Department of Physics

Indian Institute of Technology Delhi

Expectation (or mean) value for position

¥

ò
-¥
dx |y ( x, t ) |2 = 1

Using the probability interpretation,

¥
< xˆ > = ò
-¥
dx x | y |2

¥
= ò dx y *
-¥
x y

1
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Indian Institute of Technology Delhi

Probability

= 14

2
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Probability – Most probable value

= 14

3
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Probability – Median

= 14

4
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Probability – Average or Expectation Value

= 14

This is called the

Expectation Value in QM
5
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Probability – Average of squares

= 14

6
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Probability – Variance or Standard Deviation

7
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Continuous Variable…

8
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Quantum mechanical operators: Observables

Indian Institute of Technology Delhi

In QM, dynamical variables are regarded as Operators, that can operate on

the state function of the system like
• Position: "! , #! , %̂ , r̂
• +
Momentum: &̂' , &̂) , &̂* , ,
• Kinetic energy: . -
• Potential energy: 0/
• -
Hamiltonian function: 1
• / etc.
Total energy: 2,
v Denote an operator with a cap: 3/
v Such operators corresponding to measurable quantities (or dynamical
variables) are called Observables.
v Note: Operators cannot be expressed as numbers. Their meaning can be
found only when the result of operation on the state function is known.
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QM operators: Observables…
Indian Institute of Technology Delhi

1. Operator for position x is "! such that: "! Ψ ", %, & = " Ψ ", %, & .

Þ Here "! ≠ " as "! is an operator and " is a number! An operator can
only be equal to another operator.
Þ "! operates on the wave function Ψ ", %, & and as a result Ψ ", %, & is
multiplied by the x-component of the postion coordinate. Thus,
"! Ψ " = 3, %, & = 3 Ψ " = 3, %, & .

01
2. Operator for momentum px is *
+, such that: *
+, Ψ ", %, & = −.ℏ
0,
0
Thus, *
+, ⟶ −.ℏ
0,
and in general, 3 ⟶ −.ℏ 5
4
 Department of Physics

QM operators: Observables…
Indian Institute of Technology Delhi

• If ! ", $% is a dynamical variable then operator representation of ! will be:

,
!& ", $% = ! ",
& $̂% = ! ",
& −*ℏ . Two examples:-
,%
./
3. Operator for Kinetic energy of a particle, - = is
01
ℏ/ 0
2
-⟶− 4
01
4. Operator for Hamiltonian 5 of a particle in a potential field 6(8) is
ℏ/ 0
5 ⟶ − 4 + 6; 8
2
01
5. Operator for Total energy, < is
,
<; ⟶ *ℏ
,=
For a conservative (time-independent) system, since the Hamiltonian function
is equal to the total energy, we get the operator equation:
52 = <;
ℏ/ 0 ,
− 4 + 6; 8 = *ℏ
01 ,=
 Department of Physics
Indian Institute of Technology Delhi

Eigenfunction & Eigenvalue of an Operator

• Recall from Matrix theory, the Eigenvalue equation:
"!#=%#
Here, a column vector # is called the “Eigenvector” belonging to an
!
“Eigenvalue” % (a constant) of a matrix ".
• In general, if a function &(() is such that an operator +* which operates on
&(() gives +* &(() = % &((),
where % is a constant independent of (, then
i. *
The function &(() is called the Eigenfunction of the operator +.
ii. The constant % is called the Eigenvalue of the operator +* belonging to an
Eigenfunction &(().
iii. The equation is called an Eigenvalue equation.

• Thus an Eigenvalue equation states that an operator, acting on a function,

reproduces the same function multiplied by a constant factor.
 Department of Physics
Indian Institute of Technology Delhi

Eigenfunction & Eigenvalue of an Operator…

• In QM, the Eigenvalue equation is:
"! Ψ$ % = ' Ψ$ (%)
where "! is an operator acting on a state function Ψ$ % giving the above
result. Here, ' is a number independent of %. Thus Ψ$ % is called the
! having an Eigenvalue '.
Eigenfunction of the operator ",
• Note: An operator acting, in general, on any wavefunction may not
generate an eigenvalue. Example: Consider
,
.0
Ψ * =+ ℏ /

à What will happen when 2̂0 acts on Ψ * ?

à What will happen when *3 acts on Ψ * ?
 Department of Physics
Indian Institute of Technology Delhi

Eigenfunction & Eigenvalue of an Operator…

• Significance: In QM, consider the Eigenvalue equation:
"! Ψ$ % = ' Ψ$ (%)
If a system is in an Eigenstate Ψ$ of the operator "! and a measurement of the
dynamical variable " is made on the system, then the result of the
measurement will be certain and equal to the Eigenvalue '. Thus
1. Energy eigenfunctions represent states where the energy of the system is
definitely known. For example: stationary states Φ % .
2. Momentum eigenfunctions represent states where momentum is definitely
,
..%
known. Example: Ψ % = + ℏ is an eigenfunction of momentum operator
of a single particle. In this state , the momentum of the particle is definitely
known and equal to ..
 Department of Physics

Energy Eigenfunctions & Energy Eigenvalues

Indian Institute of Technology Delhi

• ! is the Hamiltonian operator and E is the Energy Eigenvalue, then the

If "
energy eigenvalue equation is:
! Φ(%) = ( Φ(%)
"
,
! ⟶ − ℏ / - + 21 % . Thus the
For a single particle, the Hamiltonian op. is "
-.
time-independent Schrӧdinger equation is
ℏ- -
− / Φ % + 21 % Φ % = ( Φ %
24
Here E is not known quantity. Only those values of E are allowed that give a
solution for Φ % satisfying the admissible conditions it has to obey. These are
the Energy eigenvalues of the system. For a given eigenvalue, this eq. can be
solved to get the corresponding eigenfunction. The eigen function here is time-
independent.
 Department of Physics

Energy Eigenfunctions & Energy Eigenvalues

Indian Institute of Technology Delhi

• Time-dependent Schrӧdinger equation is found from the operator equation:

! Ψ $, & = )( Ψ($, &)
"
ℏ. / 56($,7)
Or, − 1 + 3($) Ψ $, & = 4ℏ
/0 57
The above equation is true for any wave function Ψ $, & .

• Discussions
For the special cases of Energy eigen functions, we must have
)( Ψ $, & = ) Ψ($, &),
;
:ℏ<7
Giving the complete solution: Ψ $, & = Ψ $, 0 9
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Scalar product
Indian Institute of Technology Delhi

•
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Orthogonal wave functions

Indian Institute of Technology Delhi

• Two non-zero wave functions are said to be orthogonal if their scalar

product: Ψ", Ψ$ = 0.
• Thus the condition of Orthogonality is:-
*) ∗ *)
∫() Ψ"Ψ$ ,- = 0 or ∫() Ψ"Ψ$∗ ,- =0
• Orthogonality of eigen functions: Two different eigen functions of a real
operator are orthogonal, that is if Ψ" and Ψ$ are two different eigen
functions of a real operator, then
*) ∗
In 3-D: ∫() Ψ"Ψ$ ,- = 0
*) ∗
In 1-D: ∫() Ψ"Ψ$ ,. = 0

• For proof à see blackboard & refer to “JG_Lecture5-Handout”

 Department of Physics

Orthogonal wave functions…

Indian Institute of Technology Delhi

,+ ∗
• For ! = #, the factor $% − $' = 0. So, ∫*+ Ψ%Ψ' /0 ≠ 0.
• If the wave functions are normalized, then we must have
,+ ∗ ,+
∫*+ Ψ% Ψ% /0 = ∫*+ Ψ'∗ Ψ' /0 = 1
Þ condition of Normalization

• Orthonomality: The conditions of Orthogonality and

Normalization can be combined to write
,+ ∗
∫*+ Ψ%Ψ' /0 = 3%'
where 3%' is the Kronecker delta function defined as,
3%' = 0 for ! ≠ #
=1 for ! = #
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Operator Algebra
Indian Institute of Technology Delhi
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Linear Operators
Indian Institute of Technology Delhi
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Operator algebra..
Indian Institute of Technology Delhi
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Commutator of two operators

Indian Institute of Technology Delhi

• In QM, it is customary to use short hand notation.

• If two operators are "! and $,
# then:
! $# = "! $# − $# "!
",
is called the commutator of "! and $# (in that order!)

• ! $# = "! $# − $# "! = − $,
Property: ", # "!
• ! $# = 0: "! and $# do commute with each other.
If ",
! $# ≠ 0: "! and $# do NOT commute with each other
If ",

•
 Department of Physics

Commutator of two operators…

Indian Institute of Technology Delhi

• For conjugate variables (eg. !, #$ ), their corresponding

operators “do NOT commute”. In such cases, the commutation
relation is given by:
!,
% #̂$ = !% #̂$ − #̂$ !% = )ℏ
This commutation relation leads to the uncertainty relation:
∆! ∆#$ ≥ ℏ/2
• Discussions
i. Show that !% and #̂$ satisfy the non-commutation relation.
ii. Show that !, % -% = 0.
iii. Show that !, % #̂0 = 0
 Department of Physics

Expectation Value
Indian Institute of Technology Delhi

• If "! is an operator representing a dynamical variable ", then

the expectation value of "! is given by:
"! = ∫% Ψ∗"! Ψ () ,
where Ψ(+) is the normalized wave function specifying the state
of the system on which the measurement is performed.
•

• Complex conjugate of the expectation value is

∗
"! = ∫% Ψ "! ∗ Ψ∗ ()
(See more details on Expectation value in JG_Lecture4).
 Department of Physics

Commutator of two operators

Indian Institute of Technology Delhi

• Commutator of "! and $:

#
! $# = "! $# − $# "!
",

• ! $# = "! $# − $# "! = − $,
Property: ", # "!
• ! $# = 0: "! and $# do commute with each other.
If ",
! $# ≠ 0: "! and $# do NOT commute with each other
If ",

• Discussions
i. Show that +* and -̂. satisfy the non-commutation relation: +,
* -̂/ = 0ℏ
ii. Show that +,
* 2* = 0.
iii. Show that +,
* -̂/ = 0
 Department of Physics

Commutator Rules
Indian Institute of Technology Delhi

• Antisymmetry: ! %$ = − %,
", $ "!

• Linearity: ! %$ + )! = ",
", ! %$ + ",
! )!

• Distributivity: "! %,
$ )! = ",
! )! %$ + "! %,
$ )!

! %$ )! = ",
", ! %$ )! + %$ ",
! )!
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Adjoint of an operator
Indian Institute of Technology Delhi

. What is "! # ?

Thus,
Using integration by parts:
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Adjoint of an operator…
Indian Institute of Technology Delhi

Rules to obtain the Hermitian conjugate of any expression:

1. cyclically reverse the order of the factors
2. replace constants by their complex conjugates
3. replace wave functions by their complex conjugates and vice
versa,
4. replace operators by their adjoints.
 Department of Physics

Adjoint of an operator…
Indian Institute of Technology Delhi

• Following these rules, we can guess that

 Department of Physics

Adjoint of an operator…
Indian Institute of Technology Delhi

• Following these rules, we can guess that

 Department of Physics

Adjoint of an operator…
Indian Institute of Technology Delhi

Note: The adjoint of an operator is not, in general, equal to its

complex conjugate: "! # ≠ "! ∗

-
E.g.: Consider the momentum operator '̂( = −+ℏ -(
∗ - ∗ -
'̂( = −+ℏ -( = +ℏ -(
# - # ∗ - # - -
'̂( = −+ℏ -( = −+ℏ -(
= +ℏ − -( = −+ℏ -(
Thus, '̂( # ≠ '̂( ∗

• But notice that: '̂( # = '̂( !!

 Department of Physics

Hermitian (or Real) Operator

Indian Institute of Technology Delhi

• Self-adjoint or Hermitian operator (definition):

"! # = "!
• An operator is said to be Hermitian if it is equal to its adjoint.
• For all dynamical variables the operators must be Hermitian.
• Expectation values of a Hermitian operator are all real:
∗
!
" = " !

or, ∫' Ψ∗"! Ψ )* = ∫' Ψ "! ∗ Ψ∗ )*

where Ψ(,) is the normalized wave function specifying the
state of the system on which the measurement is performed.
• Skew-Hermitian or Anti-Hermitian operator: .! # = −.!
 Department of Physics

Hermitian Operators…
Indian Institute of Technology Delhi

• Show that the commutator of two Hermitian operators is

anti-Hermitian.

à blackboard

• Show that "! and $̂% are Hermitian operators.

à work out (HW)

 Department of Physics

Properties of Hermitian operator

Indian Institute of Technology Delhi

• Properties:
1. Sum of two Hermitian operators is Hermitian.
2. Product of two Hermitian operators is Hermitian if and only if they
commute.
• Note: According to Dirac, the term “dynamical variable” in QM is applicable to
those quantities whose operators are Hermitian, and are called Observables.
Thus even though ! and "# are dynamical variables (as their operators !$ and "
%#
are Hermitian), the product !"# is NOT a dynamical variable because the
operators !$ and "
%# do NOT commute.

3. The eigen values of a Hermitian operator are real.

4. The eigen functions of a Hermitian operator are orthogonal if they
correspond to distinct eigen values.
(For proof à refer to “JG_Lecture5-Handout”)
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Properties of Hermitian operator…

Indian Institute of Technology Delhi

3.

1.

2.
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Classical Angular Momentum

Indian Institute of Technology Delhi

• In Classical Mechanics, the angular momentum of a particle is

defined as:
& ' (
! = #×% = ) * +
,- ,. ,/
= & *,/ − +,. + ' +,- − ),/ + ( ),. − *,- ,
where ‘#’ is the position vector and ‘%’ is the linear momentum of
the particle.
Thus, writing ! = &3- + '3. + (3/ , we get:
3- = *,/ − +,.
3. = +,- − ),/
3/ = ),. − *,-
 Department of Physics

Angular Momentum Operator

Indian Institute of Technology Delhi

( ( (
• In QM, we replace "̂# ⟶ −&ℏ , "̂) ⟶ −&ℏ , "̂* ⟶ −&ℏ ,
(# () (*
to get the following operator representation of
0 0
,+ # = −&ℏ /. − 1̂ Recall, from CM
0* 0)
0 0
,+ ) = −&ℏ 1̂ − 2.
0# 0*
0 0
,+ * = −&ℏ 2. − /.
0) 0#
• Operator for total angular momentum is:
3 = 5,+ # + 7,+ ) + 8,+ *
4
0 0 0 0 0 0
= −&ℏ 5 /. − 1̂ + 7 1̂ − 2. + 8 2. − /.
0* 0) 0# 0* 0) 0#
9 9 9
• Now, ,+9 = ,+ # + ,+ ) + ,+ *
0 0 9 0 0 9 0 0 9
= −ℏ9 /. − 1̂ + 1̂ − 2. + 2. − /.
0* 0) 0# 0* 0) 0#
 Department of Physics

AM Operator: Commutation relations

Indian Institute of Technology Delhi

• The components "! # , "! % , "! & of the angular momentum operator
do NOT commute. The corresponding commutation relations
are:- "! # , "! % = (ℏ "! &
"! % , "! & = (ℏ "! #
"! & , "! # = (ℏ "! %
• "!* commutes with each of the three components "! # , "! % , "! & and
hence also +! . Thus, "!*, "! # = 0
"!*, "! % = 0
"!*, "! & = 0
"!*, +! = 0
• Derive these commutation relations.
 Department of Physics

Topics I will broadly cover

Indian Institute of Technology Delhi

Part 3: Quantum Mechanics

• Quantum mechanical operators
• Eigen functions & eigen values
• Probability Current Density, Continuity Equation & Expectation value
• Fundamental postulates of QM
• Free-particle solution
• 1-D infinite potential well (revise)
• 1-D finite potential well
• Quantum mechanical tunneling & Alpha decay
• Krӧnig-Penney model & Emergence of bands
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Fundamental Postulates of QM
Indian Institute of Technology Delhi

Postulate 1: State of a system

The state of any physical system is specified, at each time !, by a
complex variable quantity Ψ = Ψ $, &, ', ! , called the wave
function or state function which contains (and serves to extract) all
needed information about the system. Any superposition ( =
∑-*+, .* Ψ* is also a state function.

Postulate 2: Observables & operators

To every physically measurable quantity /, called a dynamical
variable or an “observable”, there corresponds a linear Hermitian
operator /0 (property: /0 1 = /0 ) whose eigenvectors form a
complete basis.
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Fundamental Postulates of QM…

Indian Institute of Technology Delhi

Postulate 3: Measurements & eigenvalues of operators

The measurements of an observable ! may be represented formally by the
action of !" on a state function Ψ $, & . The only possible result of such a
" provided
measurement is given by one of the eigenvalues '( of the operator !,
"
the system is in an eigenstate of the operator !.

Postulate 4: Expectation value of an operator

The average or expectation value of an observable quantity ! with which an
operator !" is associated is given mathematically as
!" = ∫ Ψ ∗ !" Ψ ,- [if Ψ $, & is normalized]
∫ .∗ 0/ . 12
or, !" = [if Ψ $, & is NOT normalized]
∫ .∗ . 12
(the integration is extended over the entire space).
 Department of Physics

Fundamental Postulates of QM…

Indian Institute of Technology Delhi

Postulate 5: Time evolution of a system

The time-evolution of the wave function Ψ ", $ of a system is
governed by the time-dependent Schrödinger equation:
ℏ' ( 12(",3)
− () * + ,(") Ψ ", $ = 0ℏ 13
,
ℏ '
where 4
5 = − () * ( + ,(") is the Hamiltonian operator
corresponding to the total energy of the system.