DPP 18 Quantum mechanics

1. Set up the huckel determinant for methyleneimine (H 2C=NH) taking C-N as 1 and N = +0.5 ,
where and represent the usual coulomb and resonance integral respectively , and obtain the Huckel
molecular orbital energy levels.Gate Exam
2. Consider the statements
i) The order of HMO secular determinant equals the number of electron.
ii) HMO theory does not make any distinction between cis and trans butadiene.
iii) An HMO is classified as bonding or antibonding according to whether its energy is more or less than
The correct statement above are a) i,ii
b) ii,iii
c) iii
d) ii only
3. Consider the statement
i)The total electron charge on nth carbon atom is 1. So we see that electron are uniformly distributed
around the benzene ring .
ii) From the bond order (P=2/3) calculation in benzene we find that bond are equivalent.
iii) If = -75 KJ/mole then benzene is stabilized by 150 KJ/mole.
The correct statement above are a) i,ii
b) ii,iii
c) iii
d) ii only
4 Sketch the molecular orbital energy level diagram for allyl system under huckel approximation ,and
compute the delocalization energy of allylcationGATE 1999
5 The bond order between 1 and 2 carbon atom in allylcation is
a) 1

b)

c) 1/ 2

d) none

6 Consider the statements regarding the characteristics of HMO method

i) sigma pi separability is justified by orthogonality of sigma and pi orbital in planar molecule.
ii) method does not take in any physical constant .
iii) it generally limits itself to conjugated hydrocarbon .
The correct statement above are a) i,ii
b) ii,iii
c) i,iii
d) ii only
7 Identify the huckel determinant for cyclobutadiene CSIR JUNE 2013
2

8 Ground state wave function corresponding to allyl system from HMO is

a) 1 = 1/ 3

1 +1/ 3

2 +1/ 3

3 b) 1 = 1/ 2

c) 1 = 1/ 2

1 +1/ 2

2 +1/ 2

3 d) 1 = 1/ 2

1 +1/ 2
1 +1/ 2

2 +1/ 2
2 +1/ 2

3
3

Q 10 If =0.8 A + 0.4 B is a normalized molecular orbital of a diatomic molecule AB constructed from

A and B which are also normalized the overlap between A and B is

a) 0.11
b) 0.31
c) 0.51
d) 0.71 CSIR JUNE 2014
Q 11 One molecular orbital of polar molecule AB has the form C AA + CBB where A and B are
normalized atomic orbital centered on A and B respectively . The electron in this orbital is found on atom
B with a probability of 90 % . Neglecting the overlapping integral between A and B , a possible set of
CA and CB are CSIR DEC 2012
a) CA = 0.95 , CB = 0.32
b) CA = 0.10 ,CB =0.90
c) CA = -0.95 , CB = 0.32
d)
CA = 0.32 , CB = 0.95
Q 12 . Consider the statements
(i) Overlapping Sab can have value between zero and one. In order to have a chemical bond it is necessary
that Sab> 0.
(ii) The bonding orbital change sign on inversion in px and py orbital so it is ungerade, and antibonding
orbital remain same on inversion so it is gerade.
(iii) Bonding orbital show a build up a electron density in an internuclear region while antibonding
orbital show a decrease of electron density in internuclear region.
Correct statements above are (a) i ,ii (b) ii ,iii (c) i,ii ,iii (d) none
Q 13 .Consider the statement
(i)In the case of bonding orbital of HF molecule N(C 11 + C22 ) C1<< C2
(ii) Photoelectron spectra generally support the existence of molecular orbital.
(iii)For Hetroatomic molecule higher atomic orbital contribute more to antibonding MO and lower atomic
orbital contribute to bonding.
Correct statement above are (a) i ,ii (b) ii ,iii (c) i,ii ,iii (d) none
Q 14 .Consider the statement
(i) Virial theorem apply to atom and molecule described by either by exact wavefunction or by
approximate wavefunction.
(ii) Orbitals are conserved in Molecular orbital treatment of the molecule and generally probability
amplitude can be positive or negative.
(iii) Size and energy of any atomic orbital are generally determined by quantum number n , and both play
a crucial role in determining the significant interaction between AO.
Correct statement above are (a) i,ii (b) ii,iii (c) i,ii,iii (d) none
Q 15Consider the statements
(i)Bonding and antibonding molecular orbital are orthogonal.
ii) Bonding molecular orbital leads to accumulation of electron density between the nuclei to minimize
nucleus nucleus repulsion
iii) Compared to H2+ the bond energy of H2 is greater
Correct statement above are (a) i,ii (b) ii,iii (c) i,ii,iii (d) none
Q 16 write T/F in front of the given statement
i) The sign of the wave function does not indicate anything about charge.
ii)A molecular orbital cannot hold more than two electrons