Mthode de Huckell

Modle
=
z
=
Modle
=
Justification:
systme de liaisons pi conjugues planaire
z
=
Modle
=
Justification:
systme de liaisons pi conjugues planaire
recouvrement nul entre 2p
zCi
et 2s
Ci
, 2p
xCi
, 2p
yi

z
=
Modle
=
Dveloppement LCAO pour OM du type t
base:

z
=
{ } ,.... 2 , 2 , 2
3 , 2 , 1 , C z C z C z
p p p
,.... 2 2 2
3 , 3 2 , 2 1 , 1 C z C z C z
p c p c p c + + =
Modle
=
Dveloppement LCAO pour OM du type t
base:

z
=
{ } ,.... 2 , 2 , 2
3 , 2 , 1 , C z C z C z
p p p
,.... 2 2 2
3 , 3 2 , 2 1 , 1 C z C z C z
p c p c p c + + =
inconnus
Modle
=
z
=
Hypothses:

=
=
cas autres 0
voisins si
j i si
j i ij
,C C H |
o
Modle
=
z
=
Hypothses:

=
=
cas autres 0
voisins si
j i si
j i ij
,C C H |
o
0 , 0 < < | o
Modle
=
z
=
Hypothses:

=
=
cas autres 0
voisins si
j i si
j i ij
,C C H |
o

=
=
=
j i si 0
j i si 1
ij
S
Systme d`quations pour les
coefficients LCAO
....... 2 2 2
3 3 2 2 1 1
+ + + =
zC zC zC
p c p c p c (r)
0 ... ) ( ) ( ) (
13 13 3 12 12 2 11 1
= + + + S H c S H c H c c c c
0 ... ) ( ) ( ) (
23 23 3 22 2 21 21 1
= + + + S H c H c S H c c c c
.
.
.

0 .... ) ( ) S ( ) (
33 3 32 32 2 31 31 1
= + + + c c c H c H c S H c
Systme d`quations pour les
coefficients LCAO
....... 2 2 2
3 3 2 2 1 1
+ + + =
zC zC zC
p c p c p c (r)
0 ... 0 ) (
2 1
= + + + | c o c c
0 ... ) (
3 2 1
= + + + | c o | c c c
.
.
.

0 .... ) ( 0
4 3 2
= + + + | c o | c c c
Systme d`quations pour les
coefficients LCAO
0
2 1
= +c x c
0
3 2 1
= + + c x c c
.
.
.

0
4 3 2
= + + c x c c
|
c o ) (
= x
Systme d`quations pour les
coefficients LCAO
0
2 1
= +c x c
0
3 2 1
= + + c x c c
.
.
.

0
4 3 2
= + + c x c c
Solutions non triviales
existent si et seulement si
0
.... : : : :
.... 1 1 0
.... 0 1 1
....... 0 1
=
x
x
x
quation sculaire
= quation de degr n
pour c
thylne
0
2 1
= +c x c
0
2 1
= + x c c
0 ) 1 )( 1 ( 1
1
1

2
= + = = x x x
x
x
quation
sculaire
= quation de
degr 2 (n) pour c
thylne
0
2 1
= +c x c
0
2 1
= + x c c
0 ) 1 )( 1 ( 1
1
1

2
= + = = x x x
x
x
1 =

|
c o
x
thylne
0
2 1
= +c x c
0
2 1
= + x c c
0 ) 1 )( 1 ( 1
1
1

2
= + = = x x x
x
x
1 =

|
c o
x
| o c =

thylne
0
2 1
= +c x c
0
2 1
= + x c c
0 ) 1 )( 1 ( 1
1
1

2
= + = = x x x
x
x
1 =

|
c o
x
| o c =

1 2
c c =
) 2 2 (
2 1 1 zC zC
p p c =

thylne
| o c + =

| o c =
+
1 2 1 1
) 2 2 ( t = + =
zC zC
p p c
2 2 1 1
) 2 2 ( t = =
+ zC zC
p p c
| 2
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
0 1 3
2 4
= + x x
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
( ) 0 1 3
2
2
2
= + x x
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
( ) 0 1 3
2
2
2
= + x x
5 4 3
2
= = A
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
( ) 0 1 3
2
2
2
= + x x
5 4 3
2
= = A
2
5 3
1
+
= x
2
5 3
2

= x
2
5 3
3

+ = x
2
5 3
4
+
+ = x
1-3 butadine
0
2 1
= +c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
0
1 0 0
1 1 0
0 1 1
0 0 1
=
x
x
x
x
( ) 0 1 3
2
2
2
= + x x
5 4 3
2
= = A
| o c
2
5 3
) 4 (
1
+
=
| o c
2
5 3
) 3 (
2

=
1-3 butadine
0
2 1
= +c x c
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
2
5 3
4
1
+
= x
|
|
.
|

\
|
+
=
2
5 3
1 2
c c
2 1 1 3
2
5 1
2
5 3
1 c c c c =
+
=
|
|
.
|

\
|
+
=
|
|
.
|

\
|
+
=
2
5 3
4 3
c c
1-3 butadine
0
2 1
= +c x c
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3
= + x c c
2
5 3
3
2

= x
|
|
.
|

\
|

=
2
5 3
1 2
c c
2 1 1 3
2
5 1
2
5 3
1 c c c c =

=
|
|
.
|

\
|

=
|
|
.
|

\
|

=
2
5 3
4 3
c c
cyclobutadine
0
4 2 1
= + + c c x c
quation
sculaire
0
3 2 1
= + + c x c c
0
4 3 2
= + + c x c c
0
4 3 1
= + + x c c c
0
1 0 1
1 1 0
0 1 1
1 0 1
=
x
x
x
x
( ) 0 4
2 2
= x x
2
1
+ = x
3 2
0 x x = = 2
4
= x
| o c 2
) 4 (
1
= o c =
) 3 (
2
| o 2 +
| o 2
o
cyclobutadine
1-3 butadine