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
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̶ 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
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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
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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
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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)
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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
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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.
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