.
JJ II • Dirac denoted the state vector Ψ by the symbol|Ψi, which he called

a ket vector, or simply a ket Ψ.
J I
• To every ket vector |Ψi, there exists a unique bra vectorhΨ| and vice
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versa.
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• Or the bra vector corresponding to |Ψi is defined by hΨ|.
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• In quantum mechanics kets are represented by column matrices,
Close bras by row matrices and operators by square or rectangular matri-
ces.
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• Dirac denoted the scalar(inner) product by the symbol h|i, which he

called a bra-ket.
• For example the inner product of hα| and |βi denoted by hα|βi is a
The Schrodinger . . . scalar quantity.
• In quantum mechanics, since the scalar product is a complex num-
The Harmonic . . .
ber, the ordering matters a lot.
Angular . . .
• We must be careful to distinguish a scalar product from its complex

6 hβ|αi, but hα|βi = hβ|αi∗
conjugate; hα|βi =
• An operator always acts on a ket from the left side and acts on a bra
Home Page from the right side.
Title Page • There are also illegal products: such as |αiÂ, Âhα|.
JJ II • If |αi and |βi belong to the same vector space, products of the type
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|βi|αi and hα|hβ| are forbidden.
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• They are neither kets, nor bras, nor operators, they have no mathe-
matical or physical meaning.
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• If |αi and |βi belong, however, to different vector spaces (e.g., |αi
Full Screen belongs to a spin space and |βi to an orbital angular
N momentum
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space), then the product |αi |βi, written as |αi |βi, represents a
tensor product of |αi and |βi.
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1.2. Orthogonal, Normalized and Orthonormal States
Probability and . . . • Two kets,|Ψ1 i and |Ψ2 i, are said to be orthogonal if they have a van-
The Harmonic . . . ishing scalar product
Angular . . .
hΨ1 |Ψ2 i = 0. (1)
• A vector |Ψ1 i or |Ψ2 iis called normalized if,
hΨ1 |Ψ1 i = 1 or hΨ2 |Ψ2 i = 1 (2)

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• Two kets,|Ψ1 i and |Ψ2 i, are said to be orthonormal if they are orthog-
Title Page onal and if each one of them has a unit norm
JJ II
hΨ1 |Ψ2 i = 0, hΨ1 |Ψ1 i = 1, hΨ2 |Ψ2 i = 1, ⇒ hΨ1 |Ψ2 i = δnm . (3)
J I
where the Kronecker delta symbol is defined by
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δnm = 1 if n = m
Go Back (4)
6 m.
0 if n =
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• The outer product of |Ψ1 i and |Ψ2 i denoted by |Ψ1 ihΨ2 | is an opera-
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tor.
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1.3. Products of operators
Probability and . . . • The product of two operators is generally not commutative:
The Harmonic . . . ÂB̂ 6= B̂ Â (5)
Angular . . .
• The product of operators is, however, associative:
ÂB̂ Ĉ = Â(B̂ Ĉ) = (ÂB̂)Ĉ (6)
• When the product ÂB̂ operates on a ket |Ψi (the order of application
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is important), the operatorB̂ acts first on |Ψi and then Â acts on the
Title Page new ket (B|Ψi):
ÂB̂|Ψi = Â(B̂|Ψi). (7)
JJ II
• Similarly, when ÂB̂ Ĉ D̂ operates on a ket |Ψi, D̂ acts first, then Ĉ,
J I then B̂, and then Â.
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Go Back 1.4. Types of operators

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• Unit or identity operator: it is the operator that, when it operates on
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a function leaves the function unchanged.
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• In a matrix form , the identity operator is written in the form of

ˆ 1 0
I= . (8)
0 1
• While in bra-ket form, the identity operator can be written in the
The Schrodinger . . . form X
Probability and . . . Iˆ = |Ψi ihΨi |. (9)
The Harmonic . . . i
Angular . . .
• An operator Â is said to be Hermitian if it is equal to its adjoint Â† .i.e
Â = Â† .
• An operator Â is said to be Ske-Hermitian or ant-Hermitian if Â =

−Â† .
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• An operator P̂ is said to be a projection operator if it is Hermitian

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and equal to its own square: P̂ † = P̂ and P̂ 2 = P̂ . Example: unit
JJ II operator.
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1.5. Commutation relation
Go Back • The commutator of two operators Â and B̂, denoted by [Â, B̂], is de-
fined by
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[Â, B̂] = ÂB̂ − B̂ Â, (10)
Close and the anticommutator{Â, B̂} is defined by
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{Â, B̂} = [Â, B̂]+ = ÂB̂ + B̂ Â. (11)
• Two operators are said to commute if their commutator is equal to
The Schrodinger . . . zero and hence ÂB̂=B̂ Â.
• Any operator commutes with itself:
The Harmonic . . .
Angular . . . [Â, Â] = [B̂, B̂] = 0. (12)
Properties of commutators
Using the commutator relation Eq. (10), we can establish the follow-
ing properties:
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• Antisymmetry: [Â, B̂] =-[B̂, Â]
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• Linearity: [Â, B̂ + Ĉ + D̂ + ...]= [Â, B̂] + [Â, Ĉ + [Â, D̂] + ...
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• Hermitian conjugate of a commutator: [Â, B̂]† = [B̂ † , Â† ]
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• Distributivity: [Â, B̂ Ĉ]= [Â, B̂]Ĉ + B̂[Â, Ĉ]
Page 8 of 71 [ÂB̂, Ĉ]= Â[B̂, Ĉ] + [Â, Ĉ]B̂
Go Back • Jacobi identity: [Â, [B̂, Ĉ]]+ [B̂, [Ĉ, Â]] + [Ĉ, [Â, B̂]]=0
Full Screen • Operators commute with scalars: an operator Â commutes with any
scalar b. i.e [Â, b]=0.
Close
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• Exercise:If [q̂, p̂]= i~, prove that
l
i, [q̂, p̂l ]= i~ ∂∂p̂p̂ ,
l
ii, [p̂, q̂ l ]= -i~ ∂∂q̂q̂ .
1.6. Eigenvalues and Eigenvectors of an Operator
Probability and . . . • A state vector |Ψi is said to be an eigenvector (also called an eigenket
The Harmonic . . . or eigenstate) of an operator Â if the application of Â to |Ψi gives
Angular . . .
Â|Ψi = a|Ψi, (13)
where a is a complex number, called an eigenvalue of Â.
• This equation is known as the eigenvalue equation, or eigenvalue

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problem, of the operator Â.
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• Its solutions yield the eigenvalues and eigenvectors of Â.
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• An operator has usually more than one eigenvalues and eigenstates.
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• A set of eigenstate |Ψn i is said to be orthonormal if
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hΨm |Ψn i = δnm , (14)
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and complete if
Full Screen ∞
X
Iˆ = |Ψn ihΨn |. (15)
Close
n=1
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• Exercise:Show that the eigenvalues of a Hermitian operator are real.
1.7. Pictures in Quantum Mechanics
Probability and . . . • The representations of wave functions and operators in quantum
The Harmonic . . . mechanics is called pictures.
Angular . . .
• The time evolution of a quantum system can be described in differ-
ent pictures (formalism).
• The commonly used pictures in quantum mechanics includes the

Schrodinger picture, Heisenberg picture, and the Interaction pic-
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ture.
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• In Schrodinger picture the states vectors depend explicitly on time,
JJ II but the operators donot; while in Heisenberg picture the operators
depend explicitly on time , but the state vectors donot.
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• On the other hand, in interaction picture which also called the Dirac
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picture both the states vectors and operators evolve(depend) in time
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and this picture is intermediate between the Schrodinger and Heisen-
berg pictures.
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2. Angular Momentum
Probability and . . . • In classical mechanics, the angular momentum of a particle with
The Harmonic . . . momentum → −p and →
−
r is defined by
Angular . . .
→
−
L =→
−
r ×→
−
p = (ypz − zpy )î + (zpx − xpz )ĵ + (xpy − ypx )k̂ (16)
• The orbital angular momentum operator L̂ can be obtained by re-

placing →
−
p and → −
r by the corresponding operators in the position
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representation by −i~∇ and r̂ respectively
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î ĵ k̂ î ĵ k̂
JJ II L̂ = r̂ × p̂ ⇒ x̂ ŷ ẑ ⇒ −i~ x y z . (17)
∂ ∂ ∂
J I p̂x p̂y p̂z ∂x ∂y ∂z
Page 11 of 71 From this we see that

Go Back ∂ ∂
L̂x = ŷ p̂z − ẑ p̂y = −i~ ŷ − ẑ , (18)
∂z ∂y
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Close ∂ ∂
L̂y = ẑ p̂x − x̂p̂z = −i~ ẑ − x̂ , (19)
∂x ∂z
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∂ ∂
L̂z = x̂p̂y − ŷ p̂x = −i~ x̂ − ŷ . (20)
∂y ∂x
• Angular momentum does not exist in a one-dimensional space.
Probability and . . . L̂2 = L̂2x + L̂2y + L̂2z . (21)
The Harmonic . . .
Angular . . . • Eq. (21) represents square of angular momentum operator.
• We now proceed to determine the commutation relation between

the components of angular momentum operator.
• Applying the commutation relation

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[x̂, p̂x ] = [ŷ, p̂y ] = [ẑ, p̂z ] = i~, (22)

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JJ II it can be readily established that
J I [L̂x , L̂y ] = i~L̂z , (23)

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[L̂y , L̂z ] = i~L̂x , (24)
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[L̂z , L̂x ] = i~L̂y . (25)
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• Derive Eqs. (23) - (25)
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• They do not commute, we cannot measure them simultaneously to
arbitrary accuracy.
Exercise.Show the following commutation relations
The Schrodinger . . . i, [L̂z , L̂2x ] = i~L̂x L̂y + i~L̂y L̂x ,
Probability and . . . ii, [L̂z , L̂2y ] = −i~L̂x L̂y − i~L̂y L̂x ,
The Harmonic . . . iii, [L̂x , L̂2 ] = 0,
Angular . . . iv,[L̂y , L̂2 ] = 0,
v,[L̂z , L̂2 ] = 0.
2.1. Eigenstates and eigenvalues of the angular momen-

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tum operator
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• Since L̂2 commutes with L̂x , L̂y , and L̂z , they have common eigen-
JJ II states.
J I • Denoting the common (joint) eigenstates by | λ, mi and the eigen-
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values of L̂2 and L̂z by ~2 λ and ~m, respectively, we have
Go Back L̂2 | λ, mi = ~2 λ | λ, mi, (26)

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L̂z | λ, mi = ~m | λ, mi. (27)
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• The factor ~ is introduced so that λ and m are dimensionless.

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• For simplicity, we assume that these eigenstates are orthonormal:

hλ0 , m0 | λ, mi =δλ0 , λδm0 , m.
• In order to determine the values of λ and m, we introduce the raising
The Schrodinger . . . and lowering operators defined by
L̂± = L̂x ± iL̂y . (28)
The Harmonic . . .
Angular . . . This leads to
1
L̂x = (L̂+ + L̂− ), (29)
2
1
Home Page L̂y = (L̂+ − L̂− ). (30)
2i
Title Page Hence
1
JJ II
L̂2x = (L̂2+ + L̂+ L̂− + L̂− L̂+ + L̂2− ), (31)
4
J I 1
L̂2y = − (L̂2+ − L̂+ L̂− − L̂− L̂+ + L̂2− ). (32)
4
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Exercise: Establish the relations given by Eqs. (29) - (32).
Go Back Using Eqs. (23) - (25), one can easily obtain the following commutation
relations
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[L̂2 , L̂± ] = 0, (33)
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[L̂+ , L̂− ] = 2~L̂z , (34)
[L̂z , L̂± ] = ±~L̂± . (35)

In addition L̂+ and L̂− satisfy
L̂+ L̂− = L̂2x + L̂2y + ~L̂z = L̂2 − L̂2z + ~L̂z , (36)
The Harmonic . . .
Angular . . .
L̂− L̂+ = L̂2x + L̂2y − ~L̂z = L̂2 − L̂2z − ~L̂z . (37)
These relations lead to
1
L̂2 = (L̂+ L̂− + L̂− L̂+ ) + L̂2z . (38)
2
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Title Page • Let us see how L̂± operates on | λ, mi.
JJ II • Since L̂± do not commute with L̂z , the kets | λ, mi are not eigenstates
of L̂± .
J I
Page 15 of 71 Using Eq. (35), we have

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L̂z L̂± | λ, mi = L̂± L̂z ± ~L̂± | λ, mi = ~(m ± 1)(L̂± | λ, mi). (39)
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Close • Hence the ket L̂± | λ, mi is an eigenstates of L̂z with eigenvalues

~(m ± 1).
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• Since L̂z and L̂2 commutes, (L̂± | λ, mi) must also be an eigenstate
of L̂2 .
• The eigenvalue of L̂2 when acting on L̂± | λ, mican be determined
The Schrodinger . . . by making use of Eq. (33).
• The state L̂± | λ, mi is also an eigenstate of L̂2 with eigenvalue ~2 λ.
The Harmonic . . .
Angular . . .
L̂2 (L̂± | λ, mi) = L̂± L̂2 | λ, mi = ~2 λ(L̂± | λ, mi) (40)
• From Eqs. (39) - (40) we infer that when L̂± acts on | λ, mi, it does-
not affect the 1st quantum number λ, but it raises or lowers the 2nd
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quantum number m by one unit.
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• That is L̂± | λ, mi proportional to | λ, m ± 1i.
JJ II • One can thus write
J I L̂± | λ, mi = C± | λ, m ± 1i, (41)

Page 16 of 71 where the value of C± remains to be determined.
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• Note that, for a given eigenvalue λ of L̂2 , there exists an upper limit
Full Screen for the quantum number m.
Close • This is due to the fact that the operator L̂2 -L̂2z is positive, since the
matrix elements of L̂2 -L̂2z =L̂2x +L̂2y are ≥ 0.
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• Since m has an upper limit mmax , there must exist a state | λ, mmax i
which cannot be raised further.
L̂+ | λ, mmax i = L̂+ | λ, li = 0. (42)
Using this relation along with Eq. (37), we see that
The Harmonic . . . L̂− L̂+ | λ, li = 0 = (L̂2 − L̂2z − ~L̂z ) | λ, li = ~2 (λ − l2 − l) | λ, li = 0. (43)
Angular . . .
We immediately see that
λ = l(l + 1). (44)
Furthermore, suppose l0 is the minimum value of m. We then see that
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L̂− | λ, l0 i = 0. (45)
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Using this relation along with Eq. (36), we see that
JJ II 0
L̂+ L̂− | λ, l0 i = (L̂2 − L̂2z + ~L̂z ) | λ, l0 i = ~2 (λ − l 2 + l0 ) | λ, l0 i = 0. (46)
J I
From this we observe that
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λ = l0 (l0 − 1). (47)
Full Screen Comparing Eq. (44) and Eq. (47), we obtain
Close l = −l0 (48)

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or
l0 = l + 1 (49)
• The solution l0 = l + 1 violates our assumption that the maximum
The Schrodinger . . . value of m is l .
• We therefore take the minimum value of m to be −l.
The Harmonic . . .
Angular . . . • Since l0 was reached by n application of L̂− on | λ, li it follows that
l = l0 + n (50)
Combaring this with Eq. (48), we conclude that
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n
l= (51)
Title Page 2
JJ II • Hence l can be integer or half-integer, depending on n being even or

odd.
J I
Page 18 of 71 Hence
1 3
l = 0, , 1, ... (52)
Go Back 2 2
Full Screen • For a given l, the values of m extends from −lto l in integer steps.
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m = −l, −l + 1, ...l − 1, l (53)
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• We now find it to be more convenient to denote the eigenstates of L̂2

and L̂2z by | l, mi such that
L̂2 | l, mi = ~2 l(l + 1) | l, mi, (54)
and
L̂z | l, mi = ~m | l, mi. (55)
The Harmonic . . .
Angular . . .
We recall that one can write
L̂+ | l, mi = C+ | l, m + 1i, (56)
hm, l | L̂− = hm + 1, l | C+∗ , (57)

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Multiplying Eq. (57) and Eq. (56), one can easily obtain
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p
JJ II C+ = ~ l(l + 1) − m(m + 1). (58)
J I Hence p
L̂+ | l, mi = ~ l(l + 1) − m(m + 1) | l, m + 1i. (59)
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One can also establish in a similar manner that
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p
L̂− | l, mi = ~ l(l + 1) − m(m − 1) | l, m − 1i. (60)
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Close • For m = l, we see that L̂+ | l, li = 0 and for m = −l, we see that
L̂− | l, −li = 0
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2.2. Angular momentum in spherical coordinates
Probability and . . . • We want to determine, in spherical coordinates the common eigen-
The Harmonic . . . functions of the operator L̂z and L̂2 .
Angular . . .
• For this, we need to rewrite L̂x , L̂y , and L̂z in spherical coordinates.
So
~
L̂ = r̂ × p̂ = (r × O) (61)
i
and the gradient in spherical coordinates
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∂ 1 ∂ 1 ∂
Title Page O = r̂ + θ̂ + φ̂ (62)
∂r r ∂θ r sin θ ∂φ
JJ II
and
J I r = rr̂, (63)
Page 20 of 71 so
~ ∂ 1 ∂ 1 ∂
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L̂ = rr̂ × (r̂ + θ̂ + φ̂ ) . (64)
i ∂r r ∂θ r sin θ ∂φ
Full Screen Since
r̂ × r̂ = 0, r̂ × θ̂ = φ̂, r̂ × φ̂ = −θ̂, (65)
Close
we have
Quit ~ ∂ 1 ∂
L̂ = φ̂ − θ̂ ) . (66)
i ∂θ sin θ ∂φ
• The unit vector θ̂ and φ̂ can be resolved into their cartesian compo-
The Schrodinger . . . nents
Probability and . . . θ̂ = (cos φ cos θ)i + (cos θ sin φ)j − sin θk, (67)
The Harmonic . . .
Angular . . . φ̂ = − sin φi + cos φj. (68)
Thus

~ ∂ 1 ∂
L̂ = (− sin φi+cos φj) − cos φ cos θi+cos θ sin φj−sin θk .
i ∂θ sin θ ∂φ
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(69)
Title Page
• We thus see that
JJ II
~ ∂ ∂ ∂ ∂
L̂x = − sin φ − cos φ cot θ = ~i sin φ + cos φ cot θ .
J I i ∂θ ∂φ ∂θ ∂φ
(70)
Page 21 of 71

Go Back ~ ∂ ∂ ∂ ∂
L̂y = cos φ − sin φ cot θ = −~i cos φ − sin φ cot θ .
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i ∂θ ∂φ ∂θ ∂φ
(71)
Close
∂
L̂z = −~i . (72)
Quit ∂φ
• The raising and lowering operators becomes
∂ ∂ ∂ ∂
Probability and . . . L̂+ = i~ sin φ + cos φ cot θ − i cos φ + i sin φ cot θ (73)
∂θ ∂φ ∂θ ∂φ
The Harmonic . . .
Angular . . . or
iφ ∂ ∂
L̂+ = i~e cot θ −i . (74)
∂φ ∂θ
• It can also be shown in a similar manner that
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−iφ ∂ ∂
L̂− = i~e cot θ +i . (75)
Title Page ∂φ ∂θ

JJ II ∂ 1 ∂2 ∂2
Exercise. Show that i, L̂2 = −~2 cot θ ∂θ + sin2 θ ∂φ2
+ ∂θ2
.
J I Using Eqs. (70)-(72), evaluate the commutators
ii, [L̂x , L̂y ], [L̂y , L̂z ] and [L̂z , L̂x ].
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Prove the following relation
Go Back iii, [L̂z , sin(2φ)] = 2i~(sin2 φ − cos2 φ).
iv, L̂z (cos2 φ − sin2 φ + 2i sin φ cos φ) = 2~e2iφ .
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Close
2.3. The quantum numbers l and m
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• We now seek to determine the possible values of the quantum num-

bers l and m.
• Using the eigenvalue equation
Probability and . . . L̂z | l, mi = ~m | l, mi, (76)
The Harmonic . . .
one can write
Angular . . .
hφ, θ | L̂z | l, mi = ~mhφ, θ | l, mi. (77)
Using Eq. (72), we have
∂ ∂
−~i hφ, θ | l, mi = ~mhφ, θ | l, mi = −~i Υm (θ, φ) = ~mΥm
l (θ, φ), (78)
Home Page ∂φ ∂φ l
Title Page where Υm
l (θ, φ) = hφ, θ | l, mi.
JJ II
• Since L̂z depends only on φ, the function Υm
l (θ, φ) is separable.
J I
That is Υm m m
l (θ, φ)=Υl (θ)Υl (φ).
Page 23 of 71
Go Back • The solution of Eq. (78) can be written as
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Υm
l (φ) = e
imφ
, (79)
Close where the integration constant is taken to be unity.
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2.4. The eigenfunctions of L̂z and L̂2
Probability and . . . • We seek to obtain the common eigenfunctions of L̂z and L̂2 applying
The Harmonic . . . the raising and lowering operators L̂+ and L̂− .
Angular . . .
Using
L̂+ | l, li = 0. (80)
• Since the operators L̂z and L̂2 depend only on the angles θ and φ,
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their eigenstates depend only on θ and φ.
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• Multiplying Eq. (80) from the left by hφ, θ |, we have
JJ II
hφ, θ | L̂+ | l, li = 0. (81)
J I
Employing Eqs. (74) and (79), one can write this as
Page 24 of 71

∂ ∂ ilφ l
Go Back cot θ −i e Υl (θ) = 0. (82)
∂φ ∂θ
Full Screen
∂ ilφ
Using ∂φ
e = ileilφ , we have
Close
dΥll (θ)
Quit = l cot θdθ. (83)
Υll (θ)
It then follows that
ln Υll (θ) = l ln sin θ + ln Cl = ln((sin θ)l Cl ). (84)
The Harmonic . . .
Angular . . . Υll (θ) = Cl (sin θ)l . (85)
• In view of this result, Υll (θ, φ) takes the form

Υll (θ, φ) = Cl (sin θ)l eilφ , (86)
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• where Cl is to be fixed using the normalization condition.
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• The normalization constant Cl can be expressed as
JJ II
Cl =| C | eilφ0 . (87)
J I
• Let us choose φ0 = π, so that
Page 25 of 71
Go Back
Cl =| C | (eiπ )l = (−1)l | C | . (88)
In view of this, Eq. (86) becomes
Full Screen
Υll (θ, φ) = (−1)l | C | (sin θ)l eilφ , (89)

Close
where | C | is to be fixed using the normalization condition.

Quit
Z 2π Z π
dφ | Υll (θ, φ) |2 sin θdθ = 1. (90)
0 0
What is the explicit form of Υ00 ?
Υ00 =| C |, (91)
The Harmonic . . .
so that using the normalization condition, we have
Z 2π Z π
Angular . . . 2
|C| dφ sin θdθ = 1. (92)
0 0
From this, we see that
1 2
| C |= (93)
4π
Home Page
and
1 2
Title Page Υ00 = . (94)
4π
JJ II Exercise:1. Determine the explicity form of
i,Υ11 ,
J I ii, Υ01 ,
Page 26 of 71
iii, Υ−11 ,
iv, Υ12 ,
Go Back v, Υ22 .
Full Screen
Close
2.5. Spin angular momentum
Quit
• Elementary particles such as the electron and the proton have an in-
trinsic angular momentum called spin in addition to their extrinsic
angular momentum.
• The theory of spin is identical to the general theory of angular mo-
mentum by analogy with the vector angular momentum L̂.
The Harmonic . . .
Angular . . . • The spin is also represented by a vector operator Ŝ whose compo-
nents Ŝx , Ŝy , and Ŝz obey the commutation relations as L̂x , L̂y , and
L̂z .
Home Page
[Ŝx , Ŝy ] = i~Ŝz , (95)
Title Page
[Ŝy , Ŝz ] = i~Ŝx , (96)
JJ II
J I [Ŝz , Ŝx ] = i~Ŝy . (97)
Page 27 of 71
Ŝ 2 | s, ms i = ~2 s(s + 1) | s, ms i, (98)
Go Back
and
Full Screen Ŝz | s, ms i = ~ms | s, ms i, (99)
Close p
Ŝ± | s, ms i = ~ s(s + 1) − ms (ms ± 1) | s, ms ± 1i. (100)
Quit
where
Ŝ± = Ŝx ± iŜy (101)
and the values of s are
1 3
The Schrodinger . . . s = 0, , 1, .... (102)
2 2
The Harmonic . . .
with the value of ms being
Angular . . .
ms = −s, −s + 1, ...s − 1, s (103)
• Every elementary particle has a specific value of S, which we call the

spin of that particular species.
Home Page
• Pi mesons have spin 0.
Title Page
• Electron, protons, and neutrons have spin 21 .
JJ II
• Photons have spin 1.
J I
• Delta particle have spin 32 .
Page 28 of 71
• Gravitons have spin 2 and so on.
Go Back
Full Screen
2.6. Spin 12 and Pauli matrices
Close
• For a particle with spin 21 the quantum munber ms takes only two
Quit
values:ms = 21 and ms = − 12 .
• There are two eigenstates of Ŝz :| 12 , 12 i called spin-up state and | 21 , − 12 i,
The Schrodinger . . . called spin-down state.
• The eigenvalues of Ŝ 2 and Ŝz are given by
The Harmonic . . .
Angular . . .
1 1 ~ 1 1
Ŝz | , ± i = ± | , ± i (104)
2 2 2 2 2
and
1 1 3 1 1
Ŝ 2 | , ± i = ~2 | , ± i. (105)
Home Page 2 2 4 2 2
Title Page • We next seek to obtain the matrix representations for the compo-
nents of the spin angular momentum in the basis formed by eigen-
JJ II
states of Ŝz .
J I
1 1
| αi =| , i (106)
Page 29 of 71 2 2
Go Back 1 1
| βi =| , − i. (107)
2 2
Full Screen
Close • The matrix representation for the operator Ŝz in this basis is given by
Quit

hα | Ŝz | αi hα | Ŝz | βi ~
0 ~ 1 0
Ŝz = = 2 = (108)
hβ | Ŝz | αi hβ | Ŝz | βi 0 − ~
2 2 0 −1
• To obtain the matrix representation for Ŝx and Ŝy , first we have de-
The Schrodinger . . . termine the matrix representations for Ŝ+ and Ŝ− . From Eq. (100), we
Probability and . . . see that
The Harmonic . . .
1 1
Angular . . . Ŝ+ | , i = Ŝ+ | αi = 0, (109)
2 2
1 1
Ŝ+ | , − i = Ŝ+ | βi = ~ | αi, (110)
2 2
Home Page 1 1
Ŝ− | , i = Ŝ− | αi = ~ | βi, (111)
2 2
Title Page
1 1
JJ II Ŝ− | , − i = Ŝ− | βi = 0. (112)
2 2
J I On account of these results, we have
Page 30 of 71
hα | Ŝ+ | αi = 0, (113)
Go Back
Full Screen hα | Ŝ+ | βi = ~, (114)
Close
hβ | Ŝ+ | αi = 0, (115)
Quit
hβ | Ŝ+ | βi = 0, (116)
The Schrodinger . . . hα | Ŝ− | αi = 0, (117)
The Harmonic . . .
hα | Ŝ− | βi = 0, (118)
Angular . . .
hβ | Ŝ− | αi = ~, (119)
hβ | Ŝ− | βi = 0. (120)
Home Page
Hence, the matrix representation of Ŝ+ and Ŝ− are respectively given by
Title Page

0 1
JJ II Ŝ+ = ~ , (121)
0 0
J I
0 0
Page 31 of 71 Ŝ− = ~ . (122)
1 0
Go Back Thus
1 ~ 0 1
Full Screen Ŝx = (Ŝ+ + Ŝ− ) = , (123)
2 2 1 0
Close

i ~ 0 −i
Ŝy = (Ŝ− − Ŝ+ ) = , (124)
Quit 2 2 i 0
• The spin angular momentum can be expressed as

1
Ŝ = ~σ̂, (125)
The Schrodinger . . . 2
Probability and . . . where
The Harmonic . . . σ̂ = σ̂x i + σ̂y j + σ̂z k. (126)
Angular . . . Thus the matrices become

0 1
σ̂x = , (127)
1 0

Home Page 0 −i
σ̂y = , (128)
i 0
Title Page

1 0
JJ II σ̂z = (129)
0 −1
J I
are called Pauli spin matrices.
Page 32 of 71
• The Pauli matrices are Hermitian, traceless, and have determinants
Go Back
equal to −1.
Full Screen ˆ jki σ̂i ,
• The Pauli matrices satisfy the commutation relations [σ̂j , σ̂k ] =2Iε
Close where εjki is the antisymmetric tensor called Levi-Civita tensor.
Quit
Exercise: 1. Find the matrix representation of Ŝ 2 .
2.Determine the eigenvalues and eigenstates of the operator Ŝx and Ŝy .
2.7. Total angular momentum
Probability and . . . • The total angular momentum is defined as
The Harmonic . . .
Angular . . . Jˆ = L̂ + Ŝ. (130)
From this we see that
Jˆx = L̂x + Ŝx , (131)
Home Page Jˆy = L̂y + Ŝy , (132)

Title Page and
Jˆz = L̂z + Ŝz . (133)
JJ II
Exercise:1.Evaluate [Jˆx , Jˆy ], [Jˆy , Jˆz ] , and [Jˆz , Jˆx ].
J I 2. Using the results of Q1. try to establish the following relations
Jˆ2 | j, mi = ~2 j(j + 1) | j, mi,

Page 33 of 71
(134)
Go Back
and
Full Screen Jˆz | j, mi = ~m | j, mi, (135)
Close
Jˆ± | j, mi = ~ j(j + 1) − m(m ± 1) | j, m ± 1i.
p
(136)
Quit
where
Jˆ± = Jˆx ± iJˆy (137)
and the values of j are
The Schrodinger . . . 1 3
j = 0, , 1, .... (138)
Probability and . . . 2 2
The Harmonic . . . with the value of m being
Angular . . .
m = −j, −j + 1, ...j − 1, j. (139)
Home Page
Title Page
JJ II
J I
Page 34 of 71
Go Back
Full Screen
Close
Quit
3. The Hydrogen Energy Eigenvalues and Eigen-
functions
The Harmonic . . .
Angular . . .
• The hydrogen atom is a bound system consisting of a proton and an
electron.
• Let r1 and r2 be the position vectors of the proton and electron rel-
ative to some origin 0 and m1 and m2 the masses of the proton and
electron respectively.
Home Page
• We then note that

Title Page
r = r2 − r1 . (140)
JJ II
• The Hamiltonian for the hydrogen atom is given by
J I
1 1
H = Te + Tp + v(r) = m2 ṙ22 + m1 ṙ12 + v(r), (141)
Page 35 of 71 2 2
Go Back where
e2
Full Screen
v(r) = v(r2 − r1 ) = − (142)
4π0 r
Close is the coulomb potential energy arising from the electrostatic attrac-
tion between the electron and proton.
Quit
• It depends only on the distance that separates the electron and pro-
ton.
• The position vector of the center of mass of m1 and m2 is given by
The Harmonic . . .
Angular . . .
Home Page
Title Page
JJ II
J I
Page 36 of 71
Go Back
Full Screen
Figure 1: The electron and proton in a hydrogen atom.
Close
m1 r1 + m2 r2
R= . (143)
Quit m1 + m2
One can thus write
RM = m1 r1 + m2 r2 , (144)
where M = m1 + m2 .
Probability and . . . • We also see from Eq. (140) that
The Harmonic . . .
Angular . . .
r2 = r + r1 , (145)
r1 = r2 − r. (146)
• Substituting Eqs. (144) and Eq. (146) into Eq. (144) , we get
Home Page
m2
Title Page r1 = R − r, (147)
M
JJ II
m1
r2 = R + r. (148)
J I M
Page 37 of 71 • With the aid of Eq. (147) and Eq. (148), the kinetic energy of the hy-
drogen atom can be written as
Go Back
2 2
1 m2 1 m1 1 1 2
Full Screen T = m1 Ṙ − ṙ + m2 Ṙ + ṙ = µṙ2 + M Ṙ , (149)
2 M 2 M 2 2
Close
where
m1 m2
Quit µ= (150)
m1 + m2
is the reduced mass of the system.
• If we tie our reference frame at the center of mass frame, Ṙ = 0.
• Then Eq. (149) takes the form
The Harmonic . . . 1 1 2
Angular . . .
T = µṙ2 = P , (151)
2 2µ
in which P = µṙ.
• The classical Hamiltonian of the hydrogen atom is thus expressible

Home Page as
1 2 e2 1
H= P − . (152)
Title Page 2µ 4π0 r
JJ II • On the other hand, we note that
J I L = r × P ⇒ L2 = (r × P).(r × P) = r2 P 2 − (r.P)2 (153)
Page 38 of 71
from which follows
L2
Go Back P 2 = p2r + , (154)
r2
Full Screen
where pr is the radial component of the linear momentum P .
Close
• The classical Hamiltonian can then be put in the form
Quit
1 2 L2 e2 1
H= pr + − . (155)
2µ 2µr2 4π0 r
• The quantum Hamiltonian of this expression becomes
1 2 L̂2 e2 1
Probability and . . . Ĥ = p̂r + − . (156)
The Harmonic . . .
2µ 2µr̂2 4π0 r̂
Angular . . . Exercise: Show that [Ĥ, L̂z ]=[Ĥ, L̂2 ] = 0.
• If they commute we can write a common eigenstates as | E, l, mi
Ĥ | E, l, mi = E | E, l, mi, (157)
Home Page
Title Page
L̂z | E, l, mi = m~ | E, l, mi, (158)
JJ II
L̂2 | E, l, mi = l(l + 1)~2 | E, l, mi (159)
J I E is introduced to identify the eigenvalues of Ĥ.
Page 39 of 71 • Taking into account Eq. (156), the energy eigenvalue equation for
the hydrogen atom can now be written as
Go Back
L̂2 e2 1

1 2
Full Screen p̂ + − | E, l, mi = E | E, l, mi. (160)
2µ r 2µr̂2 4π0 r̂
Close
• Multiplying from the left by hφ, θ, r |, yields

Quit
1 2 L̂2 e2 1

hφ, θ, r | p̂ + − | E, l, mi = Ehφ, θ, r | E, l, mi. (161)
2µ r 2µr̂2 4π0 r̂
• In position space this can be written as
e2 1

1 2 1 2
Probability and . . . hφ, θ, r | p̂ + l(l+1)~ − | E, l, mi = Ehφ, θ, r | E, l, mi.
2µ r 2µr2 4π0 r
The Harmonic . . .
(162)
Angular . . .
• Using the expression of the operators P̂ 2 and L̂2 in spherical coordi-
nates which can be given by
2
1 ∂2 ∂2

2 2 ∂ 2 ∂ 1 ∂
P̂ = −~ + + cot θ + + (163)
Home Page
∂r2 r ∂r r2 ∂θ sin2 θ ∂φ2 ∂θ2
1 ∂2 ∂2

2 2 ∂
Title Page
L̂ = −~ cot θ + + , (164)
∂θ sin2 θ ∂φ2 ∂θ2
JJ II
the quantum version of Eq. (154), can be written as
J I 2
∂ 2 ∂

2 2
p̂r = −~ + . (165)
Page 40 of 71 ∂r2 r ∂r

Go Back ∂ 1
Exercise: Show that p̂r = −i~ ∂r + r in position space.
Full Screen
• Now on account of Eq. (165), the energy eigenvalue equation Eq. (162)can
Close be put in the form
2 2
e2 1

Quit −~ ∂ 2 ∂ 1 2
+ + l(l + 1)~ − Ψ(φ, θ, r) = EΨ(φ, θ, r),
2µ ∂r2 r ∂r 2µr2 4π0 r
(166)
where Ψ(φ, θ, r) = hφ, θ, r | E, l, mi is the eigenfunction in position
The Schrodinger . . . space.
• Since the Hamiltonian is a sum of a radial part and angular part, we
The Harmonic . . .
can write this as a product of a radial part and angular part.
Angular . . .
hφ, θ | l, mihr | Ei = R(r)Υm

l (θ, φ). (167)
• By substituting Eq. (167) into Eq. (166), we have

Home Page 2 2
e2 1

−~ ∂ 2 ∂ 1 2
+ + l(l + 1)~ − R(r) = ER(r). (168)
Title Page 2µ ∂r2 r ∂r 2µr2 4π0 r
JJ II
• This is called radial equation.
J I
Page 41 of 71 3.1. The energy Eigenvalues and eigenfunctions

Go Back
• To determine the eigenfunction of Ĥ, L̂z , and L̂2 ; let us use separa-
Full Screen tion of variables:
Close
Ψnlm (φ, θ, r) = Rnl (r)Υm
l (θ, φ), (169)
Quit
where Υm
l (θ, φ) is the spherical harmonics and Rnl (r) is the radial
wavefunctions of the hydrogen atom.
• Since Υml (θ, φ) are normalized by definition of Eq. (90), the normal-
The Schrodinger . . . ization condition of Rnl (r) is
Probability and . . . Z ∞
The Harmonic . . . r2 | Rnl (r) |2 dr = 1. (170)
0
Angular . . .
• We can simplify the radial equation by writing

1
Rnl (r) = Unl (r). (171)
r
Home Page
We then note that
Title Page d U −U 1 dU
= 2 + (172)
dr r r r dr
JJ II
and
J I
d2 U 1 d2 U

d −U 1 dU 2U 2 dU
= + = − + . (173)
Page 42 of 71 dr2 r dr r2 r dr r3 r2 dr r dr2
Go Back Hence we see that

d2 1 d2 U

Full Screen 2 d U
+ = . (174)
dr2 r dr r r dr2
Close
In view of this result, the radial equation takes the form

Quit
2 2
e2 1

−~ d 1 2
+ l(l + 1)~ − U = EU. (175)
2µ dr2 2µr2 4π0 r
• Using this, we have
The Schrodinger . . . 2 2
l(l + 1)~2 e2 1

−~ d
Probability and . . . + − Unl (r) = Unl (r). (176)
2µE dr2 2µEr2 4π0 E r
The Harmonic . . .
Angular . . . • Setting r
−2µE
λ= , (177)
~2
ρ = λr, (178)
Home Page
and
Title Page µe2
ρ0 = , (179)
2πε0 ~2 λ
JJ II
we have
d2 U

J I l(l + 1) ρ0
= 1+ − U. (180)
dρ2 ρ2 ρ
Page 43 of 71
• Let us consider two limiting cases
Go Back
• i, for ρ → ∞ (for large values of r), we have
Full Screen
d2 U
= U. (181)
Close
dρ2
Quit
• The general solution of this equation is
U (ρ) = Ae−ρ + Beρ , (182)
• as ρ → ∞, only the minus sign solution is physically acceptable,
The Schrodinger . . . since eρ diverges for large values of ρ.
• For larger values of ρ, U (ρ) behaves like
The Harmonic . . .
Angular . . . U (ρ) → e−ρ . (183)
• ii,On the other hand, for ρ → 0(for small values of r)

d2 U l(l + 1)
2
= U. (184)
Home Page dρ ρ2
Title Page • The general solution of this equation is
JJ II U (ρ) = Aρl+1 + Bρ−l , (185)
J I
• as ρ → 0, the second term ρ−l diverges.
Page 44 of 71
• Thus the solution is, for small values of ρ,
Go Back
• U (ρ) behaves like
Full Screen U (ρ) → ρl+1 . (186)
Close • On account of Eq. (183) and Eq. (186), one can express U (ρ) in the
Quit
form
U (ρ) = ρl+1 f (ρ)e−ρ , (187)
where f (ρ) is an r-dependent function.
• We note that
dU df
The Schrodinger . . . = ρl e−ρ [(l + 1 − ρ)f + ρ ], (188)
dρ dρ
The Harmonic . . .
d2 U d2 f

l(l + 1) df
Angular . . .
2
= ρl e−ρ + ρ − 2l − 2 f + 2(l + 1 − ρ) + ρ 2 . (189)
dρ ρ dρ dρ
• Now combination of Eq. (180), Eq. (187), and Eq. (189) yields
d2 f df
Home Page ρ 2 + 2(l + 1 − ρ) + (ρ0 − 2(l + 1))f = 0. (190)
dρ dρ
Title Page
• We assume that f (ρ) can be expanded in a power series, so that
JJ II ∞
X
J I
f (ρ) = b k ρk . (191)
k=0
Page 45 of 71
• From Eq. (191), we see that
Go Back
∞
df X
Full Screen
= kbk ρk−1 . (192)
dρ k=0
Close
• Upon replacing k by k + 1, we have
Quit
∞
df X
= (k + 1)bk+1 ρk (193)
dρ k=0
and differentiating once more, we find
∞
Probability and . . . d2 f X
= k(k + 1)bk+1 ρk−1 . (194)
The Harmonic . . . dρ2 k=0
Angular . . .
• Using Eqs. ((191)-(194)), we see that

∞
X
(ρ0 − 2(l + 1))f (ρ) = (ρ0 − 2(l + 1))bk ρk (195)
Home Page k=0
∞
Title Page df X
−2ρ = − 2kbk ρk (196)
dρ
JJ II k=0
∞
J I df X
2(l + 1) = 2(l + 1)(k + 1)bk+1 ρk (197)
dρ k=0
Page 46 of 71
∞
d2 f X
Go Back ρ 2 = k(k + 1)bk+1 ρk . (198)
dρ k=0
Full Screen
• Substituting Eqs. ((195)-(198)) into Eq. (190), leads to

Close
∞
X
Quit
(2(l + 1) + k)(k + 1)bk+1 + (ρ0 − 2(l + 1 + k))bk ρk = 0. (199)
k=0
• Since ρk is quite arbitrary, we see that
2(l + 1 + k) − ρ0
Probability and . . . bk+1 = bk . (200)
The Harmonic . . .
(k + 2l + 2)(k + 1)
Angular . . .
• This recursion relation determines the coefficients and hence the
function of f (ρ).
• For large k , we see that

Home Page
2k 2
bk+1 = bk = bk . (201)
Title Page k(k + 1) k+1
JJ II • We note that
J I b1 = 2b0 , (202)
Page 47 of 71
b2 = b1 = 2b0 , (203)
Go Back
2 4
Full Screen b3 = b2 = b0 , (204)
3 3
Close and
2k
Quit
bk = b0 . (205)
k!
• Thus for large k , we get
The Schrodinger . . . ∞
X (2ρ)k
Probability and . . . f (ρ) = b0 = b0 e2ρ . (206)
The Harmonic . . . k=0
k!
Angular . . .
• Therefore, for large k Eq. (187) takes the form
U (ρ) = b0 ρl+1 eρ , (207)
which diverges for large ρ.
Home Page
• In order to have a normalizable U (ρ), the series must terminate.
Title Page
• There must be some maximum integer km such that
JJ II
bkm+1 = 0, (208)
J I
Page 48 of 71
• On account of this, expression Eq. (200)reduces to
Go Back
2(km + l + 1) − ρ0 = 0. (209)
Full Screen • Defining the principal quantum number n by

Close n = km + l + 1. (210)
Quit
• From Eq. (209) and Eq. (210), we see that
ρ0 = 2n. (211)
q
−2µE µe2
• Moreover, using λ = ~2
and ρ0 = 2πε0 ~2 λ
,one can easily get
Probability and . . . µ2 e4
λ2 = (212)
The Harmonic . . . 16π 2 ε20 ~4 n2
Angular . . .
and
µe4 E1
En = − 2 2 2 2
= 2, (213)
32π ε0 ~ n n
with n = 1, 2, 3.... and E1 is the ground state(the state of lowest en-
Home Page ergy) equal to −13.6eV .
Title Page
• Eq. (213) represents the energy eigenvalues of the hydrogen atom.
JJ II In view of Eqs. (213) and (178), Eq. (177) takes the form
12
µe2

J I 2µE r
ρ = λr = − 2 r= 2
r= , (214)
~ 4πε0 ~ n nb
Page 49 of 71
Go Back
where
4πε0 ~2
b= (215)
Full Screen µe2
Close
is called the Bohr radius.
Quit
• Substituting Eq. (187) into Eq. (171), we have
1
Rnl (r) = ρl+1 e−ρ f (ρ), (216)
r
where f (ρ) is a polynomial of degree km = n − l − 1, with the coeffi-
The Schrodinger . . . cients determined by the recursion relation given by Eq. (200).
• In view of Eq. (214), Eq. (216) turns out to be
The Harmonic . . .
Angular . . . l+1
1 r r
Rnl (r) = e− nb f (ρ). (217)
r nb
• Finally, taking into account Eq. (217) and Eq. (169), energy eigen-
Home Page function of hydrogen atom becomes
l+1
Title Page 1 r r
Ψnlm (φ, θ, r) = e− nb f (ρ)Υm
l (θ, φ). (218)
JJ II
r nb
J I • Exercise:1. Find R10 (r), R20 (r), R21 (r), Ψ100 , Ψ200 , and Ψ210 .
Page 50 of 71
Go Back 3.2. Laguerre polynomial and Associated laguerre poly-

nomial
Full Screen
Close • The associated laguerre polynomial is defined interms of laguerre

polynomials of order k, Lk (r) by
Quit
dN
LN
k (r) = Lk (r), (219)
drN
where Lk (r) is the laguerre polynomial which is given by Rodrigues
The Schrodinger . . . formula as
dk
Probability and . . . Lk (r) = er k (rk e−r ). (220)
The Harmonic . . .
dr
Angular . . . • Using Eq. (220), the first few laguerre polynomials are listed as fol-
lows
L0 (r) = 1, L1 (r) = 1 − r, L2 (r) = 2 − 4r + r2 , L3 (r) = 6 − 18r + 9r2 − r3
(221)
Home Page
and so on.
Title Page
• Similarly, using Eq. (219), the first few associated laguerre polynomi-
als are listed as
JJ II
L11 (r) = −1, L12 (r) = 2r − 4, L13 (r) = −18 + 18r − 3r2 , L22 (r) = 2 (222)
J I
and so on.
Page 51 of 71
• The radial wave function of the hydrogen atom can be expressed in-
Go Back terms of associated laguerre polynomial as
2r −r 2r
Full Screen Rnl (r) = Nnl ( )l e nb L2l+1
n+l (223)
nb nb
Close
where b is the Bohr radius and Nnl is a constant obtained by normal-
Quit
izing the radial function Rnl (r):
Z ∞
r2 Rnl
2
(r)dr = 1. (224)
0
• Using the normalization condition of the associated Laguerre func-
The Schrodinger . . . tions Z ∞ 2
2n[(n + l)!]3

−ρ 2l 2l+1
e ρ Ln+l (ρ) ρ2 dρ = , (225)
The Harmonic . . . 0 (n − l − 1)!
Angular . . . we can show that Nnl is given by
s
3
2 (n − l − 1)!
Nnl = − . (226)
nb 2n[(n + l)!]3
Home Page
• Inview of Eq. (226), Eq. (223) takes the form
Title Page
s
3
2 (n − l − 1)! 2r l −r 2l+1 2r
JJ II Rnl (r) = − ( ) e nb Ln+l (227)
nb 2n[(n + l)!]3 nb nb
J I
• Finally, the wavefunctions of the hydrogen atom are given by
Page 52 of 71 s
3
2 (n − l − 1)! 2r l −r 2l+1 2r m
Go Back Ψnlm (r, θ, φ) = − ( ) e nb Ln+l Υ (θ, φ).
nb 2n[(n + l)!]3 nb nb l
Full Screen (228)
Close • Example: 1. Find the explicit expressions of the radial wavefunction

R10 (r), R20 (r), R21 (r) and wavefunctions Ψ100 (r, θ, φ), Ψ200 (r, θ, φ).
Quit
• Homework: 1. Find the expression for R31 (r), R30 (r) and wavefunc-
tions Ψ210 (r, θ, φ).
3.3. Radial probability distribution functions
Probability and . . . • When a hydrogen atom is in the stationary state Ψnlm (r, θ, φ), t he
The Harmonic . . . quantity | Ψnlm (r, θ, φ) |2 dr3 represents the probability of finding the
Angular . . .
electron in the volume element in spherical coordinates dr3 , dr3 =
r2 sin θdrdθdφ .
• The probability of finding the electron in a spherical shell located

between r and r + dr (i.e., a shell of thickness dr) is given by
Home Page
Z Z Z
2 3
Pnl (r) = | Ψnlm (r, θ, φ) | dr = | Rnl (r) | r dr | Υm
2 2 2
l (θ, φ) | sin θdθdφ.
Title Page
(229)
JJ II
• It is convenient to normalized R and Υ individually:
J I Z ∞ Z 2π Z π
2 2
Page 53 of 71 | Rnl (r) | r dr = 1, | Υm 2
l (θ, φ) | sin θdθdφ = 1. (230)
0 0 0
Go Back
• The normalized angular wavefunctions are called spherical harmon-
Full Screen
ics.
Close
• ⇒ Z
Quit Pnl (r) = | Rnl (r) |2 r2 dr. (231)
• If we integrate this quantity between r = 0 and r = a, we obtain the
The Schrodinger . . . probability of finding the electron in a sphere of radius a centered
Probability and . . . about the origin.
The Harmonic . . .
• Hence integrating between r = 0 and r = ∞, we would obtain 1,
Angular . . .
which is the probability of finding the electron somewhere in space.
• Let us now specify the average values of the various powers of r.
• Since Ψnlm (r, θ, φ) =Rnl (r) Υml (θ, φ), we can see that the average of r
k
Home Page is independent of the azimuthal quantum number m:

Z Z
Title Page
hr i = r | Ψnlm (r, θ, φ) | dr = rk | Rnl (r) |2 r2 dr
k k 2 3
JJ II Z Z (232)
m 2 k+2 2
| Υl (θ, φ) | sin θdθdφ = r | Rnl (r) | dr.
J I
Page 54 of 71
• Example: Find hri and hr2 i for an electron in the ground state of hy-
Go Back drogen atom. Express your answers interms of the Bohr radius b.
Full Screen
Close
3.4. Quantum Numbers and Degeneracy
Quit • What is quantum degeneracy?
• States with the same energy are called degenerate.

• If two or more wavefunction have the same energy one says that they
The Schrodinger . . . are degenerate.
• The degeneracy of a level is the number of wavefunctions with the
The Harmonic . . .
same energy.
Angular . . .
• The functions are grouped in shells and subshells.
• Wavefunction with the same n belong to the same shell and wave-
functions with the same n and l belong to the same shell.
Home Page
• Since km = 0, 1, 2, 3..., the allowed values of n are non-zero integers,
Title Page n=l+1,l+2, l+3.
JJ II • For a given value of n, the orbital quantum number l can have values
J I
only between 0 and n − 1; while for each l, the azimuthal number m
takes 2l + 1 values: m = −l, −l + 1, l − 1, l.
Page 55 of 71
• For each n, there exists gn different wavefunctions Ψnlm which corre-
Go Back sponds to the same energy En , with
Full Screen ∞
X
gn = (2l + 1) = n2 . (233)
Close
l=0
Quit
• The total degeneracy is always equal to n2 .
4. Perturbation methods
Probability and . . . • Most problems encountered in quantum mechanics cannot be solved
The Harmonic . . . exactly.
Angular . . .
• However, there are approximation methods which enable us to ob-
tain approximation solutions of such equations in certain cases.
• Perturbation method/theory is a systematic procedure for obtaining
approximate solutions to the perturbed problem by building on the
Home Page
known exact solutions to the unperturbed case.
Title Page
JJ II
4.1. The time-independent perturbation method
J I
• Consider a system described by a quantum Hamiltonian Ĥ0 .
Page 56 of 71
• Suppose it is possible to obtain the energy eigenvalues and eigen-

Go Back
states satisfying time independent Schrodinger equation
Full Screen
Ĥ0 | Ψ0n i = En0 | Ψ0n i. (234)
Close
• If we perturb the system by putting a litle bump or a magnetic field
Quit in the bottom of the well then the quantum Hamiltonian of the per-
turbed system is
Ĥ = Ĥ0 + λĤp , (235)
The Harmonic . . .
Angular . . .
Home Page
Title Page
JJ II
J I
Page 57 of 71
Figure 2: Small perturbation.

Go Back
Full Screen
where Ĥp is the interaction between the system and the perturbation
Close and is very small compared to Ĥ0 (Hamiltonian of the unperturbed
system).
Quit
• λ is a dimensionless parameter and is very small compared to 1.
• Let us solve the new eigenfunction and eigenvalues.
Ĥ | Ψn i = En | Ψn i ⇒ (Ĥ0 + λĤp ) | Ψn i = En | Ψn i. (236)
The Harmonic . . .
• Expanding the perturbed eigenvalues and eigenstates in power se-
Angular . . .
ries of λ, we have
En = En0 + λEn1 + λ2 En2 + λ3 En3 + ... (237)
Home Page | Ψn i =| Ψ0n i + λ | Ψ1n i + λ2 | Ψ2n i + λ3 | Ψ3n i + ... (238)

Title Page • Here En1 is the first-order correction to the nth eigenvalue and | Ψ1n i is
JJ II
the first-order correction to the nth eigenfunction; En2 and | Ψ2n i are
the second-order corrections and so on.
J I
• Plugging Eq. (237) and Eq. (238) into Eq. (236), we have
Page 58 of 71
(Ĥ0 + λĤp ) | Ψ0n i + λ | Ψ1n i + λ2 | Ψ2n i + ...
Go Back (239)
= (En0 + λEn1 + λ2 En2 ) | Ψ0n i + λ | Ψ1n i + λ2 | Ψ2n i + ....
Full Screen
• The coefficients of successive powers of λ on both sides of this equa-
Close
tion must be equal.
Quit
• Equating like powers of λ, we see that
Zero order in λ : Ĥ0 | Ψ0n i = En0 | Ψ0n i (240)

Probability and . . . F irst order in λ : Ĥ0 | Ψ1n i + Ĥp | Ψ0n i = En0 | Ψ1n i + En1 | Ψ0n i (241)
The Harmonic . . .
Angular . . .
Second order in λ : Ĥ0 | Ψ2n i+Ĥp | Ψ1n i = En0 | Ψ2n i+En1 | Ψ1n i+En2 | Ψ0n i.
(242)
Home Page
4.2. The first-order correction
Title Page
• To determine the first-order correction En1 to En , multiply both sides
JJ II of Eq. (241) by hΨ0n |
J I
hΨ0n | Ĥ0 | Ψ1n i + hΨ0n | Ĥp | Ψ0n i = hΨ0n | En0 | Ψ1n i + hΨ0n | En1 | Ψ0n i
Page 59 of 71 (243)
⇒
Go Back En1 = hΨ0n | Ĥp | Ψ0n i (244)
Full Screen
• Eq. (244) represents the first-order correction to the energy eigen-
Close values En0 .
Quit • It says that the first-order correction to the energy is the expectation
value of the perturbation in the unperturbed state.
4.3. The first-order correction to the energy eigenstates
Probability and . . . • Let us determine | Ψ1n i.
The Harmonic . . .
• Assuming the set of the unperturbed state | Ψ0n i form a complete
Angular . . .
orthonormal basis;
• Using the completeness relation

X
Iˆ = | Ψ0m ihΨ0m |, (245)
Home Page m
Title Page we have X

| Ψ1n i = | Ψ0m ihΨ0m | Ψ1n i (246)
JJ II
m
J I or X
| Ψ1n i =| Ψ0n ihΨ0n | Ψ1n i + | Ψ0m ihΨ0m | Ψ1n i. (247)
Page 60 of 71 m6=n
Go Back • Multiplying Eq. (238) by hΨ0n |, we have

Full Screen
hΨ0n | Ψn i = hΨ0n | Ψ0n i + λhΨ0n | Ψ1n i + λ2 hΨ0n | Ψ2n i + ... (248)
Close
• Now imposing the normalization condition hΨ0n | Ψn i = 1, Eq. (247)
Quit
reduces to X
| Ψ1n i = | Ψ0m ihΨ0m | Ψ1n i. (249)
m6=n
• On the other hand, multiplying Eq. (241) by hΨ0m | for m 6= n, we find
Probability and . . . hΨ0m | Ĥ0 | Ψ1n i + hΨ0m | Ĥp | Ψ0n i = En0 hΨ0m | Ψ1n i + En1 hΨ0m | Ψ0n i. (250)
The Harmonic . . .
Angular . . . • Now in view of the fact that
hΨ0m | Ĥ0 | Ψ1n i = Em

0
hΨ0m | Ψ1n i (251)
and
Home Page
hΨ0m | Ψ0n i = 0, (252)
we see that
Title Page
JJ II
0
hΨ0m | Ĥp | Ψ0n i = En0 hΨ0m | Ψ1n i − Em hΨ0m | Ψ1n i. (253)
J I ⇒
hΨ0m | Ĥp | Ψ0n i
Page 61 of 71
hΨ0m | Ψ1n i = . (254)
En0 − Em 0
Go Back
• Combination of this result with Eq. (249)
Full Screen
X hΨ0 | Ĥp | Ψ0 i
m n
| Ψ1n i = 0 − E0
| Ψ0m i. (255)
Close
m6=n
E n m
Quit
• This represents the first-order correction to the energy eigenstates.

4.4. The second-order shift
Probability and . . . • To determine En2 we need to multiply both sides of Eq. (242) by hΨ0n |,
The Harmonic . . . hence
Angular . . . hΨ0n | Ĥ0 | Ψ2n i+hΨ0n | Ĥp | Ψ1n i = En0 hΨ0n | Ψ2n i+En1 hΨ0n | Ψ1n i+En2 hΨ0n | Ψ0n i.
(256)
• Using the fact that
hΨ0n | Ĥ0 | Ψ2n i = En0 hΨ0n | Ψ2n i = 0, (257)
Home Page
Title Page
hΨ0n | Ψ0n i = 1 (258)
JJ II we find
En2 = hΨ0n | Ĥp | Ψ1n i. (259)
J I
Page 62 of 71
• Introducing Eq. (255) into Eq. (259)
X | hΨ0 | Ĥp | Ψ0 i |2
m n
Go Back En2 = 0 − E0
. (260)
m6=n
En m
Full Screen
Close
• Exercise: Consider a particle with charge q in a harmonic oscillator
potential. Suppose the system is perturbed by applying a constant
Quit electric field E0 pointing in the positive x direction. The potential
energy associated with this electric field is −qE0 x. Find an expres-
sion for the first and second -order energy shift (En1 and En2 ).
4.5. The time-dependent perturbation method
Probability and . . . • This method is most useful for studying process absorption and emis-
The Harmonic . . . sion of radiation by atoms or treating the transitions of quantum sys-
Angular . . .
tems from one energy level to another.
• Consider a two-level atom with the upper and lower levels denoted
by | Ψf i and | Ψi i respectively.
• The main objective of time-dependent perturbation method is to

Home Page
determine the probability of finding the system in another unper-
Title Page
turbed eigenstate | Ψf i; if the system is initially in an unperturbed
eigenstate | Ψi i.
JJ II
• The state vector of the system evolves in time according to
J I
d
Page 63 of 71 i~ | ΨI (t)i = Ĥp | ΨI (t)i, (261)
dt
Go Back
with Ĥp being the Hamiltonian that describes the interaction be-
Full Screen tween the system and the perturbation.
Close • or it characterizes the interaction of the system with the external

source of perturbation.
Quit
• When the system interacts with Ĥp (t) , it either absorbs or emits en-
ergy.
The Harmonic . . .
Angular . . .
Home Page
Title Page
JJ II
J I
Page 64 of 71
Figure 3: Energy eigenstates.

Go Back
Full Screen
• This process causes the system to under go transitions from one un-
Close
perturbed eigenstates to another.
Quit • A formal solution of Eq. (261) can be written as
| ΨI (t)i = UI (t) | Ψi i, (262)

where UI (t) is the evolution operator, with UI (0) = 1.
• Differentiating both sides of Eq. (262), we have
The Harmonic . . . d dUI (t)
Angular . . .
| ΨI (t)i = | Ψi i, (263)
dt dt
so that on account of Eq. (261) and Eq. (262), there follows
d
[i~ UI (t) − Ĥp UI (t)] | Ψi i = 0. (264)
Home Page dt
Title Page • Since | Ψi i is quite arbitrary, we note that

JJ II d
i~ UI (t) = Ĥp UI (t). (265)
J I
dt
Page 65 of 71 • A formal solution of this equation can be put in the form
i t
Z
Go Back
UI (t) = 1 − Ĥp (t0 )UI (t0 )dt0 . (266)
~ 0
Full Screen
Close • The first-order approximation is obtained by inserting UI (t0 ) = 1 into

in the integral sign of Eq. (266), leading to
Quit
i t
Z
1
UI (t) = 1 − Ĥp (t0 )dt0 . (267)
~ 0
• Substituting UI (t0 ) =UI1 (t) in the integral sign of Eq. (266) we get the
The Schrodinger . . . second-order approximation:
Probability and . . . Z t Z t Z t0
i 0 0 1 0 0
The Harmonic . . . UI2 (t) =1− Ĥp (t )dt − 2 Ĥp (t )dt Ĥp (t00 )dt00 . (268)
Angular . . . ~ 0 ~ 0 0
• We may continue this process, always substituting the nth order ap-
proximation into the right side of Eq. (266) and hence obtaining (n +
1)th -order approximation.
Home Page
• This series, known as the Dyson series, allows for the calculation of
Title Page the state vector up to the desired order in the perturbation.
JJ II • Using Eq. (262) and Eq. (267), the state vector in first-order approxi-
J I
mation has the form
i t
Z
0 0
Page 66 of 71 | ΨI (t)i = 1 − Ĥp (t )dt | Ψi i. (269)
~ 0
Go Back
⇒ Z t
i
Full Screen | ΨI (t)i =| Ψi i − Ĥp (t0 ) | Ψi idt0 . (270)
~ 0
Close
• The probability amplitude for the atom to make a transition from
Quit | Ψi i to | Ψf i is given by
cif = hΨf | ΨI (t)i. (271)

⇒ Z t
i
cif = hΨf | Ψi i − hΨf | Ĥp (t0 ) | Ψi idt0 . (272)
Probability and . . . ~ 0
The Harmonic . . .
• Since the energy eigenstates of the unperturbed system | Ψf i and
Angular . . .
| Ψi i are orthogonal, we see that
i t
Z
cif = − hΨf | Ĥp (t0 ) | Ψi idt0 . (273)
~ 0
Home Page
• Assignment Q. Suppose the interaction Hamiltonian Ĥp (t) is of the
Title Page form Ĥp (t)= (Âe−i(ω−ω0 )t +Â† e−i(ω−ω0 )t ), where the transition frequency
Ψ −Ψ
JJ II
ω0 = f ~ i is positive,hΨf | Â | Ψi i 6= 0 and hΨf | Â† | Ψi i = 0, with
the operator Â being time independent. Find the probability for the
J I system to absorb some energy and make a transition to the energy
eigenstate | Ψf i.
Page 67 of 71
Go Back
4.6. The Zeeman effect
Full Screen
Close
• When hydrogen atom is placed in a uniform external magnetic field,
its energy levels are shifted.
Quit
• The change in the energy levels of an atom caused by an external
uniform magnetic field is called the Zeeman effect.
• The Zeemen effect without the spin of the electron is called the nor-
The Schrodinger . . . mal Zeeman effect.
• When the spin of the electron is considered, we get what is called the
The Harmonic . . .
anomalous Zeeman effect.
Angular . . .
Home Page
Title Page
JJ II
J I
Page 68 of 71
Go Back
Full Screen
Close
Quit
5. Basics of Cold Atomic Gases
5.1. Identical particles in classical and quantum me-
The Harmonic . . .
Angular . . .
chanics
• In classical mechanics, when a system is made of identical particles,
it is possible to identify and distinguish each particle from each oth-
ers.
Home Page
• In quantum mechanics, however, identical particles are turly indis-
Title Page tinguishable.
JJ II • The wavefunction of a system of N identical particles is either sym-

metric or antisymmetric under the interchange of a pair of particles.
J I
• The sign is related to the spin of the particles:
Page 69 of 71
• The negative sign corresponds to particles with half-odd-integral spin

Go Back
and the positive sign corresponds to particles with integral spin.
Full Screen
• That is the wavefunctions of particles with integral spins are sym-
Close metric and the wavefunctions of particles with half-odd-integral spins
are antisymmetric.
Quit
• In fact, experimental observation show that, in nature, particles come

in two classes:
• Paticles with integral spin, S = 0, 1~, 2~, 3~, ... such as photons, pi-
The Schrodinger . . . ons, alpha particles are called bosons.
• Particles with half-odd-integral spin S = ~2 , 3~ , 5~ , 7~ , ... such as elec-
2 2 2
The Harmonic . . .
tron, quarks, positrons , neutrons are called fermions.
Angular . . .
• That is, particles occurring in nature are either bosons or fermions.
• Particles with integral spins, or bosons, have symmetric states while
particles with half-odd-integral spins, fermions, have antisymmetric
Home Page states.
Title Page • Pauli Exclusion Principle: states that no two electrons can occupy
simultaneously the same quantum state on the same atom; there
JJ II can be only one electron occupying a state of quantum numbers.
J I • What about bosons? Do they have any restriction like fermions?Not
Page 70 of 71
at all
Go Back
• There is no restriction on the number of bosons that can occupy a
single state.
Full Screen
• Insteady of the exclusion principle of fermions, bosons tend to con-
Close dense all in the same state, the ground state; this is called boson
condensation.
Quit
• This phenomenon is known as Bose-Einstein condensation.

The Harmonic . . .
Angular . . .
Home Page
Title Page
Thank you!
JJ II
J I
Page 71 of 71
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The Schrodinger . . .

Home Page Department of Physics

Full Screen • An operator is a mathematical rule that transforms a given function

JJ II • Dirac denoted the state vector Ψ by the symbol|Ψi, which he called

• Dirac denoted the scalar(inner) product by the symbol h|i, which he

• We must be careful to distinguish a scalar product from its complex

• A vector |Ψ1 i or |Ψ2 iis called normalized if,

hΨ1 |Ψ1 i = 1 or hΨ2 |Ψ2 i = 1 (2)

Go Back 1.4. Types of operators

• An operator Â is said to be Ske-Hermitian or ant-Hermitian if Â =

• An operator P̂ is said to be a projection operator if it is Hermitian

where a is a complex number, called an eigenvalue of Â.

• This equation is known as the eigenvalue equation, or eigenvalue

• The commonly used pictures in quantum mechanics includes the

• The orbital angular momentum operator L̂ can be obtained by re-

Page 11 of 71 From this we see that

• We now proceed to determine the commutation relation between

• Applying the commutation relation

[x̂, p̂x ] = [ŷ, p̂y ] = [ẑ, p̂z ] = i~, (22)

JJ II it can be readily established that

J I [L̂x , L̂y ] = i~L̂z , (23)

2.1. Eigenstates and eigenvalues of the angular momen-

Go Back L̂2 | λ, mi = ~2 λ | λ, mi, (26)

• The factor ~ is introduced so that λ and m are dimensionless.

• For simplicity, we assume that these eigenstates are orthonormal:

[L̂z , L̂± ] = ±~L̂± . (35)

Title Page • Let us see how L̂± operates on | λ, mi.

Page 15 of 71 Using Eq. (35), we have

Close • Hence the ket L̂± | λ, mi is an eigenstates of L̂z with eigenvalues

JJ II • One can thus write

J I L̂± | λ, mi = C± | λ, m ± 1i, (41)

Full Screen Comparing Eq. (44) and Eq. (47), we obtain

Close l = −l0 (48)

JJ II • Hence l can be integer or half-integer, depending on n being even or

• We now find it to be more convenient to denote the eigenstates of L̂2

L̂+ | l, mi = C+ | l, m + 1i, (56)

hm, l | L̂− = hm + 1, l | C+∗ , (57)

• We now seek to determine the possible values of the quantum num-

Go Back • The solution of Eq. (78) can be written as

• In view of this result, Υll (θ, φ) takes the form

Υll (θ, φ) = (−1)l | C | (sin θ)l eilφ , (89)

where | C | is to be fixed using the normalization condition.

J I [Ŝz , Ŝx ] = i~Ŝy . (97)

• Every elementary particle has a specific value of S, which we call the

Full Screen hα | Ŝ+ | βi = ~, (114)

• The spin angular momentum can be expressed as

Home Page Jˆy = L̂y + Ŝy , (132)

Jˆ2 | j, mi = ~2 j(j + 1) | j, mi,

• We then note that

• The classical Hamiltonian of the hydrogen atom is thus expressible

• Multiplying from the left by hφ, θ, r |, yields

hφ, θ | l, mihr | Ei = R(r)Υm

• By substituting Eq. (167) into Eq. (166), we have

Page 41 of 71 3.1. The energy Eigenvalues and eigenfunctions

• We can simplify the radial equation by writing

Go Back Hence we see that

In view of this result, the radial equation takes the form

• ii,On the other hand, for ρ → 0(for small values of r)

• Using Eqs. ((191)-(194)), we see that

• Substituting Eqs. ((195)-(198)) into Eq. (190), leads to

• For large k , we see that

Full Screen • Defining the principal quantum number n by

Go Back 3.2. Laguerre polynomial and Associated laguerre poly-