99.11.

26

_______________________________

Y(,)
a. b. c. d. e.

= l (l+1) ( )

Y(,)

? Operates on Y to find the square of angular momentum.

Y(,)

? angular part wave function

2

l (l+1) ( ) ?

square of angular momentum ( ) (10%)

l ? angular momentum quantum number. d ? ( )=

n, l,m(r,,) n, l,m(r,,) = Rn, l(r) Yl,m(,) Yl,m(,) = l,m() m() R2,1(r) = 1,0() = m() = a. b. cos ,

e-/2 ,

= r/a0,

a0 : Bohr radius. sin ,

Y1,1 + Y1,-1 =1,1() =

x

( ei + e-i ) cos

1,1() =

sin

im

im

= cos m + i sin m
x

px Yp (,) = 2pz

sin cos

Yp (,) =
=

(Y1,1 + Y1,-1) sin cos

(5%)

Yp (,) = Y1,0 = 1,1()

z

cos

cos

2pz = R2,1(r) Yp 2pz =

e-/2

cos =

e-/2 cos

(5%)

? (10%) 1. ionization energy of the molecule (M). occupied MO. M. -8 8 H 2p (radial) (5%)
+

2. the energies of occupied MO. 3. the symmetries of 5. vibrational and electronic energies of

4. identities of the constituent elements.

LCAO-MO (10%) 1. heavy overlap of orbitals involved. 2. matched parities (or phases). 3. similar orbital energies. O C 2s-2p (10%) 1.The size of oxygen atom is smaller than that of carbon. 2. Oxygen atom has bigger nucleus than carbon atom has. These facts show that orbitals of oxygen atom have greater

-1 -8 0 8

opportunity to be near to its nucleus than those of carbon. Hence orbitals of oxygen atom have the lower energies. 1. Zeff, 2s electrons are less shielded than 2p ones by 1s electrons. of 2s and 2p, where 2s is the lower one. Comparison of O against C: Since 2s orbital of oxygen atom has the greatest probability of being at the neighborhood of its nucleus, its energy drops faster than those of 2p. (E ~ -1/r). Therefore the splitting between 2s and 2p orbitals of oxygen atom is the larger one. (x-z) A B gu nl: aA,2s - B,2s x (10%) (b). A,2pz + B,2pz z 2. 2s orbital has higher penetration ability against nucleus than 2p ones. These facts cause the splitting of orbital energies

A Page 233 & 234. z A B x

u2s*
parity (phase): + -

u2p*

LCAO-MO VB H2O2 (15%) Suppose H2O2 is formed by two steps from H atoms and O2 2H + O2 H + HOO HOOH. Effective orbital The lowest unfilled MO of O2 are * orbitals.

overlapping may occur only when H atom attaches to one of the four * lopes. Therefore the formed intermediate molecule HOO is nonlinear, with H-O-O angle greater but near 90. The second H atom can only combine with the other * orbital in the same manner. As two * orbitals are perpendicular to each other, two H-O bonds are. When the electronic repulsion is counted, 1.these two OH bonds must not be at the same oxygen atom and 2.when viewed along the O-O axis, the angle formed by these two H-O bonds is few degrees greater than 90.

H
90

O H

H
90

O O

CO CO H (10%) It is the empty 2p* orbital which may combine with the 1s orbital of H atom. The part of antibonding orbital contributed by the less electronegative atom has the larger contour of wave function, that is it may extent farther and accommodate higher electron distribution probability than the other part of the bonding one if electrons are available. H atom will bond to where the greater orbital overlapping and

99.11.26

_______________________________

the higher electron distribution probability is expected. Therefore, it is the carbon end where H atom attaches to. LCAO OF (a) ( 1s ) (b) (c) OF (d)OF ? (10%) (a)

O 2p

*2p *2p F 2p
2 2 2 3 (b) 2s *2s 2p 2p *2p

(c) (8-5)/2 = 1.5

(d) Yes.

2s

2p 2p *2s 2s

*2s

2s *2p