CYLI10: SEMESTER II 2007-2008, MAJOR EXAM

Date: May 1, 2008 Time: 2 hour/Marks 200

IMPORTANT: 1. Note that there is a choice in Q. 1.

2. Answer ALL parts of a question TOGETHER.
Q 1. This question concerns many-electron atoms. .
(a) Write the Hamiltonian for many-electron atom with nuclear charge +Ze
and N electrons. ( 10)
(b) Explain the approximation used in order to separate the many-electron
Hamiltonian into a sum of one-electron Hamiltonians and define the term
atomic orbitf;ll. (10)
(c) Two types of functions frequently used to represent atomic orbitals are
Slater orbitals and Gaussian orbitals. A Slater orbital is of the form
n+ 1 .

(2~) 2 rn-le-i;r ym( 8 cjJ) , while a Gaussian orbital is of the form

~(2n)! I' .

Nnrn-le-aryr(8,cjJ). Discuss, with reference to the appropriate eigenvalue

equations, if these wavefunctions correctly represent: .'

(i) the behaviour as the electron approaches very close to the nucleus. .
(5)
(ii) the behaviour as the electron moves far from the nucleus.
. (5)
(iii) the angular distribhtion of the electrons. (10)
(iv) or is there something missing? (10)

OR

Ql. Using the LCAO-MO approach, a trial wavefunction for Hz+ may be written
as cjJ=Cll/lls +C2l/l1s ,where l/lls and l/llS are hy dro g enic atomic orbitals
A 8 A 8

centered on nuclei A and B, respectively. Answer the following questions:

(a) Write secular determinant explaining each term in the determinant. (5)
(b) Express matrix elements in your secular determinant using Coulomb
integral, exchange integraL overlap integral and energy of hydrogenic
atomic orbital. (10)
(c) Solve the secular equation and represent the energies in terms of Coulomb
integraL exchange integraL overlap integral and .energy of hydrogenic
atomic orbital. (10)
(d) Obtain the energies of Hz"'-relative to the completely dissociated species,
H+ and H. (5)
(e) Plot the two energies obtained in part (d) versus the internuclear
separation, R. (5)
(D Plot the separate contributions of the Coulomb integral and the exchange
integral to the stability of Hz+versus the internuclear separation, R. (5)
(g) Based on your plots in part (fL explain the reason of chemical bonding in
Hz+. _:: (1 0) -,-
/' /'

I
 Q2. Consider a porphyrin molecule having 18 electrons which can be IT
modeled either as a square (length 1000 pm) or a circle (diameter 1000 pm).
The experimental lowest energy absorption transition of this porphyrin occurs at
770 nm. (h = 6.626x10-34 Js, C = 2.998x108 ms-I, me = 9.109x10--31 kg, 1 amu =
1.661 X 10-27 kg)
(a) For the square and circular models draw (no derivation required) the
energy level diagrams up to the first unoccupied state. (10+10)
(b) Using appropriate and complete mathematical calculations determine the
lowest energy absorption transition for the two models and suggest which
(and why) would be a better model for this porphyrin. (15+15)

Q3. A wavefunction for hydrogen atom is

3/2
1 1 r r
q;(r,e,cf»- - 2-- exp --
./32 Tl( ao ) ( ao ) ( 2ao )

(a) Assign n, 1, ml and name the atomic orbital. (5)

(b) Calculate the most probable distance of this electron from the nucleus in
terms of aD. (10)
(c) Calculate the average distance of this electron from the nucleus in terms
of aD. (10)
(d) Calculate the most probable point for this electron in terms of aD. (10)
(e) Sketch the radial wave function and the radial distribution function versus
r for this orbital indicating most probable distance, average distance, and
IX) I
(5 + 5 + 5)
most probable point. (Given: [rne-ar dr=
;.... a~~l )

Q4. (a) Decide whether the following statements are true or false giving
reasoning. (5+5)
i. For a system composed of C components with chemical potentials Pi and n;
the number of moles of the i-th component, Lf Pin i will always have its
smallest possible value. .
ii. A body in equilibrium and in thermal and mechanieal contact with a I
reservoir at constant temperature and pressure will have the lowest
possible value of the Gibbs energy for that body.
(b) One mole of a pure substance at constant pressure
1<1
is found to melt at T m and boil at Tv. For a
-5'" 1\ l~
temperature range T low<T m<T v<T highand constant
pressure, sketch plots of the molar enthalpy and !-It-
molar Gibbs energy with temperature. (15) 11
(c) Consider the phase diagram of a binary system A ~
and B given alongside. ~_.~ ~-- ,~
\.T'iv~
i. What is the degree of freedom at points L, M,
and N? (6)
ii. If the system is in the state E in the figure, what
are the two phases present in the mixture? Find \

~
1M
the overall mole fraction of B in the system and J
in each p~ase present in the system. PE is 1110 " ~ N
XY and P'i.fis 112 XY. (6+4) ' f"
4 2.- iii. Let the .system at point E contain 10 mol of B, - ( (
'b find the number of moles of A present in each
~
~

phase. CL~ (9) mole fractionofB Y ~ C.

~ -~
~~
~
~o
')( 3 -
'>'--::: ~
b 2:.-2-
')~
+
-
( Lf~- 8 dJ 110
b I~).
1-J- -.!;{ -f~ 'L
8 '1 2: