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Quantum Mechanics (Remaining)

This document discusses key concepts in quantum mechanics including: 1. Operators are mathematical instructions that operate on functions to produce other functions. Linear operators produce results that are the sum of operating on functions separately. 2. Eigenvalues and eigenfunctions are constants and functions that remain unchanged when an operator acts upon them, except for being multiplied by the constant eigenvalue. 3. The Schrodinger wave equation describes the wave function of a quantum system and is used to find allowed energy levels. It takes different forms depending on whether a particle is in an infinite or finite potential well. 4. The laws of quantum mechanics include postulates about wave functions, Hermitian operators, eigenvalues and eigenfunctions,

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600 views7 pages

Quantum Mechanics (Remaining)

This document discusses key concepts in quantum mechanics including: 1. Operators are mathematical instructions that operate on functions to produce other functions. Linear operators produce results that are the sum of operating on functions separately. 2. Eigenvalues and eigenfunctions are constants and functions that remain unchanged when an operator acts upon them, except for being multiplied by the constant eigenvalue. 3. The Schrodinger wave equation describes the wave function of a quantum system and is used to find allowed energy levels. It takes different forms depending on whether a particle is in an infinite or finite potential well. 4. The laws of quantum mechanics include postulates about wave functions, Hermitian operators, eigenvalues and eigenfunctions,

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You are on page 1/ 7

REKHA G R

Lecturer in Chemistry

QUANTUM MECHANICS

Operators

An operator is a mathematical instructions or procedure to be carried out on a


function so as to get another function.

Linear operator

An operator  is said to be linear if its application on the sum of two functions


gives the result which is equal to the sum of the operations on the two functions
separately.

i.e., ̂ [f(x) + g(x)] = A


A ̂ f(x) + A
̂ g(x)

Example:

i. d/dx is a linear operator


d/dx [axm +bxn]
= d/dx (axm) + d/dx(bxn)
ii. √ is not a linear operator
√𝑓(𝑥) + 𝑔(𝑥) ≠ √𝑓(𝑥) + √𝑔(𝑥)

Laplacian operator

This is very common operator used in quantum mechanics. It is represented by


∇2 and is defined as
𝜕2 𝜕2 𝜕2
∇2 = 2
+ 2
+
𝜕𝑥 𝜕𝑦 𝜕𝑧 2

Eigen value and Eigen functions

If an operator  operated on a will behave function.(i.e., finite, continuous,


single valued) functions ‘f’ to give the same function but multiplied by a
constant then the constant is called the ‘eigen value’ of the operator and the
function ‘f’ and is called the ‘eigen function’
̶ ax
f=e

1|QUANTUM MECHANICS
̶ ax
d/dx (e ) = ̶ ae ̶ ax
↓ ↓
Eigen value Eigen function

Hermitian property of operators


̂ has eigen two functions Ψ and ϕ and if
‘If an operator A

̂ 𝜙)𝑑𝜏 = ∫(A
∫ 𝛹(A ̂ 𝛹)𝜙𝑑𝜏

Where Ψ and ϕ are real


∗
̂ ϕ)dτ = ∫(𝐴̂𝛹) 𝜙𝑑𝜏
Or ∫ 𝛹 ∗ (A

Where Ψ and ϕ are complex

Ψ* is the complex conjugate of Ψ

dτ is the volume element of space

Examine d2/dx2 is a Hermitian operator.

Let Ψ = eix and ϕ = sinx be the two acceptable eigen functions. Then,
𝑑2
∫ 𝛹 ∗ (𝐴̂𝜙)𝑑𝜏 = ∫ 𝑒 −𝑖𝑥 𝑑𝑥 2
(𝑠𝑖𝑛𝑥)𝑑𝑥

= ̶ ∫ 𝑒 −𝑖𝑥 𝑠𝑖𝑛𝑥 𝑑𝑥
∗ 𝑑 2 ∗
= ∫ 𝜙(𝐴̂𝛹) 𝑑𝜏 = ∫ 𝑠𝑖𝑛𝑥 [ 2 (𝑒 𝑖𝑥 ) ] 𝑑𝑥
𝑑𝑥
∗
= ∫ 𝑠𝑖𝑛𝑥(𝑖 2 𝑒 𝑖𝑥 ) 𝑑𝑥

= ̶ ∫ 𝑠𝑖𝑛𝑥 𝑒 −𝑖𝑥 𝑑𝑥

Hamiltonian operator

It is total energy operator including both potential energy and kinetic energy
̶ ℎ2
Ĥ= ∇2 + V
8𝜋2 𝑚

2|QUANTUM MECHANICS
Schrodinger wave equation

The SWE is a linear partial differential equation that describes the wave
function or state function of a quantum mechanical system.
∂2 Ѱ ∂2 Ѱ ∂2 Ѱ 8𝜋2 𝑚(𝐸−𝑉)
+ + + 𝛹=0
∂𝑥 2 ∂𝑦 2 ∂𝑧 2 ℎ2

E → Total energy of the particle

Ψ → wave function which represents the state of the particle

V → potential energy of the particle

m→ mass of the particle

h→ planck’s constant

Importance of Schrodinger wave equation

It is used to find the allowed energy levels of quantum mechanical systems. The
associated wave function gives the probability of finding the particle at a certain
position.

Schrodinger wave equation for a particle in one dimensional box

The Schrodinger wave equation for one dimension is


∂2 Ѱ 8𝜋2 𝑚
+ (𝐸 − 𝑉)𝛹 = 0 ……………..(i)
∂𝑥 2 ℎ2

Where Ψ has been taken as the function of x-coordinate only

3|QUANTUM MECHANICS
As outside the box V= ∞ therefore for outside the box equation (i) becomes
∂Ѱ 8𝜋2 𝑚
+ (𝐸 − ∞)𝛹 = 0 ………………..(ii)
∂𝑥 2 ℎ2

Neglecting E in comparison to ∞, equation (ii) reduces to


∂2 Ѱ 8𝜋2 𝑚
− ∞𝛹 = 0 [ × ∞ = ∞]
∂𝑥 2 ℎ2

∂2 Ѱ
= ∞𝛹
∂𝑥 2

1 ∂2 Ѱ
Ψ= =0 ………………………… …..(iii)
∞ ∂𝑥 2

This proves that outside the box Ψ=0 which implies that the particle cannot go
outside the box

For the particle within the box V=0, therefore the Schrodinger wave equation (i)
takes the form
∂2 Ѱ 8𝜋2 𝑚
+ (𝐸𝛹) = 0………………..(iv)
∂𝑥 2 ℎ2

8𝜋2 𝑚𝐸
Which may be simplified by putting =k2
ℎ2

Where k2 is a constant, independent of x


∂2 Ѱ
Equation (iv) then becomes + k2Ψ=0
∂𝑥 2

The general solution of this differential equation is given as

Ψ = A sin kx + B cos kx

where A and B are constants.

The values of A, B and k are determined by the boundary conditions as follows

At x= 0, Ψ = 0 equation (iii) becomes

0 = A sin 0 + B cos 0 ( ∵ sin 0 = 0 𝑎𝑛𝑑 cos 𝑜 = 1)

or B = 0 and hence

Ψ = A sin kx ………………..(v) for all values of x

4|QUANTUM MECHANICS
When x=L we can write the above equation as

Ψ = A sin kL ………………..(vi)

Equation (vi) is satisfied if either A=0 or kL =nπ.

However if both A and B become zero, Ψ will be zero at all values of x, which
is impossible. Therefore the other solution i.e., kL =nπ is acceptable.

Hence k = nπ / L

Where n is an integer i.e, n = 1,2,3,……..

But not zero

Substituting the value of k in equation (v)


nπ
We get Ψ = A sin x …………………(vii)
L

This gives the expression for the eigen function Ψ .

The expression for the eigen value of the energy may be obtained as follows

2 8𝜋2 𝑚𝐸
Since k =
ℎ2

𝑘 2 ℎ2
E=
8𝜋2 𝑚

Substituting the value of k we get


2
(𝑛𝜋⁄𝐿) ℎ2
E =
8𝜋2 𝑚

𝑛2 𝜋2 ℎ 2
E=
8𝜋2 𝑚𝐿2

𝑛2 ℎ 2
E= ………………..(viii)
8𝑚𝐿2

Equations (vii) and (viii) are the solutions of the Schrodinger wave equation for
a particle in one dimensional box.

Laws of quantum mechanics

I postulate: The physical state of a system at a time ‘t’ is described by the wave
function Ψ(x,t)
5|QUANTUM MECHANICS
II postulate: The wave function Ψ(x,t) and its first and second derivatives
𝜕𝛹(𝑥,𝑡)
and 𝜕 2 𝛹(𝑥, 𝑡)/ 𝜕x2 are continuous, finite and single valued for all values
𝜕𝑥
of x. Also the wave function Ψ(x,t) is normalised.
∞
i.e ∫−∞ 𝛹 ∗ (𝑥, 𝑡)𝛹(𝑥, 𝑡)𝑑𝑥 = 1

where Ψ* is the complex conjugate of Ψ formed by replacing i with ̶ i wherever


it occurs in the function Ψ(i=√−1 )

III postulate: A physically observable quantity can be represented by a


̂ is said to be Hermitian if it satisfies the
Hermitian operator. An operator A
following condition.
∗
∫ 𝛹𝑖∗ 𝐴̂𝛹𝑗 𝑑𝑥 = ∫ 𝛹𝑗 (𝐴̂𝛹𝑖 ) 𝑑𝑥

Where Ψi and Ψj are the wave functions representing the physical states of the
quantum system such as a particle, an atom or a molecule.

IV postulate: If Ψ is a well-behaved function for the given state of a system


and 𝐴̂ is a suitable operator for the observable quantity or property, then the
operation on Ψ by the operator 𝐴̂ gives Ψ multiplied by a constant value (a) of
the observable property ie.,

𝐴̂Ψ =aΨ

The given state is called the eigen state of the system, Ψ is called the eigen
function and ‘a’ is called eigen value.

V postulate: The operator representing the momentum (p) in the direction of


any coordinate q is the differential operator.
h ∂ –ih ∂
or
2πi ∂q 2π ∂q

Where h is planck’s constant and i= √−1

VI postulate: If a number of measurements are made over the configuration


space, then the average value of the quantity (represented by 𝑎̅) is given by

∫ y∗Â ydt
𝑎̅ =
∫ y ∗ ydt

6|QUANTUM MECHANICS
Physical interpretation of wave function

The wave function ‘Ψ’ represents the amplitude of the electron wave at
any instant of time when the co-ordinates of the electron are x,y,z. The Ψ2 at
any point gives the probability of finding the electron at that point. Ψ2 is called
probability amplitude. But the probability is directly related to the density of the
electron cloud. Thus Ψ2 gives the electron density at any given point. Since the
region around the nucleus which represents the electron density at different
points is called an orbital, that is why the wave function for an electron in an
atom is called orbital wave function or atomic orbital.

*****

7|QUANTUM MECHANICS

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