CHM 112M: Lecture 3

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Arnab Ghosh
August 16, 2023

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1 Introduction
The central postulate1 in the Schrödinger formulation of quantum mechanics
(QM) is the existence of a unique mathematical function Ψ, called the wave func-

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tion, which is assumed to contain all information about the system. Through
a set of prescribed procedures, other postulates then extract information about
the system by utilizing the wave function Ψ. One of these postulates is on
quantum mechanical operators. In classical mechanics (CM), one encounters
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quantities such as displacement (x), linear momentum (p), angular momentum
(L), total energy (W ) — which are called dynamical variables. In Schrödinger’s
formulation, for each such dynamical variable a definite linear mathematical
operator is postulated. Quantum mechanical method is structured around the
wave function and these linear operators. The following are the basic postulates
of quantum mechanics, presented here for a one-particle system, for simplicity2 .
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2 Postulates of Quantum Mechanics

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Postulate 1: The wave function Ψ, for a single particle moving in space, is a

function of position coordinates x, y, z of the particle and time t, i.e Ψ(x, y, z, t) ≡
Ψ(r, t). (For a system of two particles 1 and 2, it would be Ψ(r1 , r2 , t)).
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Postulate 2: The QM linear operators for some dynamical variables in CM

are given by:
Dynamical variable (A) Operator (Â)
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x, y, z x, y, z
V (x, y, z) V (x, y, z)
∂ ∂ ∂
px , py , pz −ih̄ ∂x , −ih̄ ∂y , −ih̄ ∂z
∂
W ih̄ ∂t
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1 We limit ourselves to practical aspects of the postulates and we will not get into very

fundamental aspects of quantum measurements. See for instance article by W. E. Lamb, Jr.
Physics Today, 22, 23 (1969).
2 Note: This is Brief Overview of Class Topics (For Internal Use): Not a Lecture Substitute.

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 By linear operators we imply that they obey

 (c1 Ψ1 + c2 Ψ2 ) = c1 ÂΨ1 + c2 ÂΨ2 . (1)

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Examples of linear operators are dx , x etc, whereas examples of non-linear

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√
operators are , sin() etc. Some other important properties of operators will
be discussed later.
The total energy W of a single particle in CM is given by:
1 2
(p + p2y + p2z ) + V (x, y, z) = W. (2)
2m x

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Its quantum equivalent is obtained by substituting the classical dynamical vari-
ables by their respective quantum mechanical operators as follows3

h̄2
 2
∂2 ∂2

∂ ∂
− + 2 + 2 + V (x, y, z, t) = ih̄ , (3)

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2m ∂x 2 ∂y ∂z ∂t
| {z }
Hamiltonian operator or simply “Hamiltonian”

which upon inserting Ψ(x, y, z, t), reduces to

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h̄2
 2
∂2 ∂2
  
∂ ∂Ψ(x, y, z, t)
− 2
+ 2
+ 2
+ V (x, y, z, t) Ψ(x, y, z, t) = ih̄ , (4)
2m ∂x ∂y ∂z ∂t

time-dependent Schrödinger equation (TDSE) for the single particle.

Above procedure can be used to construct operator representations for other
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dynamical variables such as classical mechanical angular momentum L = r × p.

Since in Cartesian coordinate (mnemonic only)
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i j k
L= x y z = i(ypz − zpy ) + j(zpx − xpz ) + k(xpy − ypx )
px py pz
≡ iLx + jLy + kLz . (5)
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Using the operator representation for px , py and pz , we obtain

     
∂ ∂ ∂ ∂ ∂ ∂
L̂x = −ih̄ y −z , L̂y = −ih̄ z −x , L̂z = −ih̄ x −y , (6)
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∂z ∂y ∂x ∂z ∂y ∂x
3 LHS is called Hamiltonian operator in analogy to CM, H = T + V , where T and V is the

KE and PE respectively.
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 P(r, θ, ϕ)
z
θ

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r y
φ
x

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Figure 1: Spherical polar coordinates.

z = r cos θ), Lx , Ly and Lz become

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In spherical polar coordinates (where x = r sin θ cos φ, y = r sin θ sin φ and


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∂ ∂
L̂x = −ih̄ − sin(φ) − cot(θ) cos(φ) (7)
∂θ ∂φ
 
∂ ∂
L̂y = −ih̄ cos(φ) − cot(θ) sin(φ) (8)
∂θ ∂φ
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∂
L̂z = −ih̄ . (9)
∂φ
Further, since L2 = L2x + L2y + L2z , one gets the following operator form for L2
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in spherical polar coordinates

∂2
   
2 2 1 ∂ ∂ 1
L̂ = −h̄ sin(θ) + . (10)
sin(θ) ∂θ ∂θ sin2 (θ) ∂φ2
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Postulate 3: Ψ(x, y, z, t) and ∂Ψ/∂x, ∂Ψ/∂y, and ∂Ψ/∂z are finite, continuous
and single-valued for all values of x, y and z, i.e., in the entire configuration
space.
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Postulate 4:
Z Z
Ψ∗ (x, y, z, t)Ψ(x, y, z, t)dτ = |Ψ(x, y, z, t)|2 dτ = 1, (11)
all space all space
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i.e., Ψ is normalized. Ψ∗ is the complex conjugate of Ψ; dτ is the volume

element. For Cartesian coordinates dτ = dxdydz; in spherical polar coordinates
dτ = r2 sin θdrdθdφ. Finally, Ψ∗ Ψ represents the probability density in the
volume element dτ and this is due to 1926 Copenhagen interpretation by Born.
Above two postulates characterize the criterion for any well-behaved wave
functions. For example, it must be single valued, otherwise it will correspond

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 to different probability density at a particular position, which is not possible.
Note that probability density is always positive irrespective of the form of the
wave function and the wave function must be square integrable to allow for Born
interpretation.

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Postulate 5: The average value (or the quantum mechanical expectation
value) hÂi of any dynamical variable A, associated with the quantum mechanical
operator  ≡ Aop , can be calculated as
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hÂi = Ψ∗ Aop Ψdτ . (12)
all space

If the wave function Ψ is not normalized, then the above expression modifies as

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follows:
Ψ∗ Aop Ψdτ
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all space
hÂi = R . (13)
all space
Ψ∗ Ψdτ
Expectation values of operators representing physical variables must be real. In

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order that a linear operator has a real expectation value it is required that
Z Z
(Aop Ψ)∗ Ψdτ = Ψ∗ Aop Ψdτ. (14)
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Operators which satisfy this criterion are called Hermitian operators. All quan-
tum mechanical operators representing physical observables are Hermitian op-
erators.

3 Stationary States:
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A considerable simplification of SE can be obtained if the PE does not depend

on time. The general solution can then be expressed as
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Ψ(x, y, z, t) = ci ψi (x, y, z)fi (t), (15)
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where ci ’s are the weight factors. A particular solution of TDSE (Eq. (4)) can
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be written as Ψ(x, y, z, t) = ψ(x, y, z)f (t). Upon substituting in Eq. (4) and
dividing both sides of the equation by ψ(x, y, z)f (t), we find
h̄2
 2
∂2 ∂2
  
1 ∂ ih̄ df (t)
− 2
+ 2 + 2 ψ(x, y, z) + V (x, y, z) = . (16)
ψ(x, y, z) 2m ∂x ∂y ∂z f (t) dt
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Since, LHS depends only on (x, y, z) (Note PE is time independent) and RHS
only on t, both sides can only be a constant (say, E), independent of (x, y, z) or
t in order to satisfy the above equation. Thus, we get two set of equations:
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df (t)
(i) ih̄ = Ef (t) =⇒ f (t) = Ce−iEt/h̄ , (17)
dt
h̄2 ∂2 ∂2 ∂2
   
(ii) − 2
+ 2 + 2 + V (x, y, z) ψ(x, y, z) = Eψ(x, y, z),
2m ∂x ∂y ∂z
(18)

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 and the full solution takes the following form:

Ψ(r, t) ≡ Ψ(x, y, z, t) = ψ(x, y, z)e−iEt/h̄ (19)

Both Eqs. (17) and (18) are of a same type where an operator acting on an

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operand and yields the operand with a multiplication constant. This type equa-
tions of are called eigenvalue equations, where the operand is called an eigenfunc-
tion and the generated constant is called an eigenvalue. The solutions ψ(x, y, z)
of the TISE Eq. (18) are called stationary states as they are independent of time
or more generally Ψ(r, t) of the form of Eq. (19), are called stationary states as
the probability density Ψ∗ Ψ is independent of time.

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4 Uncertainty Principle
In nature, there are fundamental limitations on measuring physical observables

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accurately. Certain pairs of these observables cannot be simultaneously known
with arbitrary accuracy. When one is measured with high accuracy, the other
becomes increasingly uncertain. This is known as the uncertainty principle,
first enunciated by Heisenberg. These paired observables are referred to as
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conjugate pairs. As an example, position coordinate x and the corresponding
linear momentum px are such conjugate pairs. If the uncertainty in measuring
x is ∆x and px is ∆px , then according to uncertainty principle, the product
∆x∆px , can’t be made arbitrarily small and it will be precisely given by
h̄
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∆x∆px ≥ . (20)
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Here the quantum mechanical uncertainty related to q
any of the physical vari-
able ∆A is given by the positive square root ∆A = hÂi2 − hÂi2 . A similar
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relationship between energy and time also holds

h̄
∆E∆t ≥ , (21)
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which is often stated as an example of the same uncertainty principle. This is

not quite true as time appears as a parameter in QM. A correct interpretation
of Eq. (21) is that shorter the time interval of the energy measurement, larger
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will be the uncertainty in energy measured.

Mathematically, uncertainty principle can be expressed a commutator of two
operators  and B̂, defined via
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[Â, B̂] = ÂB̂ − B̂ Â. (22)

If the two operators represent two physical observables and their commutator
is zero, they are said to commute and they can be simultaneously determined
with any arbitrary degree of accuracy. For conjugate pairs, for which uncer-
tainty principle restricts the limit of accuracy of simultaneous measurement, the

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 operators don’t commute, leaving a non-zero value for the commutator. This
immediately suggests that uncertainty relation is fundamental and it has noth-
ing to do with accuracy of the experimental measurement. Using the operator
representation, one can verify

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[x̂, p̂x ] = [ŷ, p̂y ] = [ẑ, p̂z ] = ih̄, (23)

[x̂, p̂y ] = [x̂, p̂z ] = [ŷ, p̂x ] = [ŷ, p̂z ] = [ẑ, p̂x ] = [ẑ, p̂y ] = 0. (24)

So, variables of conjugate pairs can’t be simultaneously known, whereas position

coordinate in one direction and momentum along some other direction, can be

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simultaneously specified with any desired level of accuracy. Applying the same
to the angular momentum commutators, one finds

[L̂x , L̂y ] = ih̄L̂z , [L̂y , L̂z ] = ih̄L̂x , [L̂z , L̂x ] = ih̄L̂y , (25)

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[L̂x , L̂2 ] = [L̂y , L̂2 ] = [L̂z , L̂2 ] = 0.
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Thus, the total angular momentum can be accurately determined along with any
one of its components. However, two or more components of angular momentum
can’t be simultaneously determined with arbitrary accuracy. The uncertainty
principle is therefore a fundamental law of nature and it is equally applicable
to macroscopic systems as well as microscopic objects. Because of very small
value of h, however, it is of little significance for macroscopic bodies and most
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significant for atomic scales.

NOTE: In order to derive Eq. (26), make use of the following operator
commutation relation:
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[Â, B̂ Ĉ] = [Â, B̂]Ĉ + B̂[Â, Ĉ]. (Try to derive!) (27)

Reference:
1. Atomic Electronic Structure by P. K. Ghosh and P. K. Shukla. (PKG)
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