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For Homework Assignment

Use 3
rd
Edition

L
0 1
2
1
0
Electron configuration:

Term Symbols:
1 1
3 2 p p
S
2
1
D
1
1
P
0
1
S
1 , 2 , 3
3
D
0 , 1 , 2
3
P
1
3
S
2 2 2
2 2 1 : p s s C
M
L
: total orbital-orientation quantum No.

L m M
l L
= =

,.... 2 , 1 , 0
L=max(M
L
)
2L + 1 possible values
For a given value of S, there will be 2S+1 spin
states characterized by M
S.

M
S
= m
s


=0,1, 2,.S for even # unpaired electrons
=1/2,3/2,5/2,.S for odd # of electrons.


S=max (M
S
)

2 2 2
2 2 1 : p s s C
S=0 Ms=1


S=1 Ms=1

Ms=-1


Ms=0

S=0 Ms
N =
(2y)!
x!(2y x)!

In general, the total No. of ways N that x
electrons can be placed into y orbitals of
equivalent energy with either spins is given by

2 2 2
2 2 1 : p s s C
15
! 4 ! 2
! 6
=
microstates
2 2 2
2 2 1 : p s s C
S=0 Ms=0


S=1 Ms=1

Ms=-1


Ms=0

S=0 Ms=0
Step I:
Sum all m
s
and m
l
for each microstates,
Determine M
S,
M
L
for each
l
m
+1

0

-1
s
M
L
M
0 0 0 0 0 0 0 0 0 1 -1 1 -1 1 -1
-2 0 2 -1 -1 0 0 1 1 -1 -1 0 0 1 1
Step II:
Starting with maximum M
S
, partition
microstates into sets.

Note: A term
2S+1
L corresponds to
(2L+1)(2S+1) microstates

S=max (M
S
)
L=max(M
L
)

+1

0

-1
s
M
L
M
0 0 0 0 0 0 0 0 0 1 -1 1 -1 1 -1
-2 0 2 -1 -1 0 0 1 1 -1 -1 0 0 1 1
1 ) max( =
s
M
S=1
1 , 0 , 1 =
s
M
1 =
s
M
For ,
1 ) max( =
L
M
L=1
1 , 0 , 1 =
L
M
J=2,1,0
9 microstates
0
3
1
3
, 2
3
, P P P
+1

0

-1
s
M
L
M
0 0 0 0 0 0 0 0 0 1 -1 1 -1 1 -1
-2 0 2 -1 -1 0 0 1 1 -1 -1 0 0 1 1
S=0
J=2
5 microstates
0 ) max( =
S
M
0 =
s
M
L=2
2 ) max( =
L
M
2 , 1 , 0 , 1 , 2 =
L
M
2
1
D
+1

0

-1
s
M
L
M
0 0 0 0 0 0 0 0 0 1 -1 1 -1 1 -1
-2 0 2 -1 -1 0 0 1 1 -1 -1 0 0 1 1
S=0
J=0
1 microstate
0 ) max( =
S
M
0 =
s
M
L=0 0 ) max( =
L
M
0 =
L
M
0
1
S
E
2 2 2
2 2 1 : p s s C
0
1
S
2
1
D
2
3
P
1
3
P
0
3
P
Ground State Terms for many-electron atoms:
: decide which of several energy states will be lowest in energy.

1.The ground state term always has maximum spin multiplicity.
there fore, for the carbon atom, the
3
P
2,1,0
terms will be more stable
than the
1
D
2
and
1
S
0

2. When comparing two states of the same spin multiplicity, the state
with the higher L value is usually more stable. This is the case with
the
1
D
2
and
1
S
0
of the carbon atom.

3. For given S and L values, the minimum J value is most stable if
there is a single open subshell that is less than half-full, and the
maximum J is most stable if the subshell is more than half-fill. Thus
for the carbon atom, the
3
P
0
state is the ground state term.

Example:

2 3 14
6 5 4 ] [ : s d f Xe Ta
Rule 1. S=3/2 2S+1 =4
Rule 2. max (ML) L=3

Rule 3. Jmin=3/2
2 / 3
4
F
Ground state
Periodic Trends
Generally, atoms with same outer-orbital structure appear
in the same Column.
Effective atomic radius (covalent radius)

effective atomic radius
=1/2(dAA in the molecule A2)







Example:

H2: d=0.74 - rH=0.37
Estimating bond distance (covalent):

R----C-H: d C-H = rC + rH =0.77 + 0.37 =1.14
Trend 1. Atomic radii increase down a group (Z
eff

~constant while n increases).

Trend 2: Atomic radii decrease across a period (Z
eff

increase)
Na



K




Rb
1 6 2 2
3 2 2 1 s p s s
2 . 2 2 85 . 0 8 11 = =
eff
Z
2 . 2 10 85 . 0 8 19
4 3 3 2 2 1
2 6 2 6 2 2
= =
eff
Z
s p s p s s
Zeff=2.2
Na Mg Al Si P S Cl
[Ne]


Z



o



Zeff
1
3s
2
3s
1 2
3 3 p s
2 2
3 3 p s
3 2
3 3 p s
4 2
3 3 p s
5 2
3 3 p s
11 12 13 14 15 16 17
8.8 9.15 9.5 9.85 10.2 10.55 10.9
2.2 2.85 3.5 4.15 4.8 5.45 6.1
1 = AZ
35 . 0 = Ao
65 . 0 = A
eff
Z
Ionization energy:
Energy required to remove an electron from a gaseous atom or ion.






Trend 1: IE
1
decrease down a group( n, r increase while Z
eff
constant).

Trend 2: IE
1
increases across a period (Z
eff
increase, r decrease)

Exception: B, O ionization energy lower than Be, N: empty or half filled
orbitals contribute to the stability.
Similarly: Al, S

+ +
+
+
+
e g A g A
e g A g A
) ( ) (
) ( ) (
2
2
1
IE E
IE E
= A
= A
2 2
2 1 : s s B
+
3 2 2
2 2 1 : p s s O
+
Electron affinity= energy required to remove an electron from the
gaseous negative ion (ionization energy of anion).


maximum for halogens
usually positive, difficult to measure, but can be
negative.
EA(F) lower than EA(Cl):
smaller diameter, strong e-e repulsion


+ e g A g A ) ( ) (
EA E = A
Total energies of an ion in various charge states:
E=oq +|q
2
(q =ionic charge)
The slope of this curve near the origin gives us an idea of how
readily the atom accepts and give up electrons.

Total energy E
0
Charge q
+1
-1
Electronegativity (EN)
The power of an atom in a molecule to attract electrons to itself

Mulliken definition: EN =1/2(IE
1
+EA)



EN
A
EN
B
= 0.208 DE
AB
DE
A
2
DE
B
2

Pauling definition:

DE =bond dissociation energy in kcal/mol
EA(A) EA(B) small A-B bonding mostly covalent
EA(A)-EA(B) large A-B bonding has ionic component
EN(F)=3.98
Example:

HF

DE (H2) =103 kcal/mol
DE(F2) =37 kcal/mol
DE(HF)=135 kcal/mol
mol kcal DE DE
F H
/ 62
2 2
=
EN(F)-EN(H) =
78 . 1 62 135 208 . 0 =
EN(H) =2.2
Trend 1. EN decrease down a group

Trend 2: EN increase across a period

H
2.20
<>
Li
0.98
Be
1.57
<>
B
2.04
C
2.55
N
3.04
O
3.44
F
3.98
Na
0.93
Mg
1.31
<>
Al
1.61
Si
1.90
P
2.19
S
2.58
Cl
3.16
K
0.82
Ca
1.00
Sc
1.36
Ti
1.54
V
1.63
Cr
1.66
Mn
1.55
Fe
1.83
Co
1.88
Ni
1.91
Cu
2.00
Zn
1.65
Ga
1.81
Ge
2.01
As
2.18
Se
2.55
Br
2.96
Rb
0.82
Sr
0.95
Y
1.22
Zr
1.33
Nb
1.60
Mo
2.16
Te
1.90
Ru
2.20
Rh
2.28
Pd
2.20
Ag
1.93
Cd
1.69
In
1.78
Sn
1.96
Sb
2.05
Te
2.10
I
2.66
Cs
0.79
Ba
0.89
La
1.10
Hf
1.30
Ta
1.50
W
2.36
Re
1.90
Os
2.20
Ir
2.20
Pt
2.28
Au
2.54
Hg
2.00
Tl
2.04
Pb
2.33
Bi
2.02
Po
2.00
At
2.20
Symmetry & Group Theory


MT Chap. 4
Vincent: Molecular Symmetry and group theory
Symmetry:
The properties of self-similarity
Re2(CO)10
W(CO)6
C2F4
C60
Symmetry:

Construct bonding based on atomic orbitals

Predict spectra

Access reaction pathway

Determine optical activity
Symmetry Operation:

Movement of an object into an equivalent or indistinguishable
orientation
Symmetry Elements:

A point, line or plane about which a symmetry operation is
carried out
5 types of symmetry operations/elements
Identity: this operation does nothing, symbol: E

Element is entire object
Proper Rotation:

Rotation about an axis by an angle of 2t/n
m
n
C
n
n
n
n
n
C C
E C
=
=
+1
Rotation 2tm/n
C4
1
2
3
4
PtCl4
C2
The highest order rotation axis is called the principle axis.
How about:
NFO2?
H2O
NH3
Identity E
Proper Rotation Cn

Reflection: o
reflection through a mirror plan
NH3
H2O

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