Topic: Atomic Structure Instructor: Prof.

Amit Nag

1. Consider the H atom in a state which has radial part of the wavefunction as
3
4 Z
( ) 2 ¿ ¿, Where σ = (Z/a0)r
81 √ 6 a 0

Identify the Orbital and Sketch the corresponding radial distribution function.

3p wavefunction

2. One of the p orbitals is proportional to sin sinφ. Which p orbital is it? Identify the nodal plane.

Py, xz plane

3. Solution to Schrodinger wave equation for Hydrogenic atom gives the spin of the electron.
Justify for or against this statement and briefly state how spin was discovered?

No. It gives only the radial and angular part of the wave function. Spin is obtained through passing
beam of Ag atoms through an inhomogenous magnetic field and the beam splits into two.

4. Calculate the most probable radius, r* in pm, at which an electron will be found when it occupies
a 1s orbital of Be3+ and C5+. The 1s hydrogenic wavefunction is given below:

5. What is the orbital angular momentum of an electron in the orbitals (a) 2s, (b) 4p, (c) 4d? Give
the numbers of angular and radial nodes in each case.
(a) zero, radial node =1, angular node= zero (b) √ 2ℏ, radial node = 2, angular node =1 (c) √ 6 ℏ, radial
node =1, angular node =2.
 6. Consider the H atom in a state which has radial part of the wavefunction as,
−σ
4 Z 3
( ) 2 σ 2 e 3 , Where σ = (Z/a0)r
81 √3 a0

(i) What are the values of n and l for this state? (ii) What are number of radial and angular
nodes for this orbital? (iii) What is the radial wavefunction for this electron? (iv) What is
the most probable radius to find the electron? Sketch this radial function and the
corresponding radial distribution function.

(i) n= 3, l=2: 3d orbital. (ii) Radial node = 0; angular node = 2.

(iii) Radial wavefunction = constant (r2. e(-r/3a0))

(iv) Most probable radius = The most probable radius for the electron can be found by taking the derivative of the
probability density, r2R2(r) with respect to r and setting this to zero.

r2R2 3,2(r) = (constant)2 r6 e(−2r/3a0)

d(r2R2)/dr = (constant)2 [6r5 e(−2r/3a0) + r6 (− 2/3a0) e(−2r/3a0)] = 0

= (constant)2 r5 e(−2r/3a0) (6− 2r/3a0) = 0.

This is true at r = 0, r = ∞, and when the expression in square brackets is zero. The first two options are not
interesting, thus 6 = 2r/3a0 and thus, r = 9a0.

The radial function will not have any node. Both the functions will be similar, however the amplitude of the
rdf will be slightly higher and the maxima will be little shifted to higher r value.

7. Is (1,2) = 1sα(1)1s(2) +1sα(2)1s(1), an acceptable electronic wavefunction? Comment.

ψ(1,2) = ψ(2,1), not acceptable.

8. What are the boundary conditions for wavefunction of an electron in hydrogenic atom? Also
mention the name of quantum numbers which arise from each of the boundary conditions?

 → 0 as r →  (n, principal quantum number)

 (0) is same as  () (azimuthal quantum number)
 (0) is same as  () (magnetic quantum number)

9. Draw the 1s and 2s orbitals. Sketch radial part of the wavefunction for 1s and 2s.
10. For the ground state n = 1, l = 0, m = 0 of hydrogen, calculate the probability P(r)δr of finding the
electron in the range δr = 0.05ao at r = ao/2.
P100(r)δr = (4r2) [100(r)]2 δr
where 100(r) = e(-r/a0)/a and [100(r)]2 = e(-2r/a0)/a
P100(a0/2)δr = (a02) [e(-a0/a0)/a] a0 = 0.018

11. What is the Schrodinger wave equation for the H-atom in terms of Cartesian coordinates.

Where V = - e2/40r

12. Normalize the 1s wavefunction of an electron in H atom (use d𝜏 in terms of spherical harmonics).
 = N e-r/a0
d𝜏 = r2sindrdd
1 =   * dV = N2 0e(-2r/a0) r2dr osin d 02d
N = (1/a03)1/2

13. Calculate the initial energy level when an electron in a hydrogen atom transitions into n = 2 and
emits a photon at 410.1 nm.
1/ = R [1/n22 -1/n12]; substituting the values and taking R as 1.097 x 107 m-1, n = 6

14. Calculate the magnitude of angular momentum of “p” electron? Also, calculate the smallest angle
at which projection of angular momentum is made on “z” axis?
l =1 therefore, L = [l(l+1)]1/2 h/2 = 2 h/2 = 1.49 x 10-34 J.s
angle is cosθ = (Lz/L) = ml(h/2)/2 (h/2) = 1/2 = 45

15. Predict the ionization energy of Li2+, given that the ionization energy of He+ is 54.36 eV.

I =En =∞ ← En=1=−hc R H Z
2
( ∞1 − 11 )=hc R Z
2 2 H
2

I
Since I He +¿
=¿¿ 4hc R H , we may write Li 2 +¿ 9
=9 hc RH = I
4 He +¿ 9
= × 54.36 eV =122.31 eV ¿
¿
4
16. For the ground state n = 1, l = 0, m = 0 of hydrogen, calculate the probability P(r)δr of finding the
electron in the range δr = 0.05ao at r = ao/2.
P100(r)δr = (4r2) [100(r)]2 δr
where 100(r) = e(-r/a0)/a and [100(r)]2 = e(-2r/a0)/a
P100(a0/2)δr = (a02) [e(-a0/a0)/a] a0 = 0.018

17. The ground state term of carbon atom with configuration 1s 22s22p2 is 3P. What levels arise from
this term? Identify the ground state with reasoning.
J = 2, 1, 0. Ground state 3P0 Since, according to Hund Rule, Lowest J value lies low in energy.

18. Calculate the ground state ‘term symbol’ for the electronic configuration 1s22s22p4. Ans: 3P2

19. Identify the ‘term’ with ML= 0 and MS = ½ and -1/2. How many degenerate states are there in this
‘term’?
2
S, 2 states

20. For the excited state configuration 1s 1 2s1, write the total wave function of the lowest and highest
energy states.
Highest energy state or term is 1S; singlet state wave function:
Ψ= N {1s(1) 2s(2) +1s(2) 2s(1)] [ἀ(1)β(2) -- ἀ(2)β(1)]
Lowest energy term or state is 3S corresponds to triplet wave functions
Ψ= N {1s(1) 2s(2) -1s(2) 2s(1)] [ἀ(1)β(2) + ἀ(2)β(1)]
Ψ= N {1s(1) 2s(2) -1s(2) 2s(1)] [ἀ(1) ἀ(2)]
Ψ= N {1s(1) 2s(2) -1s(2) 2s(1)] [β (1) β (2)]

21. Work out the ground state term symbol for 3d2 and how many states belong to the lowest level?
Since L = 3, and S = 1,0, 3F4, 3F3, 3F2 are the term symbols. Among these 3F2 lies the lowest. There are
2J+1 states totaling 5 states.

22. Fraunhoffer observed two distinct spectral lines at around 589 nm (D lines) in the solar
spectrum. Account for the spectral lines in detail through proper energy level diagram.

23. State which of the following transitions are allowed / forbidden and why?
A) 2s → 1s, B) 3P2 → 1F2 C) 5d → 2s, D) 3F4 → 3D3 ?
A) Forbidden since 𝞓l is not = +/- 1 B) Forbidden since 𝞓S is not equal to zero.
C) Forbidden, since 𝞓l is not = +/- 1 D) Allowed since 𝞓S=0 and 𝞓J=+/-1 and 𝞓L= +/-1