OBAFEMI AWOLOWO UNIVERSITY,ILE-IFE,NIGERIA

DEPARTMENT OF CHEMISTRY
B.Sc. Degree (Chemistry) Examination Part III
CHM 303:Quantum
Chemistry
Harmattan Semester Test 2022/2023 Session

Time Allowed: 1% hrs

Date: 20th November 2023

Useful constants: mp = 1.67262 x 10-27 kg,me =9.10939× 10-31 kg,h= 1.05457 x 1034 Js,
electric =1.60218 x
charge (e) 10-19 C,Eo =
8.854190 10-12j-1c²m-1,T × =
3. 1415927, h =6.62608x 1034 J.s, c =2.998 x 108 m s',RH =1.09738× 10" 1 Hartree m,
=4.35975 × 10-18 J, 1 Hartree =27.2116 eV

INSTRUCTION: Attempt all questions

(1.)The one-electron hydrogen molecule ion, H$, has the wavefunction y =c1t Cz2,
where 1, 2 are normalized ls orbitals and Ci, C are çoefficients of the linear

combination of the two hydrogen atomic orbitals, give an equation that links c to Cz. Show
the steps to arrive at this equation. [10 marks]

(2.)If the z-componentof the angular momentum operator in spherical polar coordinate is

given as Lz =-ih determine the eigenvalues of the following functions:

i.) = Aeim ii.) =Asin m¢ [10marks]

(3.) Normalize the function =Aem, within the entire space possible, assuming A is the
normalization constant. [10marks]

(4.)What is Compton effect? Definition should not be more than 3 lines. [10marks]

(5.) Mention one area of chemistrywhere quantum mechanicshas found great application. [10

marks]

(6.) Calculate the ionization energy (IE)required to remove an electron from the ground state
(N= 1) of hydrogen nucleus in Joule, eV and Hartree. [10 marks]

Total =60 marks

 OBAFEMIAWOLOWO UNIVERSITY, LEIEE, NIGERIA
DEPARTMENT OF CHEMISTRY
BSe Degree (chemiery)Examinaton Part 11
CHM e:Qantan Chemiatry
Harmattan Semeeter Test It 2022/2021 Seion

Time ABewed:

Usefel eonetents:
eleetrie
135 hrs

chenge
1415927, A6.62608 x 10
m67262 10" kg. m,9.10919 x 10" kg. 1.05457 104,
()-L60218 x 10"C,t, 8854190x 10-12|-cm
Js,e 2.998
,
10 m , R
Date:

1.09738
1 3h peeemher Z02

10 m'. 1 Hartree
3.
-4.35975 x 1e 1 Hartree 27.2116 eV

INSTRUCTION: Attempt all questions

(1)Dernve the commutator:

- 0 marke)

(2)Find the result of operating with =-4x² on the function =e. What must

be the value of a if y is to be an eigenfunction ofthis operator? [15marks]

(3)The function = Ax(1-x) is a legal wave function in 0<<1.

the interval Calculate

)
the normalization constant, A,and (ii.) the averages (2)and (). [15marks]

Total 40 marks

Question 4 is a bonus question for a free 10marks

(4) The formulasfor the 1-dimensional particle in a box have been used to approximate the
energies of the pielectrons in linear conjugated molecules. For example,butadiene:

HCCH-CCH,
isapproximated as a linear "box" with a length equal to the sum of the bond lengths -
0424 nm in this case. The resulting energy levels are "filled" with the available pi

electrons (4 in this case) with two per level (spin-up and spin-down). Estimate the

absorption frequencyof butadiene with this model. The observed value is 5.72 eV.

/hethut
21.416eV
Enz
 OBAFEMI AWOLOWO UNIVERSITY, ILE-IFE,NIGERIA
DEPARTMENT OFCHEMISTRY
Part II
B.Sc. Degree (Chemistry) Examination
CHM 303: Quantum Chemistry
Harmattan SemesterExanmination (2022/2023 Session)

Time Allowed: 2% hrs Date: 26h February2024

= 1.673 × kg, me =9.110 x 1031 kg,Th ==3.143,

Usefulconstants: mp 10-27 1.055 x1034 J8,
h=6.626 × 104
electric

charge (e) =1.602 x C, E = 854

10-19 x 10-12j-C'm1,
8.

c= 3.0 x 108 m s,RH =1.097 x 107 m1,1Hartree =4.360 x

J.s,
J, 1 Hartree= 27.212 10-18

eV, ao=5.292 x 10-11 m.

INSTRUCTION: ATTEMPT ALL QUESTIONS

SECTION A

QUESTION ONE

(a.)Find the commutators:

(3mks]

(b.) Find the results of operation of:

s i) =x- (d/dx) and =x +(d/dx) on the

ß function f(x) =e**/2 [3mks]

f(G) = an eigenfunction. What is the eigenvalue?

(iüi) =ion
do
3e and state if it is

[3mks]
frequencies in cm for the equivalent tothe Balmer series
(i) Calculate the wavenumber
(c.)

N=3and 4, assuming RHet =4RH. (3mks]

=
(N, 2) for He* for that

Bohr orbit of hydrogen. [2mks]

the velocity of the electron in the
first
(ü)Calculate
[Total:14 marks]

nmh
2724
1
3 LBA

3
 QUESTION TWO
(a.) (i) What is the connection between Rutherford's nuclear and Bobr's atomic models?

[1 mk

(Gi) How did Bohr surmount the barrier of Rutherford's theory to progress? [1 mk

(ii) What is Bohr's correspondence principle and how is it related to the Newtonianlaw?

(2 mks]

(iv) Calculate the de Broglie wavelength of a l-g projectile traveling at 500 m s and an

electron moving at half the speed oflight. [2mks]

(b.) )Calculate the value of A so that yn = Asin(rx/a)is normalized in the region 0<x<

a. (Hint: fsin"x dx =-Zcos x sin"-i x+ fsin"-2 xdx) [4%mks]

(ii) Calculate the value of (&) for 1-dimensional particle in a box in the region )<x<a.
(Hint: use integration by part, i.e. fu dv =uD- fv du) 14 mks]

(iii) Calculate the energy difference in cm of the first two energy levels of a particle in a

box, AB,.-1= Bz -E, for an electron in a box of 2 A in length. [1 mk]

[Total: 16 marks]

SECTION B

QUESTION THREE

(a) The total energy of quantum harmonic oscillator can b expressed as:

) Derive the expression

[3 mks]
for the energy gap of successive vibrational states in the oscillator.

2
 energy and
be deduced from the expressions of
the total
(i) State fourconclusions that could

energy gap. (2
mks]
is 1.319 x
whose vibrational frequency
gap, AB of the oscillator
(iiü)Calculate the energy

1014 s.(h=6.626 x 1034 Js). (2mks]

of mass, m and spring constant k =

ofclassical harmonicoscillator
(b)Given the wave function

mo as: x(t) = o)where A and are constants,

Asin(ot +

A,m, o, t

. as a function of
ofthe oscillator
for the potential energy
()write the expression

and (2 mks]
[1 mk
of the oscillator(dx/dt).
for the velocity
derive the expression
a function ofA, m, o,t
(iü)

of the oscillator as

. expression forthe kinetic energy

(ii) write the

and [2 mks]
oftime. Hint:sinu
is constant, independnt
the total energy
ofthe oscillator
(iv) show that

(3mks]
+ costu =1]. [Total: 15 marks]

QUESTION FOUR
wave, function is b=
harmonic oscillator
unperturbed
(-0)
(a) The normalized

system is = H +'=
4 while a perturbed Hamiltonian for
the

24
2m dx2 [2mks]
potential term(s)?
the H is/are the perturbation
(1) Which term(s)from
correction to the energy.
perturbation
(i) Determine the

x'e-dx = 0; xez*'dx =)“]8 mks]

[Hint:

3
2

3
2m
 (b)The trial variation function for a particle in a one-dimensional box of length lis given as:

=x(l-) for 0Sx<l

0 Elsewhere

d²
Using the Hamiltonian: derive the expression for
2m dx23

()(4•(H)) [4 mks]

(i)(°l),and hence (4 mks]

(ii)the tightest bound energy, E, for the particle (2mks]

[Total: 20 marks

2a