CHAPTER 1 Quantum Mechanics – I 29

 Quantum Mechanical Operators and Their Commutation Relations

An operator may be simply defined as a mathematical procedure or instruction which is carried out
over a function to yield another function.

(Operator) . (Function) = (Another function) (67)

The function used on the left-hand side of the equation (67) is called as the operand i.e. the function
over which the operation is actually carried out. The operator alone has no significance but when operated over
a certain mathematical description, these operators can provide very detailed insights into those functions.
Some of the simple illustrations of equation (67) are given below.
i) Consider the differential operator d/dx whose operation has to be studied over the function y = x5. The
mathematical treatment is

𝑑𝑦 𝑑 5 (68)
= 𝑥 = 5𝑥 4
𝑑𝑥 𝑑𝑥
The operation of d/dx on y means that the rate of change of function y w.r.t. the variable x. The expression x5
is the operand while the 5x4 is the final result of our differential operator.
ii) Consider the integral operator ʃ (y) dx whose operation has to be studied over the function y = x5. The
mathematical treatment is

𝑥6 (69)
∫ 𝑦(𝑑𝑥) = ∫ 𝑥 5 (𝑑𝑥) =
6

The operation of ʃdx on y means that we can find the function whose derivative is x5. The expression x5 is the
operand while the x6/6 is the final result of our integral operator.
In a similar way, the multiplication of a function by a constant number, or taking the square and cube
roots of any function are also the operators which give some other function after operating them over the
operand. The symbol of the operator typically carries a cap over it (Â) which differentiates it from the function
used in the whole procedure.

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 30 A Textbook of Physical Chemistry – Volume I

 Algebra of Operators
Just like the normal algebra, the resultants like addition or the multiplication of operators also follow
certain rules; however, these rules are different from the typical algebra. Some of the most important rules of
operator algebra are given below.
1. Addition and subtraction of operators: Let A and B as two different operators; f as the function that has
to be used as the operand. Then, the addition and subtraction of these two operators must be carried out in the
manner discussed below.

(𝐴̂ + 𝐵̂)𝑓 = 𝐴̂𝑓 + 𝐵̂𝑓 (70)

and

(𝐴̂ − 𝐵̂)𝑓 = 𝐴̂𝑓 − 𝐵̂𝑓 (71)

2. Multiplication of operators: If A and B as two different operators; and f as the function that has to be used
as operand. Then, the multiplication of these two operators must be carried out in the manner discussed below.

𝐴̂𝐵̂𝑓 = 𝑓 ′′ (72)

The interpretation of the above equation is that first we need to operate B on f, which would give us another
function f´, which in turn is further used as the operand for operator giving the final result fʺ. In other words,
we can say that when multiplication of two or more operators is used, we should follow from left to right.
Moreover, the square or cube of a particular operator must be considered as double or triple multiplication of
the operator itself; mathematically, it can be shown as given below.

𝐴̂2 𝑓 = 𝐴̂𝐴̂𝑓 (73)

At this point it also very important to discuss one of the most fundamental properties of operator
multiplication, the commutation relation or the commutation rule. Consider two operators, A and B which can
be operated over the function f.

𝑑 (74)
𝐴̂ = ; 𝐵̂ = 𝑥; 𝑓 = 𝑥3
𝑑𝑥
Now

𝑑 𝑑 4 (75)
𝐴̂𝐵̂𝑓 = 𝑥(𝑥 3 ) = 𝑥 = 4𝑥 3
𝑑𝑥 𝑑𝑥
And

𝑑 3 (76)
𝐵̂𝐴̂𝑓 = 𝑥 (𝑥 ) = 𝑥(3𝑥 2 ) = 3𝑥 3
𝑑𝑥
From equation (75) and (76), it the clear that in this case

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 CHAPTER 1 Quantum Mechanics – I 31

𝐴̂𝐵̂𝑓 ≠ 𝐵̂𝐴̂𝑓 (77)

These operators are said to be non-commutating with the commutator given below.

𝐴̂𝐵̂ − 𝐵̂𝐴̂ = 4𝑥 3 − 3𝑥 3 (78)

However, the two operators are said to be commute if their result is the same even after reverting their order
of application. Mathematically, it can be stated as given by equation (79).

𝐴̂𝐵̂𝑓 = 𝐵̂𝐴̂𝑓 (79)

This is quite different from the normal algebra in which the product of two numbers is always the same
irrespective of the order of multiplication (x.y = y.x). Summarizing the commutation rule, it can be concluded
that

̂ 𝐵̂] = 𝐴̂𝐵̂ − 𝐵̂𝐴̂ = 0 → 𝐶𝑜𝑚𝑚𝑢𝑡𝑎𝑡𝑖𝑛𝑔

[𝐴, (80)

and

̂ 𝐵̂] = 𝐴̂𝐵̂ − 𝐵̂𝐴̂ ≠ 0 → 𝑁𝑜𝑛-𝑐𝑜𝑚𝑚𝑢𝑡𝑎𝑡𝑖𝑛𝑔

[𝐴, (81)

3. Linear Operator: An operator  is said to be a linear operator if its application on the sum of two functions
f and g gives the same result as the sum of its individual operations. Mathematically, it can be shown as given
below.

𝐴̂(𝑓 + 𝑔) = 𝐴̂𝑓 + 𝐴̂𝑔 (82)

For example, consider the differential operator A; with f and g as the functions which have to be used as the
operand.

𝑑 (83)
𝐴̂ = ; 𝑓 = 2𝑥 2 ; 𝑔 = 3𝑥 2
𝑑𝑥
or

𝑑 𝑑 (84)
𝐴̂(𝑓 + 𝑔) = (2𝑥 2 + 3𝑥 2 ) = (5𝑥 2 ) = 10𝑥
𝑑𝑥 𝑑𝑥
or

𝑑 𝑑 (85)
𝐴̂𝑓 + 𝐴̂𝑔 = (2𝑥 2 ) + (3𝑥 2 ) = 4𝑥 + 6𝑥 = 10𝑥
𝑑𝑥 𝑑𝑥
Hence, from equation (84) and equation (85), it is clear that the differential operator is clearly linear
in nature. On the other hand, the “square root” operator is not linear as it does not give the same result when
operated individually.

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 32 A Textbook of Physical Chemistry – Volume I

 Some Important Quantum Mechanical Operators

One of the most basic and very popular operators in quantum mechanics is the Laplacian operator,
typically symbolized as ∇2, and is given by the following expression.

𝜕2 𝜕2 𝜕2 (86)
∇2 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

The popular form of the Schrodinger equation can be written in terms of Laplacian operator as well.

𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 (87)
+ + + (𝐸 − 𝑉)𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2

or

8𝜋 2 𝑚 (88)
∇2 𝜓 + (𝐸 − 𝑉)𝜓 = 0
ℎ2
The Laplacian operator is pronounced as “del squared”. This operator is also a part of the “mighty”
Hamiltonian operator which forms the basis for value evaluation for other operators, as we have already
discussed in the postulates of quantum mechanics. The Hamiltonian operator is typically symbolized as 𝐻
̂ and
is given by the following expression.

ℎ2 𝜕2 𝜕2 𝜕2 (89)
̂=−
𝐻 ( + + )+𝑉
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

or

ℎ2 (90)
̂=−
𝐻 ∇2 + 𝑉
8𝜋 2 𝑚
The popular form of the Schrodinger equation is written in terms of the Hamiltonian operator as well.

̂ 𝜓 = 𝐸𝜓
𝐻 (91)

or

ℎ2 𝜕2 𝜕2 𝜕2 (92)
[− ( + + ) + 𝑉] 𝜓 = 𝐸𝜓
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

or

ℎ2 (93)
(− ∇2 + 𝑉) 𝜓 = 𝐸𝜓
8𝜋 2 𝑚

Furthermore, we know from the third postulate of quantum mechanics that owing to the constant value of E
(eigenvalue) the wave function ψ can be labeled as eigenfunction.

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 CHAPTER 1 Quantum Mechanics – I 33

Therefore, the Schrodinger equation is also called as the “eigen value equation”. Simplifying this, we can say
that

(𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑝𝑒𝑟𝑎𝑡𝑜𝑟)(𝑊𝑎𝑣𝑒 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛) = (𝐸𝑛𝑒𝑟𝑔𝑦)(𝑊𝑎𝑣𝑒 𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛) (94)

The equation (94) is applicable to observables in the quantum mechanical world.

For three dimensional systems, like the Hamiltonian, the operator can be obtained by summing the
individual operators along three different axes. For instance, some important three-dimensional operators are:

−ℎ2 𝜕 2 𝜕2 𝜕2 (95)
𝑇̂ = ( + + )
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

ℎ 𝜕 𝜕 𝜕 (96)
𝑝̂ = ( + + )
2𝜋𝑖 𝜕𝑥 𝜕𝑦 𝜕𝑧

The list of various important quantum mechanical operators in one dimension, along with their mode of
operation is given below.

Table 2. Name and symbols of various important physical properties and their corresponding quantum
mechanical operators.

Physical property Operator

Name Symbol Symbol Operation

Position x 𝑥̂ Multiplication by x

Position squared x2 𝑥̂ 2 Multiplication by x2

Position cubed x3 𝑥̂ 2 Multiplication by x3

Momentum px 𝑝̂𝑥 ℎ 𝜕
2𝜋𝑖 𝜕𝑥
Momentum squared px2 𝑝̂𝑥2 −ℎ2 𝜕 2
4𝜋 2 𝜕𝑥 2
Kinetic energy 𝑃2 𝑇̂𝑥 −ℎ2 𝜕 2
𝑇=
2𝑚 8𝜋 2 𝑚 𝜕𝑥 2
Potential energy V(x) 𝑉̂ (𝑥) Multiplication by V(x)

Total energy 𝐸 = 𝑇 + 𝑉(𝑥) ̂

𝐻 −ℎ2 𝜕 2
+ 𝑉(𝑥)
8𝜋 2 𝑚 𝜕𝑥 2

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 34 A Textbook of Physical Chemistry – Volume I

Besides the record of different operators presented in ‘Table 2’, there still many operators which are
extremely important like angular momentum, parity, or the step-up–step-down operators. The discussion of
every operator is beyond the scope of this book; however, a brief discussion of the essential operators in
quantum mechanics is given below.
1. Angular momentum operator: In order to understand the angular momentum operator in the quantum
mechanical world, we first need to understand the classical mechanics of one particle angular momentum. Let
us consider a particle of mass m which moves within a cartesian coordinate system with a position vector “r”.
Hence, we can say that

𝑟 = 𝑖𝑥 + 𝑗𝑦 + 𝑘𝑧 (97)

The coordinates x. y and z are the functions of time, and therefore, we can define the velocity as the time
derivative of the position vector as given below.

𝑑𝑟 𝑑𝑥 𝑑𝑦 𝑑𝑧 (98)
𝑣= =𝑖 +𝑗 +𝑘
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡
or

𝑣 = 𝑣𝑥 + 𝑣𝑦 + 𝑣𝑧 (99)

Now, since we that p = mv, we can say that

𝑝𝑥 = 𝑚𝑣𝑥 ; 𝑝𝑦 = 𝑚𝑣𝑦 ; 𝑝𝑧 = 𝑚𝑣𝑧 (100)

The angular momentum of a particle with mass m and distance r from the origin is given by the following
relation.

Figure 6. The angular momentum vector.

𝐿⃗ = 𝑣 × 𝑚 × 𝑟 (101)

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𝐿⃗ = 𝑝 × 𝑟 (102)

Equation (102) can also be written in the form of a matrix as:

𝑖 𝑗 𝑘 (103)
𝐿=[ 𝑥 𝑦 𝑧]
𝑝𝑥 𝑝𝑦 𝑝𝑧

𝐿𝑥 = 𝑦𝑝𝑧 − 𝑧𝑝𝑦 ; 𝐿𝑦 = 𝑧𝑝𝑥 − 𝑥𝑝𝑧 ; 𝐿𝑧 = 𝑥𝑝𝑦 − 𝑦𝑝𝑥 (104)

Where i, j, k are the unit vectors along x, y, z axis and Lx, Ly, Lz are the component of angular momentum along
x, y, z axis. Moreover, it is also worthy to note that the angular momentum vector is always perpendicular to
the direction of the position vector of the particle i.e. the plane in which the particle is moving.
Now since the mathematical nature of any quantum mechanical operator is dependent upon the
classical expression of the same observable, the angular momentum is not any exception. The quantum
mechanical operator for angular momentum is given below.

ℎ (105)
𝐿̂ = −𝑖 (𝑟 × ∇) = −𝑖ħ(𝑟 × ∇)
2𝜋
The angular momentum can be divided into two categories; one is orbital angular momentum (due to the orbital
motion of the particle) and the other is spin angular momentum (due to spin motion of the particle). Moreover,
being a vector quantity, the operator of angular momentum can also be resolved along different axes.

𝐿̂ = 𝐿̂𝑥 + 𝐿̂𝑦 + 𝐿̂𝑧 (106)

And we know that

ℎ 𝜕 ℎ 𝜕 ℎ 𝜕 𝜕 (107)
𝐿̂𝑥 = 𝑦𝑝𝑧 − 𝑧𝑝𝑦 = 𝑦 ( )−𝑧( )= (𝑦 − 𝑧 )
2𝜋𝑖 𝜕𝑧 2𝜋𝑖 𝜕𝑦 2𝜋𝑖 𝜕𝑧 𝜕𝑦

or

ℎ 𝜕 ℎ 𝜕 ℎ 𝜕 𝜕 (108)
𝐿̂𝑦 = 𝑧𝑝𝑥 − 𝑥𝑝𝑧 = 𝑧 ( )−𝑥( )= (𝑧 −𝑥 )
2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑧 2𝜋𝑖 𝜕𝑥 𝜕𝑧
or

ℎ 𝜕 ℎ 𝜕 ℎ 𝜕 𝜕 (109)
𝐿̂𝑧 = 𝑥𝑝𝑦 − 𝑦𝑝𝑥 = 𝑥 ( )−𝑦( )= (𝑥 −𝑦 )
2𝜋𝑖 𝜕𝑦 2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑦 𝜕𝑥

ℎ 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (110)
𝐿̂ = [(𝑦 − 𝑧 ) + (𝑧 − 𝑥 ) + (𝑥 − 𝑦 )]
2𝜋𝑖 𝜕𝑧 𝜕𝑦 𝜕𝑥 𝜕𝑧 𝜕𝑦 𝜕𝑥

It is also worthy to recall that equation (107) to (110) can also be reported in terms of ħ; or by multiplying and
dividing by i, or both.

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 36 A Textbook of Physical Chemistry – Volume I

2. Ladder operator: These operators are also called as step-up–step-down or rising-lowering operators. The
reason for such terminology lies in the fact that these operators can increase or decrease the eigenvalues.
Moreover, it should also be noted that this increase or decrease is always quantized in nature.

𝐽̂+ = 𝐽̂𝑥 + 𝑖𝐽̂𝑦 (111)

and

𝐽̂+ = 𝐽̂𝑥 − 𝑖𝐽̂𝑦 (112)

The equation (111) and (112) represent the step-up and step-down operators respectively. These operators can
be used to increase or decrease the eigen values.
 Operator Evaluation
The operator evaluation simply means that we need to find the result by applying the operator over a
given function. Some general examples are given below.
i) (d/dx) (x5): In this case d/dx is the operator while the function x5 is the operand.

𝑑 5 (113)
𝑥 = 5𝑥 4
𝑑𝑥
ii) ʃ(x5): In this case, ʃ is the operator while the function x5 is the operand.

𝑥6 (114)
∫ 𝑥5 =
6

iii) (d2/dt2) (ASine 2πνt): In this particular case, (d2/dt2) is the operator while the function (A Sin 2πνt) is the
operand.
Let the function is symbolized by y. Then, we have

𝑦 = 𝐴 𝑆𝑖𝑛 2𝜋𝜈𝑡 (115)

Differentiating with respect to t, we get

𝑑𝑦 (116)
= 𝐴 2𝜋𝜈 𝐶𝑜𝑠 2𝜋𝜈𝑡
𝑑𝑡
Differentiating again

𝑑2 𝑦 (117)
= −𝐴 4𝜋 2 𝜈 2 𝑆𝑖𝑛 2𝜋𝜈𝑡
𝑑𝑡 2
The operator evaluation is frequently used as a part of the commutator calculation and will be
discussed in detail in this chapter.

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 Calculation of Resultant Operator

Sometimes the operator is simplified to another form which is easy to apply over a function. This
resultant operator is obtained by the rules of operator algebra. For instance, consider the following cases.
i) Find the resultant expression for the following operator

𝑑 2 (118)
( 𝑥)
𝑑𝑥
In order to find the resultant operator, suppose a function ψ(x) which is used as an operand, then we can say

𝑑 2
𝑑 𝑑 (119)
( 𝑥) 𝜓 = ( 𝑥) ( 𝑥) 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥
or

𝑑 2
𝑑 𝑑 (120)
( 𝑥) 𝜓 = ( 𝑥) ( 𝑥𝜓)
𝑑𝑥 𝑑𝑥 𝑑𝑥
or

𝑑 2
𝑑 𝑑𝜓 𝑑𝑥 (121)
( 𝑥) 𝜓 = ( 𝑥) (𝑥 +𝜓 )
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑 𝑑𝜓 (122)
( 𝑥) 𝜓 = (𝑥 2 + 𝑥𝜓)
𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝜓 𝑑𝜓 𝑑𝜓 𝑑𝑥 (123)
( 𝑥) 𝜓 = [𝑥 2 2 + (2𝑥)] + [𝑥 +𝜓 ]
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝜓 𝑑𝜓 𝑑𝜓 (124)
2
( 𝑥) 𝜓 = 𝑥 + 2𝑥 + 𝑥 +𝜓
𝑑𝑥 𝑑𝑥 2 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝑑 (125)
( 𝑥) 𝜓 = [𝑥 2 2 + 3𝑥 + 1] 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥

Removing ψ from both sides, we get

𝑑 2
𝑑2 𝑑 (126)
( 𝑥) = 𝑥 2 2 + 3𝑥 +1
𝑑𝑥 𝑑𝑥 𝑑𝑥
ii) Find the resultant expression for the following operator

𝑑 𝑑 (127)
(𝑥 + )
𝑑𝑥 𝑑𝑥
In order to find the resultant operator, suppose a function ψ(x) which is used as operand, then we can say that

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 38 A Textbook of Physical Chemistry – Volume I

𝑑 𝑑 𝑑 𝑑𝜓 (128)
[(𝑥 + ) ] 𝜓 = (𝑥 + )
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 𝑑 𝑑𝜓 𝑑2 𝜓
[(𝑥 + ) ]𝜓 = 𝑥 +
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 2
Removing ψ from both sides, we get

𝑑 𝑑 𝑑 𝑑2 (129)
(𝑥 + ) =𝑥 + 2
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥
iii) Find the resultant expression for the following operator

𝑑 2 (130)
( + 𝑥)
𝑑𝑥
In order to find the resultant operator, suppose a function ψ(x) which is used as operand, then we can say that

𝑑 2
𝑑 𝑑 (131)
[( + 𝑥) ] 𝜓 = [( + 𝑥) ( + 𝑥)] 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑 𝑑𝜓 (132)
[( + 𝑥) ] 𝜓 = ( + 𝑥) ( + 𝑥𝜓)
𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝜓 𝑑 𝑑𝜓 (133)
[( + 𝑥) ] 𝜓 = 2
+ 𝑥𝜓 + 𝑥 + 𝑥2𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝜓 𝑑𝜓 𝑑𝑥 𝑑𝜓 (134)
[( + 𝑥) ] 𝜓 = 2
+𝑥 +𝜓 +𝑥 + 𝑥2𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 2
𝑑2 𝜓 𝑑𝜓 (135)
[( + 𝑥) ] 𝜓 = 2
+ 2𝑥 + 𝑥2𝜓 + 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥

Removing ψ from both sides, we get

𝑑 2
𝑑2 𝑑 (136)
( + 𝑥) = 2 + 2𝑥 + 𝑥2 + 1
𝑑𝑥 𝑑𝑥 𝑑𝑥
iv) Find the resultant expression for the following operator

𝑑 𝑑 (137)
(𝑥 + ) (𝑥 − )
𝑑𝑥 𝑑𝑥
In order to find the resultant operator, suppose a function ψ(x) which is used as operand, then we can say that

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𝑑 𝑑 𝑑 𝑑𝜓 (138)
[(𝑥 + ) (𝑥 − )] 𝜓 = (𝑥 + ) (𝑥𝜓 − )
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 𝑑 𝑑𝜓 𝑑 𝑑2 𝜓 (139)
[(𝑥 + ) (𝑥 − )] 𝜓 = 𝑥𝑥𝜓 − 𝑥 + 𝑥𝜓 − 2
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

𝑑 𝑑 𝑑𝜓 𝑑𝜓 𝑑𝑥 𝑑2 𝜓 (140)
[(𝑥 + ) (𝑥 − )] 𝜓 = 𝑥 2 𝜓 − 𝑥 +𝑥 +𝜓 −
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 2

𝑑 𝑑 𝑑𝑥 𝑑2 𝜓 (141)
[(𝑥 + ) (𝑥 − )] 𝜓 = 𝑥 2 𝜓 + 𝜓 −
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 2

𝑑 𝑑 𝑑𝑥 𝑑2 (142)
[(𝑥 + ) (𝑥 − )] 𝜓 = [𝑥 2 + − 2] 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥

Removing ψ from both sides, we get

𝑑 𝑑 𝑑2 (143)
(𝑥 + ) (𝑥 − ) = 𝑥 2 + 1 − 2
𝑑𝑥 𝑑𝑥 𝑑𝑥
The resultant operator calculation is frequently used as a part of the commutator calculation and will
be discussed in detail in this chapter.
 Commutation Relations of Various Quantum Mechanical Operators
As we have discussed previously that one of the most fundamental properties of operator
multiplication is the commutation relation or the commutation rule. two operators, A and B, are said to be
commutating or non-commutating depending upon the value of their commutator.

̂ 𝐵̂] = 𝐴̂𝐵̂ − 𝐵̂𝐴̂ = 0 → 𝐶𝑜𝑚𝑚𝑢𝑡𝑎𝑡𝑖𝑛𝑔

[𝐴, (144)

̂ 𝐵̂] = 𝐴̂𝐵̂ − 𝐵̂𝐴̂ ≠ 0 → 𝑁𝑜𝑛-𝑐𝑜𝑚𝑚𝑢𝑡𝑎𝑡𝑖𝑛𝑔

[𝐴, (145)

The physical significance of the commutation relations is that when two operators commute, it means they are
having a simultaneous set of eigenfunctions; and their corresponding physical properties can be calculated
simultaneously and accurately. However, if the commutator is non-zero, the respective physical properties
cannot be obtained simultaneously and accurately. Some important commutation relations are given below.
1. Commutators of some simple operators:
i) Calculate the commutator of the following

𝑑 (146)
[𝑥, ]
𝑑𝑥
Let it be operated over a function ψ. We have

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 40 A Textbook of Physical Chemistry – Volume I

𝑑 𝑑 𝑑 (147)
[𝑥, ]𝜓 = 𝑥 𝜓− 𝑥𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑑 𝑑𝜓 𝑑𝜓 (148)
[𝑥, ]𝜓 = 𝑥 −𝜓−𝑥
𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑑 (149)
[𝑥, ] 𝜓 = −𝜓
𝑑𝑥
or

𝑑 (150)
[𝑥, ] = −1
𝑑𝑥
ii) Calculate the commutator of the following

𝑑 (151)
[𝑦, ]
𝑑𝑥
Let it be operated over a function ψ. We have

𝑑 𝑑 𝑑 (152)
[𝑦, ]𝜓 = 𝑦 𝜓− 𝑦𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑑 𝑑𝜓 𝑑𝜓 𝑑𝑦 (153)
[𝑦, ]𝜓 = 𝑦 −𝑦 −𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥
𝑑 (154)
[𝑥, ]𝜓 = 0
𝑑𝑥
iii) Calculate the commutator of the following

𝑑 𝑑2 (155)
[ , 2]
𝑑𝑥 𝑑𝑥

Let it be operated over a function ψ. We have

𝑑 𝑑2 𝑑 𝑑2 𝑑2 𝑑 (156)
[ , 2 ]𝜓 = 𝜓 − 𝜓
𝑑𝑥 𝑑𝑥 𝑑𝑥 𝑑𝑥 2 𝑑𝑥 2 𝑑𝑥

or

𝑑 𝑑2 𝑑3 𝜓 𝑑3 𝜓 (157)
[ , 2 ]𝜓 = −
𝑑𝑥 𝑑𝑥 𝑑𝑥 3 𝑑𝑥 3

𝑑 𝑑2 (158)
[ , 2 ]𝜓 = 0
𝑑𝑥 𝑑𝑥

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2. Commutators of position and linear momentum operators:

i) Find the commutator of the following

[𝑥̂, 𝑝̂𝑥 ] (159)

Let it be operated over a function ψ. We have

[𝑥̂, 𝑝̂𝑥 ]𝜓 = 𝑥̂ 𝑝̂𝑥 𝜓 − 𝑝̂𝑥 ̂𝑥 𝜓 (160)

ℎ 𝜕 ℎ 𝜕 (161)
[𝑥̂, 𝑝̂𝑥 ]𝜓 = 𝑥 𝜓− 𝑥𝜓
2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑥
ℎ 𝜕𝜓 ℎ 𝜕𝜓 ℎ 𝜕𝑥 (162)
[𝑥̂, 𝑝̂𝑥 ]𝜓 = 𝑥 − 𝑥 − 𝜓
2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑥
ℎ
[𝑥̂, 𝑝̂𝑥 ]𝜓 = − 𝜓
2𝜋𝑖
ℎ ℎ𝑖 (163)
[𝑥̂, 𝑝̂𝑥 ] = − = = 𝑖ħ
2𝜋𝑖 2𝜋
ii) Find the commutator of the following

[𝑥̂ 𝑛 , 𝑝̂𝑥 ] (164)

Let it be operated over a function ψ. We have

[𝑥̂ 𝑛 , 𝑝̂𝑥 ]𝜓 = 𝑥̂ 𝑛 𝑝̂𝑥 𝜓 − 𝑝̂𝑥 𝑥̂ 𝑛 𝜓 (165)

ℎ 𝜕 ℎ 𝜕 𝑛 (166)
[𝑥̂ 𝑛 , 𝑝̂𝑥 ]𝜓 = 𝑥 𝑛 𝜓− 𝑥 𝜓
2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑥
ℎ 𝑛 𝜕𝜓 ℎ 𝑛 𝜕𝜓 ℎ (167)
[𝑥̂ 𝑛 , 𝑝̂𝑥 ]𝜓 = 𝑥 − 𝑥 − 𝑛𝑥 𝑛−1 𝜓
2𝜋𝑖 𝜕𝑥 2𝜋𝑖 𝜕𝑥 2𝜋𝑖
ℎ (168)
[𝑥̂ 𝑛 , 𝑝̂𝑥 ]𝜓 = − 𝑛𝑥 𝑛−1 𝜓
2𝜋𝑖
Removing ψ from both sides, we get

ℎ (169)
[𝑥̂ 𝑛 , 𝑝̂𝑥 ] = − 𝑛𝑥 𝑛−1
2𝜋𝑖
The commutation relations between position and linear momentum can mainly be divided into three
categories as discussed below.
(a) When position and momentum are along the same axis:

[𝑥̂ 𝑛 , 𝑝̂𝑥 ] = 𝑛𝑖ħ𝑥 𝑛−1 (170)

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[ 𝑝̂𝑥 , 𝑥̂ 𝑛 ] = −𝑛𝑖ħ𝑥 𝑛−1 (171)

and

[𝑥̂, 𝑝̂𝑥𝑛 ] = 𝑛𝑖ħ𝑝𝑥𝑛−1 (172)

[𝑝̂𝑥𝑛 , 𝑥̂ ] = −𝑛𝑖ħ𝑝𝑥𝑛−1 (173)

(b) When position and momentum are along different axis:

[𝑥̂, 𝑝̂𝑦 ] = 0 (174)

[𝑥̂, 𝑝̂𝑧 ] = 0 (175)

[𝑦̂, 𝑝̂𝑥 ] = 0 (176)

[𝑦̂, 𝑝̂𝑧 ] = 0 (177)

[𝑧̂ , 𝑝̂𝑥 ] = 0 (178)

[𝑧̂ , 𝑝̂𝑦 ] = 0 (179)

(b) When positions are along the different axis:

[𝑥̂, 𝑦̂] = 0 (180)

[𝑥̂, 𝑧̂ ] = 0 (181)

[𝑦̂, 𝑧̂ ] = 0 (182)

(b) When positions are along the different axis:

[𝑝̂𝑥 , 𝑝̂𝑦 ] = 0 (183)

[𝑝̂𝑥 , 𝑝̂𝑧 ] = 0 (184)

[𝑝̂𝑦 , 𝑝̂𝑧 ] = 0 (185)

3. Commutators of angular momentum operators:

i) The commutator of orbital angular momentum operators along x and y-axis.

[𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝐿̂𝑥 𝐿̂𝑦 − 𝐿̂𝑦 𝐿̂𝑥 (186)

Finding the values of 𝐿̂𝑥 𝐿̂𝑦 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (187)
𝐿̂𝑥 𝐿̂𝑦 = [ (𝑦 − 𝑧 )] [ (𝑧 − 𝑥 )]
2𝜋𝑖 𝜕𝑧 𝜕𝑦 2𝜋𝑖 𝜕𝑥 𝜕𝑧

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ℎ2 𝜕 𝜕 𝜕 𝜕 (188)
= − 2 [(𝑦 − 𝑧 ) (𝑧 − 𝑥 )]
4𝜋 𝜕𝑧 𝜕𝑦 𝜕𝑥 𝜕𝑧

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (189)
= − 2 (𝑦 𝑧 −𝑧 𝑧 −𝑦 𝑥 +𝑧 𝑥 )
4𝜋 𝜕𝑧 𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑧 𝜕𝑧 𝜕𝑦 𝜕𝑧

ℎ2 𝜕 𝜕𝑧 𝜕2 2
𝜕2 𝜕2 𝜕2 (190)
= − 2 (𝑦 + 𝑦𝑧 2 − 𝑧 2 − 𝑦𝑥 2 + 𝑧𝑥 )
4𝜋 𝜕𝑥 𝜕𝑧 𝜕 𝑧𝑥 𝜕 𝑦𝑥 𝜕𝑧 𝜕𝑦𝑧

𝜕 𝜕2 𝜕2 𝜕2 𝜕2 (191)
= −ħ2 (𝑦 + 𝑦𝑧 2 − 𝑧 2 2 − 𝑦𝑥 2 + 𝑧𝑥 )
𝜕𝑥 𝜕 𝑧𝑥 𝜕 𝑦𝑥 𝜕𝑧 𝜕𝑦𝑧

Similarly obtaining the value of 𝐿̂𝑦 𝐿̂𝑥 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (192)
𝐿̂𝑦 𝐿̂𝑥 = [ (𝑧 − 𝑥 )] [ (𝑦 − 𝑧 )]
2𝜋𝑖 𝜕𝑥 𝜕𝑧 2𝜋𝑖 𝜕𝑧 𝜕𝑦

ℎ2 𝜕 𝜕 𝜕 𝜕 (193)
=− 2 [(𝑧 − 𝑥 ) (𝑦 − 𝑧 )]
4𝜋 𝜕𝑥 𝜕𝑧 𝜕𝑧 𝜕𝑦

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (194)
=− 2
(𝑧 𝑦 − 𝑧 𝑧 −𝑥 𝑦 +𝑥 𝑧 )
4𝜋 𝜕𝑥 𝜕𝑧 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑧 𝜕𝑧 𝜕𝑦

ℎ2 𝜕2 2
𝜕2 𝜕2 𝜕2 𝜕 𝜕𝑧 (195)
=− 2 (𝑧𝑦 2
− 𝑧 2
− 𝑥𝑦 2
+ 𝑥𝑧 +𝑥 )
4𝜋 𝜕 𝑥𝑧 𝜕 𝑥𝑦 𝜕𝑧 𝜕𝑧𝑦 𝜕𝑦 𝜕𝑧

2
𝜕2 2
𝜕2 𝜕2 𝜕2 𝜕 (196)
= −ħ (𝑧𝑦 2 − 𝑧 2 − 𝑥𝑦 2 + 𝑥𝑧 +𝑥 )
𝜕 𝑥𝑧 𝜕 𝑥𝑦 𝜕𝑧 𝜕𝑧𝑦 𝜕𝑦

Now putting the values of 𝐿̂𝑥 𝐿̂𝑦 and 𝐿̂𝑦 𝐿̂𝑥 in equation (183), we get the following.

𝜕 𝜕2 𝜕2 𝜕2 𝜕2 (197)
[𝐿̂𝑥 , 𝐿̂𝑦 ] = [−ħ2 (𝑦 + 𝑦𝑧 2 − 𝑧 2 2 − 𝑦𝑥 2 + 𝑧𝑥 )]
𝜕𝑥 𝜕 𝑧𝑥 𝜕 𝑦𝑥 𝜕𝑧 𝜕𝑦𝑧
𝜕2 𝜕2 𝜕2 𝜕2 𝜕
− [−ħ2 (𝑧𝑦 2
− 𝑧 2
2
− 𝑥𝑦 2
+ 𝑥𝑧 + 𝑥 )]
𝜕 𝑥𝑧 𝜕 𝑥𝑦 𝜕𝑧 𝜕𝑧𝑦 𝜕𝑦

𝜕 𝜕 (198)
[𝐿̂𝑥 , 𝐿̂𝑦 ] = −ħ2 (𝑦 −𝑥 )
𝜕𝑥 𝜕𝑦

Taking negative sign common, we get

𝜕 𝜕 (199)
[𝐿̂𝑥 , 𝐿̂𝑦 ] = ħ2 (𝑥 −𝑦 )
𝜕𝑦 𝜕𝑥

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𝜕 𝜕 (200)
[𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ħ [−𝑖ħ (𝑥 − 𝑦 )]
𝜕𝑦 𝜕𝑥

[𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ħ𝐿̂𝑧 (201)

ii) The commutator of orbital angular momentum operators along y and z-axis.

[𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑦 (202)

Finding the values of 𝐿̂𝑦 𝐿̂𝑧 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (203)
𝐿̂𝑦 𝐿̂𝑧 = [ (𝑧 − 𝑥 )] [ (𝑥 − 𝑦 )]
2𝜋𝑖 𝜕𝑥 𝜕𝑧 2𝜋𝑖 𝜕𝑦 𝜕𝑥

ℎ2 𝜕 𝜕 𝜕 𝜕 (204)
= − 2 [(𝑧 − 𝑥 ) (𝑥 − 𝑦 )]
4𝜋 𝜕𝑥 𝜕𝑧 𝜕𝑦 𝜕𝑥

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (205)
= − 2 (𝑧 𝑥 −𝑥 𝑥 −𝑧 𝑦 +𝑥 𝑦 )
4𝜋 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑧 𝜕𝑥

ℎ2 𝜕 𝜕𝑥 𝜕2 2
𝜕2 𝜕 𝜕2 (206)
= − 2 (𝑧 + 𝑧𝑥 − 𝑥 2 − 𝑧𝑦 2 + 𝑥𝑦 )
4𝜋 𝜕𝑦 𝜕𝑥 𝜕𝑥𝑦 𝜕 𝑧𝑦 𝜕𝑥 𝜕𝑧𝑥

𝜕 𝜕2 𝜕2 𝜕 𝜕2 (207)
= −ħ2 (𝑧 + 𝑧𝑥 − 𝑥 2 2 − 𝑧𝑦 2 + 𝑥𝑦 )
𝜕𝑦 𝜕𝑥𝑦 𝜕 𝑧𝑦 𝜕𝑥 𝜕𝑧𝑥

Similarly obtaining the value of 𝐿̂𝑧 𝐿̂𝑦 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (208)
𝐿̂𝑧 𝐿̂𝑦 = [ (𝑥 − 𝑦 )] [ (𝑧 − 𝑥 )]
2𝜋𝑖 𝜕𝑦 𝜕𝑥 2𝜋𝑖 𝜕𝑥 𝜕𝑧

ℎ2 𝜕 𝜕 𝜕 𝜕 (209)
=− 2 [(𝑥 − 𝑦 ) (𝑧 − 𝑥 )]
4𝜋 𝜕𝑦 𝜕𝑥 𝜕𝑥 𝜕𝑧

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (210)
=− 2
(𝑥 𝑧 −𝑥 𝑥 −𝑦 𝑧 +𝑦 𝑥 )
4𝜋 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑥 𝜕𝑥 𝜕𝑥 𝜕𝑧

ℎ2 𝜕2 2
𝜕2 𝜕2 𝜕2 𝜕 𝜕𝑥 (211)
=− 2 (𝑥𝑧 − 𝑥 − 𝑦𝑧 2
+ 𝑦𝑥 +𝑦 )
4𝜋 𝜕𝑦𝑥 𝜕𝑦𝑧 𝜕𝑥 𝜕𝑥𝑧 𝜕𝑧 𝜕𝑥

2
𝜕2 2
𝜕2 𝜕2 𝜕2 𝜕 (212)
= −ħ (𝑥𝑧 −𝑥 − 𝑦𝑧 2 + 𝑦𝑥 +𝑦 )
𝜕𝑦𝑥 𝜕𝑦𝑧 𝜕𝑥 𝜕𝑥𝑧 𝜕𝑧

Now putting the values of 𝐿̂𝑦 𝐿̂𝑧 and 𝐿̂𝑧 𝐿̂𝑦 in equation (212), we get the following.

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𝜕 𝜕2 𝜕2 𝜕 𝜕2 (213)
[𝐿̂𝑦 , 𝐿̂𝑧 ] = [−ħ2 (𝑧 + 𝑧𝑥 2
− 𝑥 2 − 𝑧𝑦 2 + 𝑥𝑦 )]
𝜕𝑦 𝜕𝑥𝑦 𝜕 𝑧𝑦 𝜕𝑥 𝜕𝑧𝑥
𝜕2 𝜕2 𝜕2 𝜕2 𝜕
− [−ħ2 (𝑥𝑧 − 𝑥2 − 𝑦𝑧 2 + 𝑦𝑥 + 𝑦 )]
𝜕𝑦𝑥 𝜕𝑦𝑧 𝜕𝑥 𝜕𝑥𝑧 𝜕𝑧

𝜕 𝜕 (214)
[𝐿̂𝑦 , 𝐿̂𝑧 ] = −ħ2 (𝑧 −𝑦 )
𝜕𝑦 𝜕𝑧

Taking negative sign common, we get

𝜕 𝜕 (215)
[𝐿̂𝑦 , 𝐿̂𝑧 ] = ħ2 (𝑦 −𝑧 )
𝜕𝑧 𝜕𝑦

𝜕 𝜕 (216)
[𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝑖ħ [−𝑖ħ (𝑦 − 𝑧 )]
𝜕𝑧 𝜕𝑦

[𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝑖ħ𝐿̂𝑥 (217)

iii) The commutator of orbital angular momentum operators along z and x-axis.

[𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝐿̂𝑧 𝐿̂𝑥 − 𝐿̂𝑥 𝐿̂𝑧 (218)

Finding the values of 𝐿̂𝑧 𝐿̂𝑥 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (219)
𝐿̂𝑧 𝐿̂𝑥 = [ (𝑥 − 𝑦 )] [ (𝑦 − 𝑧 )]
2𝜋𝑖 𝜕𝑦 𝜕𝑥 2𝜋𝑖 𝜕𝑧 𝜕𝑦

ℎ2 𝜕 𝜕 𝜕 𝜕 (220)
=− 2 [(𝑥 − 𝑦 ) (𝑦 − 𝑧 )]
4𝜋 𝜕𝑦 𝜕𝑥 𝜕𝑧 𝜕𝑦

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (221)
=− 2
(𝑥 𝑦 − 𝑥 𝑧 −𝑦 𝑦 +𝑦 𝑧 )
4𝜋 𝜕𝑦 𝜕𝑧 𝜕𝑦 𝜕𝑦 𝜕𝑥 𝜕𝑧 𝜕𝑥 𝜕𝑦

ℎ2 𝜕 𝜕𝑦 𝜕2 𝜕2 2
𝜕2 𝜕2 (222)
=− (𝑥 + 𝑥𝑦 − 𝑥𝑧 − 𝑦 + 𝑦𝑧 )
4𝜋 2 𝜕𝑧 𝜕𝑦 𝜕𝑦𝑧 𝜕𝑦 2 𝜕𝑥𝑧 𝜕𝑥𝑦

𝜕 𝜕2 𝜕2 𝜕2 𝜕2 (223)
= −ħ2 (𝑥 + 𝑥𝑦 − 𝑥𝑧 2 − 𝑦 2 + 𝑦𝑧 )
𝜕𝑧 𝜕𝑦𝑧 𝜕𝑦 𝜕𝑥𝑧 𝜕𝑥𝑦

Similarly obtaining the value of 𝐿̂𝑥 𝐿̂𝑧 , we get

ℎ 𝜕 𝜕 ℎ 𝜕 𝜕 (224)
𝐿̂𝑥 𝐿̂𝑧 = [ (𝑦 − 𝑧 )] [ (𝑥 − 𝑦 )]
2𝜋𝑖 𝜕𝑧 𝜕𝑦 2𝜋𝑖 𝜕𝑦 𝜕𝑥

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ℎ2 𝜕 𝜕 𝜕 𝜕 (225)
= − 2 [(𝑦 − 𝑧 ) (𝑥 − 𝑦 )]
4𝜋 𝜕𝑧 𝜕𝑦 𝜕𝑦 𝜕𝑥

or

ℎ2 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 𝜕 (226)
= − 2 (𝑦 𝑥 −𝑦 𝑦 −𝑧 𝑥 +𝑧 𝑦 )
4𝜋 𝜕𝑧 𝜕𝑦 𝜕𝑧 𝜕𝑥 𝜕𝑦 𝜕𝑦 𝜕𝑦 𝜕𝑥

ℎ2 𝜕2 2
𝜕2 𝜕2 𝜕 𝜕𝑦 𝜕2 (227)
= − 2 (𝑦𝑥 −𝑦 − 𝑧𝑥 2 + 𝑧 + 𝑧𝑦 )
4𝜋 𝜕𝑧𝑦 𝜕𝑧𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑦𝑥

𝜕2 𝜕2 𝜕2 𝜕 𝜕2 (228)
= −ħ2 (𝑦𝑥 − 𝑦2 − 𝑧𝑥 2 + 𝑧 + 𝑧𝑦 )
𝜕𝑧𝑦 𝜕𝑧𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝑥

Now putting the values of 𝐿̂𝑧 𝐿̂𝑥 and 𝐿̂𝑥 𝐿̂𝑧 in equation (218), we get the following.

𝜕 𝜕2 𝜕2 𝜕2 𝜕2 (229)
[𝐿̂𝑧 , 𝐿̂𝑥 ] = [−ħ2 (𝑥 + 𝑥𝑦 − 𝑥𝑧 2 − 𝑦 2 + 𝑦𝑧 )]
𝜕𝑧 𝜕𝑦𝑧 𝜕𝑦 𝜕𝑥𝑧 𝜕𝑥𝑦
2
𝜕2 2
𝜕2 𝜕2 𝜕 𝜕2
− [−ħ (𝑦𝑥 −𝑦 − 𝑧𝑥 2 + 𝑧 + 𝑧𝑦 )]
𝜕𝑧𝑦 𝜕𝑧𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦𝑥

𝜕 𝜕 (230)
[𝐿̂𝑧 , 𝐿̂𝑥 ] = −ħ2 (𝑥 −𝑧 )
𝜕𝑧 𝜕𝑥
Taking negative sign common, we get

𝜕 𝜕 (231)
[𝐿̂𝑧 , 𝐿̂𝑥 ] = ħ2 (𝑦 −𝑧 )
𝜕𝑧 𝜕𝑦

𝜕 𝜕 (232)
[𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝑖ħ [−𝑖ħ (𝑦 − 𝑧 )]
𝜕𝑧 𝜕𝑦

[𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝑖ħ𝐿̂𝑦 (233)

iv) The commutator of total orbital angular momentum squared operator and orbital angular momentum along
one of the three-axis.

[𝐿̂2 , 𝐿̂𝑧 ] = [𝐿̂2𝑥 + 𝐿̂2𝑦 + 𝐿̂2𝑧 , 𝐿̂𝑧 ] (234)

= [𝐿̂2𝑥 𝐿̂𝑧 + 𝐿̂2𝑦 𝐿̂𝑧 + 𝐿̂2𝑧 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑥 − 𝐿̂𝑧 𝐿̂2𝑦 − 𝐿̂𝑧 𝐿̂2𝑧 ] (235)

= [(𝐿̂2𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑥 ) + (𝐿̂2𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑦 ) + (𝐿̂2𝑧 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑧 )] (236)

[𝐿̂2 , 𝐿̂𝑧 ] = [𝐿̂2𝑥 , 𝐿̂𝑧 ] + [𝐿̂2𝑦 𝐿̂𝑧 ] + [𝐿̂2𝑧 𝐿̂𝑧 ] (237)

Now finding [𝐿̂2𝑥 , 𝐿̂𝑧 ] first, we get

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[𝐿̂2𝑥 , 𝐿̂𝑧 ] = 𝐿̂2𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑥 (238)

= 𝐿̂𝑥 𝐿̂𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑥 𝐿̂𝑥 (239)

= [𝐿̂𝑥 𝐿̂𝑥 𝐿̂𝑧 − 𝐿̂𝑥 𝐿̂𝑧 𝐿̂𝑥 ] − [𝐿̂𝑧 𝐿̂𝑥 𝐿̂𝑥 − 𝐿̂𝑥 𝐿̂𝑧 𝐿̂𝑥 ] (240)

= 𝐿̂𝑥 [𝐿̂𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑥 ] − [𝐿̂𝑧 𝐿̂𝑥 − 𝐿̂𝑥 𝐿̂𝑧 ]𝐿̂𝑥 (241)

= 𝐿̂𝑥 [𝐿̂𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑥 ] + [𝐿̂𝑥 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑥 ]𝐿̂𝑥 (242)

= 𝐿̂𝑥 [−𝑖ħ𝐿̂𝑦 ] + [−𝑖ħ𝐿̂𝑦 ]𝐿̂𝑥 (243)

= −𝑖ħ𝐿̂𝑥 𝐿̂𝑦 − 𝑖ħ𝐿̂𝑦 𝐿̂𝑥 = −𝑖ħ[𝐿̂𝑥 𝐿̂𝑦 + 𝐿̂𝑦 𝐿̂𝑥 ] (244)

Similarly,

[𝐿̂2𝑦 , 𝐿̂𝑧 ] = 𝐿̂2𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑦 (245)

= 𝐿̂𝑦 𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑦 𝐿̂𝑦 (246)

= [𝐿̂𝑦 𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑦 𝐿̂𝑧 𝐿̂𝑦 ] − [𝐿̂𝑧 𝐿̂𝑦 𝐿̂𝑦 − 𝐿̂𝑦 𝐿̂𝑧 𝐿̂𝑦 ]

= 𝐿̂𝑦 [𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑦 ] − [𝐿̂𝑧 𝐿̂𝑦 − 𝐿̂𝑦 𝐿̂𝑧 ]𝐿̂𝑦

= 𝐿̂𝑦 [𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑦 ] + [𝐿̂𝑦 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑦 ]𝐿̂𝑦

= 𝐿̂𝑦 [𝑖ħ𝐿̂𝑥 ] + [𝑖ħ𝐿̂𝑥 ]𝐿̂𝑦

= 𝑖ħ𝐿̂𝑦 𝐿̂𝑥 + 𝑖ħ𝐿̂𝑥 𝐿̂𝑦 = 𝑖ħ[𝐿̂𝑦 𝐿̂𝑥 + 𝐿̂𝑥 𝐿̂𝑦 ] (247)

Similarly,

[𝐿̂2𝑧 , 𝐿̂𝑧 ] = 𝐿̂2𝑧 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂2𝑧

= 𝐿̂𝑧 𝐿̂𝑧 𝐿̂𝑧 − 𝐿̂𝑧 𝐿̂𝑧 𝐿̂𝑧

[𝐿̂2𝑧 , 𝐿̂𝑧 ] = 0 (248)

Now putting the value of 𝐿̂2𝑥 𝐿̂𝑧 , 𝐿̂2𝑦 𝐿̂𝑧 and 𝐿̂2𝑧 𝐿̂𝑧 in equation (237), we get

[𝐿̂2 , 𝐿̂𝑧 ] = −𝑖ħ[𝐿̂𝑥 𝐿̂𝑦 + 𝐿̂𝑦 𝐿̂𝑥 ] + 𝑖ħ[𝐿̂𝑦 𝐿̂𝑥 + 𝐿̂𝑥 𝐿̂𝑦 ] + 0

[𝐿̂2 , 𝐿̂𝑧 ] = 0 (249)

Also

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[𝐿̂2 , 𝐿̂𝑦 ] = 0; 𝑎𝑛𝑑 [𝐿̂2 , 𝐿̂𝑥 ] = 0 (250)

Hence, the commutation relations of angular momentum operators along two different directions do not
commute with each other and hence cannot give eigenvalues simultaneously and accurately. One the other
hand, total angular momentum squared and angular momentum along one axis do commute with each other.
The commutation relations between angular momentum operators can be mainly divided into four
categories as discussed below.
(a) Orbital angular momentum commutation:

[𝐿̂𝑥 , 𝐿̂𝑦 ] = 𝑖ħ𝐿̂𝑧 ; [𝐿̂𝑦 , 𝐿̂𝑥 ] = −𝑖ħ𝐿̂𝑧 (251)

[𝐿̂𝑦 , 𝐿̂𝑧 ] = 𝑖ħ𝐿̂𝑥 ; [𝐿̂𝑧 , 𝐿̂𝑦 ] = −𝑖ħ𝐿̂𝑥 (252)

[𝐿̂𝑧 , 𝐿̂𝑥 ] = 𝑖ħ𝐿̂𝑦 ; [𝐿̂𝑥 , 𝐿̂𝑧 ] = −𝑖ħ𝐿̂𝑦 (253)

[𝐿̂2 , 𝐿̂𝑥 ] = 0; [𝐿̂𝑥 , 𝐿̂2 ] = 0 (254)

[𝐿̂2 , 𝐿̂𝑦 ] = 0; [𝐿̂𝑦 , 𝐿̂2 ] = 0 (255)

[𝐿̂2 , 𝐿̂𝑧 ] = 0; [𝐿̂𝑧 , 𝐿̂2 ] = 0 (256)

(b) Spin angular momentum commutation:

[𝑆̂𝑥 , 𝑆̂𝑦 ] = 𝑖ħ𝑆̂𝑧 ; [𝑆̂𝑦 , 𝑆̂𝑥 ] = −𝑖ħ𝑆̂𝑧 (257)

[𝑆̂𝑦 , 𝑆̂𝑧 ] = 𝑖ħ𝑆̂𝑥 ; [𝑆̂𝑧 , 𝑆̂𝑦 ] = −𝑖ħ𝑆̂𝑥 (258)

[𝑆̂𝑧 , 𝑆̂𝑥 ] = 𝑖ħ𝑆̂𝑦 ; [𝑆̂𝑥 , 𝑆̂𝑧 ] = −𝑖ħ𝑆̂𝑦 (259)

[𝑆̂ 2 , 𝑆̂𝑥 ] = 0; [𝑆̂𝑥 , 𝑆̂ 2 ] = 0 (260)

[𝑆̂ 2 , 𝑆𝑦 ] = 0; [𝑆̂𝑦 , 𝑆̂ 2 ] = 0 (261)

[𝑆̂ 2 , 𝑆̂𝑧 ] = 0; [𝑆̂𝑧 , 𝑆̂ 2 ] = 0 (262)

(c) Total angular momentum commutation:

[𝐽̂𝑥 , 𝐽̂𝑦 ] = 𝑖ħ𝐽̂𝑧 ; [𝐽̂𝑦 , 𝐽̂𝑥 ] = −𝑖ħ𝐽̂𝑧 (263)

[𝐽̂𝑦 , 𝐽̂𝑧 ] = 𝑖ħ𝐽̂𝑥 ; [𝐽̂𝑧 , 𝐽̂𝑦 ] = −𝑖ħ𝐽̂𝑥 (264)

[𝐽̂𝑧 , 𝐽̂𝑥 ] = 𝑖ħ𝐽̂𝑦 ; [𝐽̂𝑥 , 𝐽̂𝑧 ] = −𝑖ħ𝐽̂𝑦 (265)

[𝐽̂2 , 𝐽̂𝑥 ] = 0; [𝐽̂𝑥 , 𝐽̂2 ] = 0 (266)

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[𝐽̂2 , 𝐽𝑦 ] = 0; [𝐽̂𝑦 , 𝐽̂2 ] = 0 (267)

[𝐽̂2 , 𝐽̂𝑧 ] = 0; [𝐽̂𝑧 , 𝐽̂2 ] = 0 (268)

(d) Total angular momentum commutation:

[𝐿̂𝑥 , 𝑆̂𝑥 ] = 0; [𝑆̂𝑥 , 𝐿̂𝑥 ] = 0 (263)

[𝐿̂𝑥 , 𝑆̂𝑦 ] = 0; [𝑆̂𝑦 , 𝐿̂𝑥 ] = 0 (264)

[𝐿̂𝑥 , 𝑆̂𝑧 ] = 0; [𝑆̂𝑧 , 𝐿̂𝑥 ] = 0 (265)

[𝐿̂𝑦 , 𝑆̂𝑥 ] = 0; [𝑆̂𝑥 , 𝐿̂𝑦 ] = 0 (266)

[𝐿̂𝑦 , 𝑆̂𝑦 ] = 0; [𝑆̂𝑦 , 𝐿̂𝑦 ] = 0 (267)

[𝐿̂𝑦 , 𝑆̂𝑧 ] = 0; [𝑆̂𝑧 , 𝐿̂𝑦 ] = 0 (268)

[𝐿̂𝑧 , 𝑆̂𝑥 ] = 0; [𝑆̂𝑥 , 𝐿̂𝑧 ] = 0 (269)

[𝐿̂𝑧 , 𝑆̂𝑦 ] = 0; [𝑆̂𝑦 , 𝐿̂𝑧 ] = 0 (270)

[𝐿̂𝑧 , 𝑆̂𝑧 ] = 0; [𝑆̂𝑧 , 𝐿̂𝑧 ] = 0 (271)

4. Commutators of Ladder operators:

i) Find the commutator of the following

[𝐽̂2 , 𝐽̂+ ] (272)

Let

[𝐽̂2 , 𝐽̂+ ] = [𝐽̂2 , 𝐽̂𝑥 + 𝑖𝐽̂𝑦 ] (273)

= 𝐽̂2 (𝐽̂𝑥 + 𝑖𝐽̂𝑦 ) − (𝐽̂𝑥 + 𝑖𝐽̂𝑦 )𝐽̂2 (274)

= 𝐽̂2 𝐽̂𝑥 + 𝑖𝐽̂2 𝐽̂𝑦 − 𝐽̂𝑥 𝐽̂2 − 𝑖𝐽̂𝑦 𝐽̂2 (275)

= [𝐽̂2 𝐽̂𝑥 − 𝐽̂𝑥 𝐽̂2 ] + 𝑖[𝐽̂2 𝐽̂𝑦 − 𝐽̂𝑦 𝐽̂2 ] (276)

= [𝐽̂2 , 𝐽̂𝑥 ] + 𝑖[𝐽̂2 , 𝐽̂𝑦 ] (277)

= 0 + 𝑖(0) = 0 (278)

Hence

[𝐽̂2 , 𝐽̂+ ] = 0 (279)

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 50 A Textbook of Physical Chemistry – Volume I

Similarly

[𝐽̂2 , 𝐽̂− ] = 0 (280)

ii) Find the commutator of the following

[𝐽̂+ , 𝐽̂𝑧 ] (281)

Let

[𝐽̂+ , 𝐽̂𝑧 ] = [ 𝐽̂𝑥 + 𝑖𝐽̂𝑦 , 𝐽̂𝑧 ] (282)

= (𝐽̂𝑥 + 𝑖𝐽̂𝑦 )𝐽̂𝑧 − 𝐽̂𝑧 (𝐽̂𝑥 + 𝑖𝐽̂𝑦 ) (283)

= 𝐽̂𝑥 𝐽̂𝑧 + 𝑖𝐽̂𝑦 𝐽̂𝑧 − 𝐽̂𝑧 𝐽̂𝑥 − 𝐽̂𝑧 𝑖𝐽̂𝑦 (284)

= 𝐽̂𝑥 𝐽̂𝑧 − 𝐽̂𝑧 𝐽̂𝑥 + 𝑖𝐽̂𝑦 𝐽̂𝑧 − 𝑖𝐽̂𝑧 𝐽̂𝑦 (285)

= [𝐽̂𝑥 𝐽̂𝑧 − 𝐽̂𝑧 𝐽̂𝑥 ] + 𝑖[𝐽̂𝑦 𝐽̂𝑧 − 𝐽̂𝑧 𝐽̂𝑦 ] (286)

= [𝐽̂𝑥 , 𝐽̂𝑧 ] + 𝑖[𝐽̂𝑦 , 𝐽̂𝑧 ] (287)

= −𝑖ħ𝐽̂𝑦 + 𝑖(𝑖ħ𝐽̂𝑥 ) = −𝑖ħ𝐽̂𝑦 − ħ𝐽̂𝑥 (288)

= −ħ(𝐽̂𝑥 + 𝑖𝐽̂𝑦 ) = −ħ𝐽̂+ (289)

[𝐽̂+ , 𝐽̂𝑧 ] = −ħ𝐽̂+ (290)

Similarly

[𝐽̂− , 𝐽̂𝑧 ] = ħ𝐽̂− (291)

iii) Find the commutator of the following

[𝐽̂+ , 𝐽̂− ] (292)

Let

[𝐽̂+ , 𝐽̂− ] = (𝐽̂𝑥 + 𝑖𝐽̂𝑦 )(𝐽̂𝑥 − 𝑖𝐽̂𝑦 ) − (𝐽̂𝑥 − 𝑖𝐽̂𝑦 )(𝐽̂𝑥 + 𝑖𝐽̂𝑦 ) (293)

= 𝐽̂𝑥 𝐽̂𝑥 − 𝑖𝐽̂𝑥 𝐽̂𝑦 + 𝑖𝐽̂𝑦 𝐽̂𝑥 + 𝐽̂𝑦 𝐽̂𝑦 − (𝐽̂𝑥 𝐽̂𝑥 + 𝑖𝐽̂𝑥 𝐽̂𝑦 − 𝑖𝐽̂𝑦 𝐽̂𝑥 + 𝐽̂𝑦 𝐽̂𝑦 ) (294)

= 𝐽̂𝑥 𝐽̂𝑥 − 𝑖𝐽̂𝑥 𝐽̂𝑦 + 𝑖𝐽̂𝑦 𝐽̂𝑥 + 𝐽̂𝑦 𝐽̂𝑦 − 𝐽̂𝑥 𝐽̂𝑥 − 𝑖𝐽̂𝑥 𝐽̂𝑦 + 𝑖𝐽̂𝑦 𝐽̂𝑥 − 𝐽̂𝑦 𝐽̂𝑦 (295)

= −𝑖𝐽̂𝑥 𝐽̂𝑦 + 𝑖𝐽̂𝑦 𝐽̂𝑥 − 𝑖𝐽̂𝑥 𝐽̂𝑦 + 𝑖𝐽̂𝑦 𝐽̂𝑥 (296)

= −𝑖[𝐽̂𝑥 𝐽̂𝑦 − 𝐽̂𝑦 𝐽̂𝑥 ] + 𝑖[𝐽̂𝑦 𝐽̂𝑥 − 𝐽̂𝑥 𝐽̂𝑦 ] (297)

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 CHAPTER 1 Quantum Mechanics – I 51

= −𝑖[𝐽̂𝑥 , 𝐽̂𝑦 ] + 𝑖[𝐽̂𝑦 , 𝐽̂𝑥 ] (298)

= −𝑖[𝑖ħ𝐽̂𝑧 ] + 𝑖[−𝑖ħ𝐽̂𝑧 ] (299)

= ħ𝐽̂𝑧 + ħ𝐽̂𝑧 = 2ħ𝐽̂𝑧 (300)

The commutation relations between angular-momentum and Ladder operators can be mainly divided
into three categories as discussed below.
(a) Ladder operator and total angular momentum commutation:

[𝐽̂2 , 𝐽̂+ ] = 0; [ 𝐽̂+ , 𝐽̂2 ] = 0 (301)

[𝐽̂2 , 𝐽̂− ] = 0; [ 𝐽̂− , 𝐽̂2 ] = 0 (302)

[𝐽̂+ , 𝐽̂𝑧 ] = −ħ𝐽̂+ ; [ 𝐽̂𝑧 , 𝐽̂+ ] = ħ𝐽̂+ (303)

[𝐽̂− , 𝐽̂𝑧 ] = ħ𝐽̂− ; [ 𝐽̂𝑧 , 𝐽̂− ] = −ħ𝐽̂− (304)

[𝐽̂+ , 𝐽̂− ] = 2ħ𝐽̂𝑧 ; [ 𝐽̂− , 𝐽̂+ ] = −2ħ𝐽̂𝑧 (305)

(b) Ladder operator and orbital angular momentum commutation:

[𝐿̂2 , 𝐿̂+ ] = 0; [ 𝐿̂+ , 𝐿̂2 ] = 0 (306)

[𝐿̂2 , 𝐿̂− ] = 0; [ 𝐿̂− , 𝐿̂2 ] = 0 (307)

[𝐿̂+ , 𝐿̂𝑧 ] = −ħ𝐿̂+ ; [ 𝐿̂𝑧 , 𝐿̂+ ] = ħ𝐿̂+ (308)

[𝐿̂− , 𝐿̂𝑧 ] = ħ𝐿̂− ; [ 𝐿̂𝑧 , 𝐿̂− ] = −ħ𝐿̂− (309)

[𝐿̂+ , 𝐿̂− ] = 2ħ𝐿̂𝑧 ; [ 𝐿̂− , 𝐿̂+ ] = −2ħ𝐿̂𝑧 (310)

(b) Ladder operator and spin angular momentum commutation:

[𝑆̂ 2 , 𝑆̂+ ] = 0; [ 𝑆̂+ , 𝑆̂ 2 ] = 0 (311)

[𝑆̂ 2 , 𝑆̂− ] = 0; [ 𝑆̂− , 𝑆̂ 2 ] = 0 (312)

[𝑆̂+ , 𝑆̂𝑧 ] = −ħ𝑆̂+ ; [ 𝑆̂𝑧 , 𝑆̂+ ] = ħ𝑆̂+ (313)

[𝑆̂− , 𝑆̂𝑧 ] = ħ𝑆̂− ; [ 𝑆̂𝑧 , 𝑆̂− ] = −ħ𝑆̂− (314)

[𝑆̂+ , 𝑆̂− ] = 2ħ𝑆̂𝑧 ; [ 𝑆̂− , 𝑆̂+ ] = −2ħ𝑆̂𝑧 (315)

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Table of Contents
CHAPTER 1 ................................................................................................................................................ 11
Quantum Mechanics – I ........................................................................................................................ 11
 Postulates of Quantum Mechanics .................................................................................................. 11
 Derivation of Schrodinger Wave Equation...................................................................................... 16
 Max-Born Interpretation of Wave Functions .................................................................................. 21
 The Heisenberg’s Uncertainty Principle.......................................................................................... 24
 Quantum Mechanical Operators and Their Commutation Relations............................................... 29
 Hermitian Operators – Elementary Ideas, Quantum Mechanical Operator for Linear Momentum,
Angular Momentum and Energy as Hermitian Operator ................................................................. 52
 The Average Value of the Square of Hermitian Operators ............................................................. 62
 Commuting Operators and Uncertainty Principle (x & p; E & t) .................................................... 63
 Schrodinger Wave Equation for a Particle in One Dimensional Box.............................................. 65
 Evaluation of Average Position, Average Momentum and Determination of Uncertainty in Position
and Momentum and Hence Heisenberg’s Uncertainty Principle..................................................... 70
 Pictorial Representation of the Wave Equation of a Particle in One Dimensional Box and Its
Influence on the Kinetic Energy of the Particle in Each Successive Quantum Level ..................... 75
 Lowest Energy of the Particle ......................................................................................................... 80
 Problems .......................................................................................................................................... 82
 Bibliography .................................................................................................................................... 83
CHAPTER 2 ................................................................................................................................................ 84
Thermodynamics – I .............................................................................................................................. 84
 Brief Resume of First and Second Law of Thermodynamics .......................................................... 84
 Entropy Changes in Reversible and Irreversible Processes ............................................................. 87
 Variation of Entropy with Temperature, Pressure and Volume ...................................................... 92
 Entropy Concept as a Measure of Unavailable Energy and Criteria for the Spontaneity of Reaction
...........................................................................................................................................................94
 Free Energy, Enthalpy Functions and Their Significance, Criteria for Spontaneity of a Process ... 98
 Partial Molar Quantities (Free Energy, Volume, Heat Concept) ................................................... 104
 Gibb’s-Duhem Equation ................................................................................................................ 108
 Problems ........................................................................................................................................ 111
 Bibliography .................................................................................................................................. 112
CHAPTER 3 .............................................................................................................................................. 113
Chemical Dynamics – I ........................................................................................................................ 113
 Effect of Temperature on Reaction Rates ...................................................................................... 113
 Rate Law for Opposing Reactions of Ist Order and IInd Order..................................................... 119
 Rate Law for Consecutive & Parallel Reactions of Ist Order Reactions ....................................... 127
 Collision Theory of Reaction Rates and Its Limitations ............................................................... 135
 Steric Factor................................................................................................................................... 141
 Activated Complex Theory ........................................................................................................... 143
 Ionic Reactions: Single and Double Sphere Models ..................................................................... 147
 Influence of Solvent and Ionic Strength ........................................................................................ 152
 The Comparison of Collision and Activated Complex Theory ..................................................... 157
 Problems ........................................................................................................................................ 158
 Bibliography .................................................................................................................................. 159
CHAPTER 4 .............................................................................................................................................. 160
Electrochemistry – I: Ion-Ion Interactions ..................................................................................... 160
 The Debye-Huckel Theory of Ion-Ion Interactions ....................................................................... 160
 Potential and Excess Charge Density as a Function of Distance from the Central Ion ................. 168
 Debye-Huckel Reciprocal Length ................................................................................................. 173
 Ionic Cloud and Its Contribution to the Total Potential ................................................................ 176
 Debye-Huckel Limiting Law of Activity Coefficients and Its Limitations ................................... 178
 Ion-Size Effect on Potential ........................................................................................................... 185
 Ion-Size Parameter and the Theoretical Mean - Activity Coefficient in the Case of Ionic Clouds with
Finite-Sized Ions ............................................................................................................................ 187
 Debye-Huckel-Onsager Treatment for Aqueous Solutions and Its Limitations ............................ 190
 Debye-Huckel-Onsager Theory for Non-Aqueous Solutions........................................................ 195
 The Solvent Effect on the Mobility at Infinite Dilution ................................................................ 196
 Equivalent Conductivity (Λ) vs Concentration C1/2 as a Function of the Solvent ......................... 198
 Effect of Ion Association Upon Conductivity (Debye-Huckel-Bjerrum Equation) ...................... 200
 Problems ........................................................................................................................................ 209
 Bibliography .................................................................................................................................. 210
CHAPTER 5 .............................................................................................................................................. 211
Quantum Mechanics – II .................................................................................................................... 211
 Schrodinger Wave Equation for a Particle in a Three Dimensional Box ...................................... 211
  The Concept of Degeneracy Among Energy Levels for a Particle in Three Dimensional Box .... 215
 Schrodinger Wave Equation for a Linear Harmonic Oscillator & Its Solution by Polynomial Method
.........................................................................................................................................................217
 Zero Point Energy of a Particle Possessing Harmonic Motion and Its Consequence ................... 229
 Schrodinger Wave Equation for Three Dimensional Rigid Rotator .............................................. 231
 Energy of Rigid Rotator ................................................................................................................ 241
 Space Quantization ........................................................................................................................ 243
 Schrodinger Wave Equation for Hydrogen Atom: Separation of Variable in Polar Spherical
Coordinates and Its Solution ......................................................................................................... 247
 Principal, Azimuthal and Magnetic Quantum Numbers and the Magnitude of Their Values ....... 268
 Probability Distribution Function .................................................................................................. 276
 Radial Distribution Function ......................................................................................................... 278
 Shape of Atomic Orbitals (s, p & d) .............................................................................................. 281
 Problems ........................................................................................................................................ 287
 Bibliography .................................................................................................................................. 288
CHAPTER 6 .............................................................................................................................................. 289
Thermodynamics – II ........................................................................................................................... 289
 Clausius-Clapeyron Equation ........................................................................................................ 289
 Law of Mass Action and Its Thermodynamic Derivation ............................................................. 293
 Third Law of Thermodynamics (Nernst Heat Theorem, Determination of Absolute Entropy,
Unattainability of Absolute Zero) And Its Limitation ................................................................... 296
 Phase Diagram for Two Completely Miscible Components Systems ........................................... 304
 Eutectic Systems (Calculation of Eutectic Point) .......................................................................... 311
 Systems Forming Solid Compounds AxBy with Congruent and Incongruent Melting Points ....... 321
 Phase Diagram and Thermodynamic Treatment of Solid Solutions.............................................. 332
 Problems ........................................................................................................................................ 342
 Bibliography .................................................................................................................................. 343
CHAPTER 7 .............................................................................................................................................. 344
Chemical Dynamics – II ...................................................................................................................... 344
 Chain Reactions: Hydrogen-Bromine Reaction, Pyrolysis of Acetaldehyde, Decomposition of
Ethane ............................................................................................................................................ 344
 Photochemical Reactions (Hydrogen-Bromine & Hydrogen-Chlorine Reactions) ....................... 352
 General Treatment of Chain Reactions (Ortho-Para Hydrogen Conversion and Hydrogen-Bromine
Reactions) ....................................................................................................................................... 358
  Apparent Activation Energy of Chain Reactions .......................................................................... 362
 Chain Length ................................................................................................................................. 364
 Rice-Herzfeld Mechanism of Organic Molecules Decomposition (Acetaldehyde) ...................... 366
 Branching Chain Reactions and Explosions (H2-O2 Reaction) ..................................................... 368
 Kinetics of (One Intermediate) Enzymatic Reaction: Michaelis-Menten Treatment .................... 371
 Evaluation of Michaelis's Constant for Enzyme-Substrate Binding by Lineweaver-Burk Plot and
Eadie-Hofstee Methods ................................................................................................................. 375
 Competitive and Non-Competitive Inhibition ............................................................................... 378
 Problems ........................................................................................................................................ 388
 Bibliography .................................................................................................................................. 389
CHAPTER 8 .............................................................................................................................................. 390
Electrochemistry – II: Ion Transport in Solutions ....................................................................... 390
 Ionic Movement Under the Influence of an Electric Field ............................................................ 390
 Mobility of Ions ............................................................................................................................. 393
 Ionic Drift Velocity and Its Relation with Current Density .......................................................... 394
 Einstein Relation Between the Absolute Mobility and Diffusion Coefficient .............................. 398
 The Stokes-Einstein Relation ........................................................................................................ 401
 The Nernst-Einstein Equation ....................................................................................................... 403
 Walden’s Rule ............................................................................................................................... 404
 The Rate-Process Approach to Ionic Migration ............................................................................ 406
 The Rate-Process Equation for Equivalent Conductivity .............................................................. 410
 Total Driving Force for Ionic Transport: Nernst-Planck Flux Equation ....................................... 412
 Ionic Drift and Diffusion Potential ................................................................................................ 416
 The Onsager Phenomenological Equations ................................................................................... 418
 The Basic Equation for the Diffusion ............................................................................................ 419
 Planck-Henderson Equation for the Diffusion Potential ............................................................... 422
 Problems ........................................................................................................................................ 425
 Bibliography .................................................................................................................................. 426
INDEX ......................................................................................................................................................... 427