1. What temperature is needed for a blackbody to emit a radiation with λmax = 550 nm?

Ans: T= (2.9 × 10-3 mK)/ 550 nm= 5273 K

2. If the threshold wavelength for potassium metal is 564 nm, what is its work function?
What is the kinetic energy of the ejected photoelectrons, if a radiation of wavelength
410 nm is used?

Ans: Work function, φ= hc/λ0= (6.626 × 10-34 J/s × 3 × 108 m/s)/ (564 × 10-9 m) =
3.52 × 10-19 J
E=hc/λ – φ= (6.626 × 10-34 J/s × 3 × 108 m/s)/ (410 × 10-9 m) - 3.52 × 10-19 J= 1.32 ×
10-19 J

3. If the electron in the ground state of a hydrogen atom absorbs a photon having a
wavelength of 97.2 nm and then emits a photon with a wavelength of 486 nm, what is
the final energy state of the electron?

Ans: First, we find the state of the hydrogen atom n2 after absorption of photon.
1/(97.2 × 10-7 cm)= 109677 (1-1/n22)
n2=4
The final state after gives off the photon is:
1/(486 × 10-7 cm)= -109677 (1/42-1/nf2)
nf=2

4. The surface temperature of the Sun actually is 6000K. Suppose if the surface
temperature of the Sun was about 12000 K then,
(i) Calculate the ratio of emittance, M12000K/M6000K.
(ii) What would be the λmax of the radiation emitted by the Sun at 12000K?
(iii) Do you think it is possible to have life on the Earth at 12000K? Provide
argument.

Ans: Emittance (M) = Power/area of the emitter

M = a.T4 where a = 5.67 × 10−8 W.m-2.K-4
(i) Ratio of Emittance, M12000K/M6000K = (12000/6000)4 = 24=16
(ii) λmax= 2.9 mmK/12000 K= 241.66 nm
(iii) As the λmax of the radiation falls in the UV region, it’s impossible to have life
on the Earth at this temperature.

5. Calculate the de Broglie wavelength of an electron traveling at 2% of the speed of

light.
Ans: mass of an electron= 9.11 × 10-31 kg
Two percent of the speed of light is v= (0.02)(3.00 × 108) =6 × 106 ms-1
The momentum of electron is given by
p=mv=(9.11 × 10-31 kg) ( 6 × 106 ms-1)=5.46 × 10-24 kg.m.s-1
The de Broglie wavelength of this electron is
λ=h/p=6.626 × 10-34 Js/5.46 × 10-24 kg.m.s-1= 1.21Å
6. What is the uncertainty of the momentum of an electron if we know its position is
somewhere in a 10 pm interval?
Ans: ΔxΔp ≥ h/4 x 3.14
Δp≥ (6.626×10-34 Js)/ 4 x 3.14 x(10×10-12)m= 5.2 × 10-24 kgms-1

7. Show that eikx is an eigenfunction of the momentum operator: -iħ∂/∂x. What is the
eigen value?

Ans: -iħ∂/∂x(eikx) = ħkeikx

Eigen function: eikx and eigen value: ħk.

8. A microscopic particle of mass m moves in a one-dimensional box of length L, with

infinite barriers at x=0 and x=L. Assuming that the particle is in an
𝟐 𝒏𝝅𝒙
eigenstate, 𝝍𝒏 (𝒙) = √𝑳 𝒔𝒊𝒏 , what is the probability value in the region 0 ≤ x ≤ L/4,
𝑳
when the particle is in its ‘second’ excited state?

Solution:
2 𝐿/4 2 𝑛𝜋𝑥
𝑃𝑛 = ∫ sin ( ) 𝑑𝑥
𝐿 0 𝐿
1 𝐿/4 2𝑛𝜋𝑥 1 𝐿 2𝑛𝜋𝑥 𝐿/4
= ∫ (1 − cos ( )) 𝑑𝑥 = [𝑥 − sin( )]
𝐿 0 𝐿 𝐿 2𝑛𝜋 𝐿 0
1 1 𝑛𝜋
𝑃𝑛 = 4 − 2𝜋𝑛 sin( 2 )
1 1 3𝜋
For the second excited state, n=3, hence, 𝑃3 = 4 − 6𝜋 sin ( 2 ) = 0.303

9. What is the SI unit of a stationary state wave function  for a particle in a one and
two-dimensional box?
Solution: 𝑓𝑜𝑟 1𝐷 𝑏𝑜𝑥 ∫ 𝜓𝜓 ∗ 𝑑𝑥 = 1, 𝑆𝐼 𝑢𝑛𝑖𝑡 𝑜𝑓 𝜓𝜓 ∗ = 𝑚−1 , 𝑠𝑜 𝜓 = 𝑚−1/2
𝑓𝑜𝑟 2𝐷 𝑏𝑜𝑥 ∫ 𝜓𝜓 ∗ 𝑑𝑥𝑑𝑦 = 1, 𝑆𝐼 𝑢𝑛𝑖𝑡 𝑜𝑓 𝜓𝜓 ∗ = 𝑚−2 , 𝑠𝑜 𝜓 = 𝑚−1

10. In a square box of side length 100 pm, calculate the energy required from the
transition of an electron from the first double degenerate level to the next higher level.

Solution: The first double 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).
(8 − 5)ℎ2
Δ𝐸 = 𝐸22 − 𝐸21 = = 1.8 × 10−17 𝐽
8𝑚𝑙 2

11. Calculate the probability that a particle will be found between 0.65L and 0.67L, in a
box of length L, when it is in n=2 level. Consider the wave function to be constant in
this range.

Solution: P = [2 (0.02L)/L] sin2 [2(0.66π)] = 0.029

12. (i) How many nodes are there in the probability density plot for the energy level with
energy 9h2/8mL2 for a particle of mass m in a one-dimensional box. (ii) Write the
expression for wavefunction for this energy level (iii) Is the function symmetric or
antisymmetric under reflection about the middle of the box? (iv) What is the value
(substituting n and L) of the momentum and de Broglie wavelength of the particle in
this energy level?

Solution: (i) The energy 9h2/8mL2 corresponds to the state with n=3. The number of
nodes = n-1 =2. The probability density plot can be represented as:

2 3𝜋𝑥
(ii) 𝜓3 = √𝐿 sin 𝐿
(iii) The wave function for this energy level has even parity is symmetric. The wave
function for this level can be represented as:

(iv) P =nh/2L = 3h/2L,

λ = 2L/n = 2L/3
13. Assuming the π-electrons of benzene are confined in a 2D square box of the length of
0.5 nm. Estimate the wavelength of the light absorbed by benzene from its ground
state to the next higher excited state. Ignore the repulsion between the electrons.
Solution: Benzene has 6 π electrons. The statement states benzene can be assumed as
a 2D square box. So, the highest occupied energy level is degenerated E21 or E12.
Therefore, it will be the ground state, and the energy transition will be from E21 or E12
to the excited state E22.
ΔE = hc/λ = (8h2/8mL2) – (5h2/8mL2) = 3h2/8mL2
λ = (3 x 108 x 8 x 9.11 x 10-31 x 0.5 x 0.5 x 10-18)/(3 x 6.626 x 10-34) m = 274.9 nm

14. A small toy car of 400 g is moving back and forth along an air track between two
bumpers located 2.0 m apart. We assume no friction; collisions with the bumpers are
perfectly elastic so that between the bumpers, the car maintains a constant speed of
0.50 m/s. Treating the car as a quantum particle trapped in a 1-D box, estimate the
value of the quantum number that corresponds to its classical energy.

Solution: The kinetic energy of the car is K=1/2 (mu2)=1/2 (0.40 kg) (0.50 m/s)2 =
0.050 J.

Treating the car as a quantum particle which is trapped in a 1D box,

 𝑛2 ℎ2
= 0.05
8𝑚𝐿2
Therefore, n = (0.05 x 8𝑚𝐿2 /ℎ2 )1/2 = 2×1032

15. (a) Why the value of quantum number n = 0 is not allowed for a particle in a one-
dimensional box? (b) How do the spacings between energy levels change in particle in
a box (𝚫𝐄𝒏 ) and harmonic oscillator (𝚫𝑬𝒗 )?
Solution: (a) The ground state energy cannot be 0, but it is h2/8mL2, with n=1. This is
a consequence of the uncertainty principle. Particle is within the box, so uncertainty in
position cannot be infinite; therefore uncertainty in momentum also can not be zero.
Thus, n = 0 is not allowed.
(b) ΔE𝑛 increases with the increase in quantum number in the 1D box
and Δ𝐸𝑣 remains constant with the increase in quantum number in the harmonic
oscillator.
16. (i) Calculate the energy (in J) of a particle of mass 910-25 kg freely rotating on the
surface of a sphere of radius 50 pm in a state with l = 2. (ii) Determine the degeneracy of
this state. (iii) What is the maximum value of z-component of angular momentum (in Js)
for the particle in this state?
(i) Energy, E = l(l+1)(ħ2/2I) = 2(2+1)(h2/82mr2) =
6(6.62610-34 Js)2/8(3.14)2910-25 kg(5010-12m)2 = 1.4810-23 J
(ii) Degeneracy = 2l+1 = 22 + 1 = 5
(iii) The maximum value of z-component of angular momentum = +2ħ = +2(h/2)
= +(h/) = 6.62610-34 Js/3.14 = 2.1110-34 Js

17. (i) Estimate the magnitude of the orbital angular momentum (in Js) for an electron in
3p orbital of a hydrogenic atom. (ii) What is the minimum angle that the angular
momentum vector creates with the z-axis for this 3p electron? (iii) Give the number
of angular and radial nodes.
(i) Orbital angular momentum for an electron in 3p orbital = (l(l+1)) ħ
= (2) ħ = 1.4910-34 Js
(ii) cos = ħ/(2) ħ = 1/(2). So,  = 45o
(iii) Number of angular node = l = 1; Number of radial node = n - l -1 = 3 - 1 – 1 = 1
18. At what radius (in pm) does the probability of finding a 1s-electron in a small volume
element located at a point in the hydrogen atom fall to 60% of its maximum value?

1s = (1/ao3)1/2e-r/ao. Maximum value of 1s is at r = 0 = (1/ao3)1/2

Maximum probability = (1/ao3)dV
 Say, at r = r1, the probability of finding a 1s-electron in a small volume element dV is
60% of its maximum value.
(1/ao3)e-2r1/aodV = (1/ao3)(60/100)dV
Or, r1 = 0.255ao = 0.25552.92 pm = 13.464 pm

19. (i) Give the radial part of the wavefunction that is a function of r for a 2p electron in
the hydrogen atom writing rest part as a constant. (ii) Estimate the most probable radius
(in ao) for a 2p electron.
(i) R2,1(r) = Constantre-r/2ao
(ii) Radial distribution function, P(r) = r2 R(r)2 = r2(constant)2r2e-2r/2ao
= (constant)2r4e-r/ao. At the most probable radius, dP(r)/dr = 0
Therefore, dP(r)/dr = (constant)2[r4 e-r/ao(-1/ao) + e-r/ao(4r3) = 0
Or, (constant)2 r3e-r/ao[4 – (r/ao)] = 0. r = 0 or r =  does not correspond to a maximum.
Therefore, r = 4ao is a most probable radius.

20. Which of the following transition is forbidden in the hydrogen atom and why?
(A) 4p → 2s (B) 3p → 2s (C) 3d → 2s (D) 4d →2p
For an allowed transition, l =  1. So, 3d → 2s is a forbidden transition as l = - 2.

21. Which of the following electronic transitions [indicated by the (n, l, ml) quantum
numbers] of the hydrogen atom occur with the same value of E and why?
(A) (2, 1, 1) → (3, 2, 2) (B) (3, 2, 2) → (4, 1, 1)
(C) (3, 1, 0) → (5, 2, 1) (D) (3, 2, 0) → (5, 3, 0)

For hydrogen atom, E depends on the principal quantum number, n. For both (C) (3, 1, 0) →
(5, 2, 1) and (D) (3, 2, 0) → (5, 3, 0), n1 = 3 and n2 = 5, therefore, E for these two transitions
are the same.

22. Give the total wavefunction for a triplet state with Ms = 0 for helium atom with
electronic configuration 1s12p1.
triplet(1,2) (Ms = 0) = [1s(1)2p(2) - 1s(2)2p(1)][(1) (2) + (2) (1)]

23. Between an s-electron and a p-electron of the same shell in a many-electron atom,
which one is more tightly bound to the atom and why? How does it affect to the energy of
the orbital?
s and p electrons have different wavefunctions and therefore different distributions around the
nucleus. An s electron has a greater penetration through inner shells than a p electron of the
same shell. Thus an s electron is more likely to be found close to the nucleus than a p electron
of the same shell. As a result of this greater penetration, an s electron experiences less shielding
than a p electron of the same shell and therefore experiences a larger effective nuclear charges.
Consequently, by the combined effect of penetration and shielding, an s electron is more tightly
bound than a p electron of the same shell. Due to this reason, an s orbital has lower energy than
a p orbital of the same shell.

24. Considering the electron to be in the ground state of H, what is the probability of
finding it in an infinitesimal volume of 5 pm3 situated at 1.5𝑎0 from the nucleus?
Probability = Ψ2dV = (1/ao3)2/2e-2r/ao (at r=1.5a0) x 5 pm3 = 0.0497 x 5/(3.14 x 1.48 x 105) =
5.34 x 10-7
25. Calculate the probability that the 1s electron in hydrogen atom will be found between
a shell of radius 𝑎0 and a shell of radius 1.0 pm greater.

Radial probability = 42r2Ψ2dr = 42(a0)2(1/ao3)2/2e-2r/ao (at r=a0) x 1.0 pm = 1.1 x 105 x

0.135/(3.14 x 1.48 x 105) x 1 = 3.19 x 10-2
26. At what values of r does the P(r) for 2s orbital in H-atom exhibit maximum?
P(r) for 2s of H-atom is r2Rn,l(r)2 with Rn,l is Ψ2s = r2/8a03 (2-r/a0)2 e-2r/2a0
dP(r)/dr = 1/8a03 [2r(2 – r/a0)2e-r/a0 – 2r2/a0(2-r/a0)e-r/a0 – r2/a0(2-r/a0)2e-r/a0]
The maximum of P(r) is when dP(r)/dr = 0 at rmax
0 = 2(2-rmax/a0) – 2rmax/a0 – rmax/a0(2-rmax/a0)
0 = 4a02 – 2a0rmax – 2a0rmax - 2a0rmax + r2max
0 = r2max – 6a0rmax + 4ao2
So, r = (35)a0

27. What are the units of h2/2me2 and e2/40(r)?

J2.s2.m-2.kg-1 = J and C2/(C2.s2.kg-1.m-3.m) = J

28. Calculate the radii of the nodal surfaces for 2s orbitals in H, He+ and Li2+ systems.
Calculate the probability density at the nucleus and the radial distribution function for
r=1.5 Å for hydrogen.
(2-Zr/a0) = 0; r = 2a0/Z
r=1.058 x 10-10 m for H
r = 0.529 x 10-10 m for He+, 0.352 x 10-10 m for Li2+
Probability density at nucleus i.e. at r=0 is
 3 3
   
1  Z   1   1  Z 
 2
=  4  = 
a   4   8  a 

4( 2)  0   0 

= 2.68 x 10-7 pm-3 for hydrogen

The radial probability function = 4πr2ψ2

 1  
2
1.5  −1.5 / 0.529
4r  = 4 1.5 
2 2
 2−
3  
2
 e
 32ao   0.529 

= 7.78 x 10-2 Ǻ-1 for hydrogen

29. (a) The functional form of a hydrogen-like wave function is given below, with r in
atomic units
𝒛𝒓
𝒛𝒓 −
𝝍 = (𝒂 ) 𝒆 𝟐𝒂𝟎
𝒔𝒊𝒏 𝜽𝒔𝒊𝒏 𝝋
𝟎

(i) Determine the quantum numbers n and l by inspection. (ii) Identify the orbital. (iii)
Calculate the number of radial node(s). (iv) Identify the angular nodal plane. (v) Sketch
the radial distribution function for the identified orbital with proper axes labels.
(i) n = 2, l = 1
(ii) 2py as sin goes to 1 when  is 90 meaning the lobe is oriented along y-axis as
per the definition of .
(iii) Radial node is zero.
(iv) Angular nodal plane is xz
(v)

30. If the wavefunction for 1s orbital of H-atom be expressed as Ne-r/a0, then determine N
(hint: use polar coordinates and respective limits for expressing dV).
dV = r2 dr sin d d with intervals 0 to  for r, 0 to  for  and 0 to 2 for 
Thus, for normalization, N2 0 r2 e-2r/a0 dr 0 sin d 02 d = 1
For solving integral refer standard integral table or internet sources
In general, the value for 0 x2 e-kx dx = 2/k3
N2 . 2/(2/a0)3 . 2 . 2 = 1
Thus N = 1/(a03)1/2