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CHEM F111 General Chemistry Lecture 05

Particle in a box
 Review of lecture 04

• Time-dependent Schrödinger equation in 1-D

• Variable separation and time-independent SE
• Stationary states
• Well-behaved wavefunction
• Average value of observable property
• Operators, eigenvalue equations, degeneracy
• Postulates of quantum mechanics

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Free particle in one
Dimension (translational motion)
Free particle → No external forces → P.E.=0
The (time independent) Schrödinger equation becomes:
2
ℏ2 d ψ( x ) d 2 ψ( x ) 2 mE
− =E ψ( x) + 2 ψ( x )=0
2 m dx 2
dx 2
ℏ
2 mE 2 d 2 ψ( x ) 2
We substitute 2
=k and it follows 2
+k ψ( x)=0
ℏ dx

What are the possible solutions? ψ( x )=sin(kx) OR ψ( x )=cos (kx )

OR ψ( x )=e ikx OR ψ( x )=e−ikx

ℏ 2 2
k p 2
h 2π h
We have, E= = . It follows, p=ℏ k= =
2m 2 m 2π λ λ
(de Broglie relation)

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 Particle in a (1D) box

Consider a particle in one dimension confined to a length L by infinite

potential barriers at x = 0 and x = L (infinitely deep potential well)

2
ℏ 2 d ψ( x)
− +∞ ψ( x)=E ψ( x)
2 2 m dx 2
ℏ 2 d ψ( x)
− =E ψ( x ) This equation is
2 m dx 2
well-behaved only
if the wavefunction
is zero in this
region.
V= V=
V = 0 inside box

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Boundary conditions

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx
ψ( x )= A sin (kx)+ B cos(kx)

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx
ψ( x )= A sin (kx)+ B cos(kx)
To solve further, we apply the boundary conditions.
Using ψ(0)=0; we get B=0; hence, ψ( x )= A sin (kx)

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx
ψ( x )= A sin (kx)+ B cos(kx)
To solve further, we apply the boundary conditions.
Using ψ(0)=0; we get B=0; hence, ψ( x )= A sin (kx)

Also, we have ψ(L)=0; This results two possibilities:

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx
ψ( x )= A sin (kx)+ B cos(kx)
To solve further, we apply the boundary conditions.
Using ψ(0)=0; we get B=0; hence, ψ( x )= A sin (kx)

Also, we have ψ(L)=0; This results two possibilities:

Either A=0; OR, sin(kL)=0.

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 1D-PIB wavefunctions

For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx
ψ( x )= A sin (kx)+ B cos(kx)
To solve further, we apply the boundary conditions.
Using ψ(0)=0; we get B=0; hence, ψ( x )= A sin (kx)

Also, we have ψ(L)=0; This results two possibilities:

Either A=0; OR, sin(kL)=0.
The solution, A=0 is discarded at it makes wavefunction identically zero.
Thus, we have sin(kL)=0.; which means, kL=nπ; n=1,2,3,….
Thus, the final solution is:
ψn ( x)= A sin ( )
nπ x
L
; n=1,2,3,... .
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Quantized energy levels and wavefunctions

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

The subscript n in the wavefunction is to indicate that the wavefunction depends

on the quantum number, n.

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Quantized energy levels and wavefunctions

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

The subscript n in the wavefunction is to indicate that the wavefunction depends

on the quantum number, n.
Why did we discard n=0?
What about n=-1,-2,-3,….. ? Are they allowed? Which states do they represent?
(Find it out)

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Quantized energy levels and wavefunctions

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

The subscript n in the wavefunction is to indicate that the wavefunction depends

on the quantum number, n.
Why did we discard n=0?
What about n=-1,-2,-3,….. ? Are they allowed? Which states do they represent?
(Find it out)

Homework: Normalize the wavefunction to show that constant, A=

√ 2
L
.

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Quantized energy levels and wavefunctions

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

The subscript n in the wavefunction is to indicate that the wavefunction depends

on the quantum number, n.
Why did we discard n=0?
What about n=-1,-2,-3,….. ? Are they allowed? Which states do they represent?
(Find it out)

Homework: Normalize the wavefunction to show that constant, A=

The normalized wavefunctions are thus, given by

√ 2
L
.

2
ψn ( x)=
L
sin
√nπx
L( )
Energy of the system is quantized.
; n=1,2,3 ,…

ℏ 2 k 2 h2 k 2 n2 h2
E n= = 2 = ; n=1,2,3 ,…
2 m 8 π m 8 mL 2

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1D-PIB wavefunctions

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 1D-PIB

Homework: Plot qualitatively, the probability densities of the 1D-PIB

wavefunctions

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Characteristics of 1D-PIB wavefunctions

Wavelength in a given state equals to 2L/n.

The number of nodes in the wavefunction equals to n-1.

The ground state wavefunction does not have nodes.
Energy increases with increase in the number of nodes. (Why?)

The wavefunctions are all symmetric or antisymmetric about the midpoint of the
box.
What will be the form of the function if the origin is shifted to the midpoint of
the box?
Non-zero energy for the ground state: E1 = h2/8mL2,

Note the dependence of the energy on m and L. As they increase, the separation
between the energy levels decreases.

As the quantum number, n tends to infinity, the probability distribution becomes

uniform over the entire length of the box.
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PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
Schrödinger equation for particle in a 2D box:

( )
2 2
ℏ2 ∂ ψ ∂ ψ
− + =E ψ
2m ∂x ∂ y2 2

The motions along the two directions being independent of each other, the
wavefunction must be expressible as ψ( x , y )=ψ x ( x) ψ y ( y)
Let E = Ex + Ey. Then, one can solve to get:

−
ℏ2
2m (
ψy
d2 ψx
dx 2
+ψx
d2 ψ y
dy 2 )
=( E x +E y ) ψx ψ y

( )
2 2
ℏ 2
1 d ψ x 1 d ψy
− ψ + ψ =( E x + E y )
2m x d x 2
y d y
2

Rearranging, we have:
2 2
ℏ 2 1 d ψx ℏ2 1 d ψ y
− −E x = +E y
2 m ψ x d x2 2 m ψ y d y2

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PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
We have obtained: ℏ 2 1 d 2 ψx 2
ℏ 1 d 2
ψy
− ψ −E x = ψ +E y
2m x d x 2
2m y d y 2

The LHS is a function of x alone and RHS is a function of y alone, and x and y are
independent variables. Therefore, each side would be equal to a constant. Since Ex
and Ey are unknown constants, their values may be tuned such that each side in the
above equation equals
2
to zero, and we have:
ℏ 1 d ψx
2
d 2 ψ x 2 mE x
− −E x =0 ⇒ + 2 ψ x =0 ;0≤x≤a
2 m ψ x d x2 dx 2
ℏ
2
ℏ2 1 d ψ y d 2 ψ y 2 mE y
+ E y =0 ⇒ + 2 ψ y =0 ; 0≤ y≤b
2 m ψ y d y2 dy 2
ℏ
Thus, we obtain two 1D equations which can be solved by applying the boundary
conditions to get:
( ) (
nx π x
)
ny π y
(
n2x n2y
)
2
2 h
ψn , n ( x , y)=ψx , n ( x) ψ y , n ( y )= sin sin En ,n = +
x y x y
√ ab a b x y
8 m a2 b2
n x =1,2,3 ,…; n y =1,2,3 ,…
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PIB – 3D
3D box: [V(x,y,z)=0 for 0 ≤x≤a ; 0 ≤y≤b;
≤y≤b 0 ≤z≤c and V(x,y,z)=∞ otherwise]
The logic can be extended to 3D box or even multidimensional case.

( )
2 2
For 3D, the kinetic energy operator is given by − ℏ ∂2
∂ 2
∂ 2
ℏ 2
+ + ≡− ∇
2 m ∂ x2 ∂ y2 ∂ z 2 2m

The normalized wavefunction and energy are:

ψn , n
x y z
√
, n ( x , y , z)=
8
abc (
sin
a ) (
nx π x
sin
b ) ( )
ny π y
sin
nx =1,2,3 ,…; n y =1,2,3 ,…; n z =1,2,3 ,…
nz π z
c En ,n
x y ,n
z
=
h2
n
(
2
x
+
n 2
y
8 m a2 b2 c 2
+
n 2
z
)
Special cases:
Square box (2D box with both the sides equal)
Cubic box (3D box with all the sides equal)
Cuboid box (3D box with two sides equal)

Energetic degeneracy – two or more energy levels having same energy

Homework – For Square and cubic boxes, find the energies of first ten levels and
the degeneracy of each level.
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