-:_-_~Q

~!!8.~~~~1Ey__~--9l!~~~_i_oE_S.:.l'~-~!--~~~-8.
(Special credit wi_~-be g!_~~~-~?P!:_t?cJ~?_?__~l-~~E.::_~l~~~~~-~?_-_!!!e-p_~int
a~swer~

l. Consider a trigonal bipyrarnidal MLr, transition metal complex. (a.) Construct a sim-
plified sigma-only MO schornc, assuming that only (n - l)d orbitals on the central
metal participate in bonding interactions with ligand o·-SALCs (i.e., ignore interac-
tions with metal ns and np AOs). Assume that the energies of SALCs lie lower than
those of the metal AOs. (b) How docs the electron filling in this MO scheme compare
with the pmmmcd filling in the d orbitals in the CFT model? (7+3)

2. Determine the number of frequencies, their symmetries, and the Ill and Raman activi-
tics of the normal modes for (a) BeF;i (b) PFli. (5+5)

3. Using projection operators, derive normalized functions for four 11 SALCs in the
(10)

4. Detcnninc the sets of specific AOs that can be combined to form hybrid orbitals with
the following geometrics: (a) trigonal planar (b) trigonal bipyramid.

5. Assuming a trigonal planar geometry for BH:i, develop a general MO scheme for BH:1•
Derive the SALCs. Assume that only 2s and 2p orbitals of B interact with the H ls or-
bitals, i.e., B ls orbital is non-bonding. (10)

6. Using group theory and Hiickel method, develop a qualitative 1r-MO scheme for cyclic
(C 11 h system in planar geometry. Find the representation choosing a proper ba-
sis. Then derive the form of MOs. Show filling of electron::;in the scheme for rwutral
molecule, +1cation and -1 anion. Discuss their relative stability in terms of usual u, {-J
integrals. (10)

7. Consider three degenerate p orbitals P:c,Py, Pz, for an isolated atom M. If M is sur-
rounded by several X atoms, the electrostatic field may lift the degeneracy among
them. Describe the degree of degeneracy among p orbitals allowed by symmetry for
each of the following structures: (a) MX2, linear (b) MX2, bent (c) MX:i, trigonal pla-
nar (d) MX;1, pyramidal (e) MX4, tetrahedral (f) MX4, square planar (g) MX5, square
pyramidal (h) MX5, trigonal bipyrarnidal (i) MXr;, octahedral. (10)
 A 1 1 1 1 z2; :r:2;y2

JJ1 1 1 1 1 z, n, :r:y
JJ2 1 1 ] ·-1y;Ry :r:z

~~-~-=-~--=~-----~ 11;; J~::j:'JZ --

D:ih E 2C:i 3C2 2S:i 3uv

r-----1
Uh

A'1 1 1 1 1 1 1 x2 + y2; z2

A~ 1 1 --1 1 1 ·--1 Rz
E' 2 -1 0 2 -1 0 (:i:,y) \(:r;2-y2,:r:y)

A~ 1 1 1 --1 -1 -1
-1 -1 --1
A~ G 1
--2 1
1 I z
I (:r:z, yz)
E" 2_ 1 0 0 (Jlx, Ry)