Assignment 2

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Assignment 2

© All Rights Reserved

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Course Number: CHEM F111

Course Title: General Chemistry

Marks: 10

Tutorial Problem Set 2 (based on Lecture No.s: 10-13 in the course hand out)

Instructions to the student: The following problems should be solved as home assignment

within a week of display. Any one problem will be assigned as a closed book class test in the

following tutorial hour.

Q. 1 (a) What atomic terms are possible for the electron configuration np1nd1? Which

term is likely to lie lowest in energy? (b) Give the possible term symbols for (a) Sc:

[Ar]3d14s2, (b) Br: [Ar]3d104s24p5

[4+2+2+2]

Q. 2 (a) Suppose that an atom has 2 electrons in different orbitals. What are the possible

values of the total spin quantum number S? What is the multiplicity in each case?

[2+2]

(b) What values of J may occur in the terms (i) 2P, (ii) 3P? How many states

(distinguished by the quantum number MJ) belong to each level?

[3+3]

+

2

Q. 3 (a) Arrange the species O2 , O2, O2 , O2 in order of increasing bond length. (b)

From the ground-state electron configurations of B2 and C2, predict which molecule

should have the greater bond dissociation energy.

[4+4]

2

1/2

1/2

Q. 4 (a) Show that the sp hybrid orbital (s + 2 p)/3 is normalized to 1 if the s and p

orbitals are normalized to 1. (b) Normalize the molecular orbital A +B in terms of the

parameter and the overlap integral S.

[4+4]

Q. 5 (a) Write the term(s) corresponding to the ground state electronic configuration of

Cu2+ ion ([Ar]3d9) and identify the lowest energy level. (b) Which of the following

molecules N2, C2 and O2 would you expect to be stabilized by (i) the addition of an

electron to form A2-; (ii) the removal of an electron to form A2+?

[5+5]

Q. 6 (a) Obtain all possible terms and the levels arising from the excited electronic

configuration 1s12s1 of helium atom. State the degeneracy of each term and each level.

[2+2+2]

(b) Write the wavefunctions (ignoring normalization) corresponding to the MS=0-triplet

and singlet states arising from this configuration if the wavefunction corresponding to

MS=1-triplet is

triplet(1,2)(MS=1) = [1s(1) 2s(2) 2s(1)1s(2)](1)(2)

[2+2]

Q. 7 (a) Determine the hybridization of each of the following hybrid atomic orbitals

formed from combination of two pure atomic orbitals: s and pz.

[2+2+2]

(b) Write the ground state electronic configuration of O2 molecule using LCAO-MO

orbitals. What will be the bond order of the molecule if one of the electrons in the highest

occupied MO (HOMO) is excited to one of the lowest occupied MO (LUMO) ?

[2+2]

Q. 8 (a) Does the bond order of a molecule in the given electronic state depend on the

spin-multiplicity of the state? Justify your answer using the excited electronic

configuration of H2 molecule: g1u1.

[2+2]

(b) Using LCAO-MO approximation, express the molecular orbitals g and u of H2

molecule as linear combination of atomic orbitals 1sa and 1sb centered on atoms a and b.

[2]

(c) Express the normalized ground state wavefunction of H2 in terms of the molecular

orbitals and explicitly written spin-part. Calculate the bond order.

[2+2]

Q. 9 (a) A valence bond of a diatomic molecule is expressed by the following normalized

wavefunction:

(1,2) = ccovalent covalent + cionic ionic

(I) Assuming that (1,2), covalent and ionic are normalized, state whether the bond is

dominantly covalent or ionic if ccovalent = 0.6. Calculate the % ionic character of the bond.

[3]

(II) If a and b are the atomic orbitals (centered on the atoms, A and B) involved in the

valence bond, express the covalent in terms of a and b ignoring the normalization

constant and the spin-part.

[1]

(b) Can a wavefunction of a two-electron system be antisymmetric with respect to both

spatial and spin parts simultaneously? What is the spin multiplicity of a two-electron

wavefunction corresponding to symmetric with spin-part? Explain using the spin

expressions.

[6]

Q. 10 (a) How many electronic states of an atom are represented by the term 4G.

[1]

(b) Determine all the possible levels corresponding to this term.

[4]

(c) State the degeneracy of all the levels.

[4]

(d) Assuming the given term to be ground term corresponding to electronic configuration

with a less than half-full subshell and the rest of the subshell either full or empty, identify

the ground level.

[1]

******END******

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