General Chemistry

CHEM F111

Tutorial, Section 4 (T-4)

Tutorial-3

Instructor: Prof. Tanmay Chatterjee

Chamber Consultancy Hour: Friday (11 am – 12 pm)

Email: [email protected]
Website:
https://www.bits-pilani.ac.in/hyderabad/tanmay
 The Schrödinger Equation
(Eigenvalue equation for the Hamiltonian operator)

Simple Applications
• Free particle
(If we can solve
• Particle confined in a box
Schrödinger equation, we
• Particle on a ring
know everything about
• Particle on a sphere
the system)
• Harmonic oscillator
 Particle in a one dimensional box (Particle confined in one dimension)

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)

For regions I and III, ψ(x) = 0

Particle does not exist there
 Apply boundary condition, Ψ(0) =0 ; Ψ(L) = 0

Ψ(L) = A sin(kL) = 0
kL = nπ
k = nπ/L

Energy levels are quantized

Significance of boundary conditions:
Only certain wavefunctions and energies are acceptable. The motion is quantized.
 Normalization

Normalization constant:

Normalized wavefunction/eigenfunction:

n can not be zero; then Ψ = 0 everywhere and particle vanishes.

Wavefunctions of Particle in a 1D box

In general, λ = 2L/n with

n = 1,2,3,……
 Absorption of a photon occurs when the energy of the photon (= hν) matches the
difference between the two states involved in the transition (DE):

The energy difference between adjacent levels

For Dn = 1:

Narrow box : L small; Widely separated levels

Separation decreases with increase in mass Wide box : L large

Closely spaced levels
For a particle in a one dimensional box, the lowest energy state has the magnitude 38 eV.
Find out the magnitude of the next two energy states. If the particle is an electron, what is
the length of the box?

Calculate (i) the energy difference between n = 1 and n = 2 levels for an electron confined to a
one-dimensional box of length 4 x 10-10 m. (ii) What wavelength corresponds to a spectral
transition between these levels? (iii) In which region of the electromagnetic spectrum does
this wavelength lie?
 Home Work

Varify the Schorindger equation (ĤѰn = EѰn) for a particle in 1-D box having wavefunction,
Ѱn = (2/L)1/2Sin (nπx/L)

Hint. Apply Hamiltonian operator on the wave function to verify the Schrodinger equation.
Consider the following dye molecule, the length of which can be considered the length of the
“box” an electron is limited to:

What wavelength of light corresponds to minimum excitation?

Find out the absorption in terms of the lowest value of butadiene molecule if the π-
electrons can be treated as particle in a 1-D box confined within the length of the molecule
(5.78 Å).

n=4

n=3
Butadiene
n=2

n=1

Lowest energy absorption means transition from n = 2 to n = 3

Now for a particle in 1-D box,
DE = (2n + 1) h2/8mL2

Or, hcṽ = (2n + 1) h2/8mL2

Or, ṽ = (2n + 1) h/8mcL2
Here, n = 2, h = 6.626 x 10-34 Js, m = 9.1 x 10-31 Kg, c = 3 x 108 ms-1 and L = 5.78 x 10-10 m
Hence, ṽ = 4.54 x 104 m-1
b-Carotene is a linear polyene in which 10 single and 11 double bonds alternate along a chain
of 22 carbon atoms. If we consider each C-C bond length to be about 140 pm, the length (L) of
the molecular box in b-Carotene, is L = 2.94 nm. Estimate the wavelength of light absorbed by
the molecule from its ground state to the next higher excited state. The experimental value is
497 nm. Compare the experimental value with the calculated one and draw a conclusion.
n = 12

n = 11
.
.
.

n=2

n=1

For the absorption by the molecule from its ground state to the next higher excited state
means transition from n = 11 to n = 12
Now for a particle in 1-D box,
DE = (2n + 1) h2/8mL2

Or, hc/λ = (2n + 1) h2/8mL2

Or, λ = 8mcL2 / (2n + 1) h
Here, n = 11, h = 6.626 x 10-34 Js, m = 9.1 x 10-31 Kg, c = 3 x 108 ms-1 and L = 2.94 x 10-9 m
Hence, λ = 1240 nm

Conclusion: The model is quite crude in high π-systems.

 Probability of finding a particle in a 1-D box
• Wavefunction: n (x) = (2/L)½ sin(nx/L) , n = 1,2,3,…..
• En = n2h2/8mL2 , n = 1,2,3,..
• Probability density, n2 (x)
• Probability distribution, n2 (x) dx
(probability within the range dx)
• For the ground state, n = 1; 1 (x) = (2/L)½ sin(x/L)
L
• To get the probability of finding a particle confined in a 1-D box, you need to integrate
the probability distribution over the given range (Area under the curve)
• Probability
𝑏 of finding a particle in a 1-D𝑏 box in the region from a to b; General Formula:
𝑃 𝑛=
2
∫
𝐿 a
sin
2 𝑛𝜋 𝑥
𝐿 (𝑑𝑥=
1
∫
𝐿 a
1−)cos
2𝑛 𝜋 𝑥
𝐿 ( ( )) 𝑑𝑥=¿
1
𝐿
¿¿ ¿

Since:
• Probability of finding a particle in a 1-D box in the first quarter is

( ))
𝐿/ 4 𝐿/ 4
𝑃 𝑛=
2
𝐿
∫ sin
0
2
( 𝑛𝜋 𝑥
𝐿 )
𝑑𝑥=
1
𝐿
∫
0
1 − cos (
2𝑛 𝜋 𝑥
𝐿
1
𝑑𝑥=¿ ¿ ¿ ¿
𝐿

¿
In the ground state, n = 1; Pn = 1 = 0.09 and In the first excited state, n = 2; Pn = 2 = 0.25
According to the rule of symmetry:
P (0 ≤ x ≤ L) = P (0 ≤ x ≤ L/4) + P (L/4 ≤ x ≤ 3L/4) + P (3L/4 ≤ x ≤ L)

Q. Calculate the probability to find the particle in a 1-D box in the region from a to b
in infinite energy level.
Ans.

( ))
𝑏 𝑏
𝑃 𝑛=
2
∫
𝐿 a
sin
𝐿 (
2 𝑛𝜋 𝑥
𝑑𝑥=
1
∫
𝐿 a
1− )
cos
2𝑛 𝜋 𝑥
𝐿 ( 𝑑𝑥= ¿
1
𝐿
¿¿ ¿

Now, when, n ; ) 0

𝑃 𝑛∞= (b-a)/L (finite number)

Hence when n ∞ or n is very large, the probability of finding the particle in a 1-D box
In all the points would be a constant value or the values would be very close or same
(Classical limit).
Calculate the probability of finding a particle in the left half of a one-dimensional box in its
first excited state. Sketch the wavefunction and probability density of the particle in this
state.
and x = L. Assuming that the particle is in an eigenstate, 𝛙n (x), calculate the probability
A particle of mass m moves in a one-dimensional box of length L, with boundaries at x = 0

that the particle is found somewhere in the region 0 ≤ x ≤ L/4.

( ))
𝐿/ 4 𝐿/ 4
𝑃 𝑛=
2
𝐿
∫ sin
2
( 𝑛𝜋 𝑥
𝐿 )𝑑𝑥=
1
𝐿
∫ 1 − cos ( 2𝑛 𝜋 𝑥
𝐿
𝑑𝑥=¿
1
𝐿
¿¿¿

¿
0 0

If an electron is having a one dimensional wave function Ψ= √2 Sin πx in the range x = 0 to

1, what is the probability that the electron is found in the range from x = 0.25 to 0.75.

We need to solve the following integral between initial and final limits.
dx

Since the wavefunction is a real function, the complex conjugate does not change the function,
and the integral becomes

This intergral () has a known solution which is equal to (x/2) – (1/4π) sin 2πx | ab

Evaluating for the region x= 0.25 to 0.75

P = 2[0.375-(1/4π)(-1)-(0.125-1/4π(1)] = 2(0.409) = 0.818 = 81.8%
Particle confined in a two-dimensional box or confined on a surface
Total Energy of particle, E = Ekin + Epot

Employ method of separation of variables to get two independent ordinary

differential equations

Schrödinger Equation
Method of Separation of Variables:

Wave function is a product of two individual one dimensional wave functions.

Total energy is a sum of two energy eigenvalues
For a Square Box, Degenerate States:

2 different states, but energy is same

E1,2 = E2,1 (Degeneracy happens due to symmetry)
Degenerate States
In a square box of side 100 pm, calculate the energy required for the transition of an
electron from the first doubly degenerate level to the next higher level.

The first doubly degenerate level is the second energy level corresponding to the
quantum numbers (1,2) and (2,1).

The next higher energy level corresponds to the quantum numbers (2,2).
Particle in a 3-D box
 For a cubic box, a = b = c
Hence, Ѱnx,ny,nz = (2/a)3/2Sin(nxπx/a) Sin(nyπy/a) Sin(nzπz/a)
Enx,ny,nz = h2/8ma2 (nx2 + ny2 + nz2)

When, nx = ny = nz = 1
Ѱnx,ny,nz = (2/a)3/2Sin(πx/a) Sin(πy/a) Sin(πz/a)
E1,1,1 = 3h2/8ma2 (Singly/non degenerate)

When,
nx = 2, ny = 1, nz = 1; Ѱ2,1,1 = (2/a)3/2Sin(2πx/a) Sin(πy/a) Sin(πz/a); E2,1,1 = 6h2/8ma2 Triply
nx = 1, ny = 2, nz = 1; Ѱ1,2,1 = (2/a)3/2Sin(πx/a) Sin(2πy/a) Sin(πz/a); E1,2,1 = 6h2/8ma2 degenerate
nx = 1, ny = 1, nz = 2; Ѱ1,1,2 = (2/a)3/2Sin(πx/a) Sin(πy/a) Sin(2πz/a); E1,1,2 = 6h2/8ma2

Find out the degeneracy of a particle in a cubic box with a quantum number combination of 1,2,3

Ans. Ѱ1,2,3 ≠ Ѱ1,3,2 ≠ Ѱ2,3,1 ≠ Ѱ2,1,3 ≠ Ѱ3,1,2 ≠ Ѱ3,2,1

E1,2,3 = E1,3,2 = E2,3,1 = E2,1,3 = E3,1,2 = E3,2,1
Degeneracy of the particle in a cubic box with a quantum number combination of 1,2,3 is, 3! = 6.