Mulliken Mulliken Mulliken Mulliken
Population Analysis Population Analysis Population Analysis Population Analysis p y p y p y p y
The basics of quantum The basics of quantum q
chemistry
q
chemistry
The n-electronic wave function
2
probability of simultaneously finding
( )
2
1 1 1 1 1
,..., , ,..., ....
n s sn n n n
x z m m dx dy dz dx dy dz
probability of simultaneously finding
1 with spin m
s1
in the volume dx
1
dy
1
dz
1
at (x
1
,y
1
,z
1
)
2 with spin m in the volume dx dy dz at (x y z ) 2 with spin m
s2
in the volume dx
2
dy
2
dz
2
at (x
2
,y
2
,z
2
)
and so on.
One-electronic density One-electronic densityyy
The probability density of finding an electron The probability density of finding an electron
(ANY!!!) in the neighborhood of point (x,y,z) is
2
} }
I t k i th i k i th t !
1
2
2 2
( , , ) ... ( , , , ,..., , ,..., ) ...
n
s
n s s n
all m
x y z n x y z x z m m dx dz =
} }
In most cases - knowing the is knowing the system!
( , , ) ( , , ) A A x y z x y z dxdydz =
}}}
( , , )
s
m
Z e x y z dxdydz en = =
}}}
}}}
A 1.000.000$ question
How does look like? How does look like?
The Hartree-Fock case The Hartree-Fock case
The n-electronic wave function in the case of
Hartree Fock (HF) approximation: Hartree-Fock (HF) approximation:
(1) (1) (1) | | |
| |
|
|
1 2
1 2
(1) (1)... (1)
(1, 2,... ) det (2) (2)... (2)
n
HF n
n
| | |
| | |
|
|
|
=
|
1 2
... ... ...
( ) ( ) ( )...
n
n n n | | |
|
|
|
\ .
Home work (3 points bonus! ). Prove:
( )
2
|
n
j
is the occupation number (n
j
= 0,1,2)
( )
, ,
HF j j
j
x y z n | =
j
p (
j
, , )
The energy functional =
density functional (W Kohn)
The energy functional =
density functional (W Kohn) density functional (W. Kohn) density functional (W. Kohn)
( )
2
x y z n | =
Exact WF:
n is the generalized occupation number
( )
, ,
j j
j
x y z n | =
n
j
is the generalized occupation number
(n
j
~ 0 or 1);
j
natural orbitals j=1,,
h h E E * d E Kohn - Sham : E=E[]=*dV =E[]=?
HF: E
HF
[]=T[]+V
n
[]+(V []+V
x
[]) HF: E [] T[] V
ne
[] (V
c
[] V
ex
[])
DFT: E[]=T[]+V
ne
[]+(V
c
[]+V
ex
[]+V
cor
[])-
i l l t th i l di l ti ! single-electron theory including correlation!
MO LCAO pp xim ti n MO LCAO pp xim ti n MO-LCAO approximation MO-LCAO approximation
In the formula:
( ) ( )
2
, , , ,
HF j j
j
x y z n x y z | =
is found as the sum the probability-density
functions of all MOs
j
The MOLCAO approximation: The MOLCAO approximation:
1 1 2 2
1
...
b
j sj s j j bj b
c c c c | _ _ _ _ = = + + +
Thus
1 s=
* * * *
1 1 1 1 1 1
m b b m b b
j j j j rj sj r s rs r s
j j
n n c c D | | _ _ _ _ = = =
where m is the number of MOs;
and b is the number of AOs
1 1 1 1 1 1 j r s j r s = = = = = =
and b is the number of AOs
Density Matrix Density Matrix yy
*
m
D n c c =
C the contribution of r-AO to j-MO
1
rs j rj sj
j
D n c c
=
=
C
rj
the contribution of r-AO to j-MO
The probability density associated with
l t i is | |
2
one electron in
j
is |
j
|
2
Normalization condition:
where the Ss are overlap integrals:
2 2 2 2
1 2
| | 1 ... 2
j j j j bj rj sj rs
r s
dV c c c c c S |
<
= = + + + +
}
where the S s are overlap integrals:
rs r s r s
S dv dv _ _ =
} }
rs r s r s
S dv dv _ _
} }
Mulliken population analysis Mulliken population analysis
2 2 2 2
1 2
| | 1 ... 2
j j j j bj rj sj rs
r s
dV c c c c c S |
<
= = + + + +
}
An electron in the MO
j
contributes :
+ n
rj
=n
j
c
rj
2
to the net population in AO
r
, n
rj
n
j
c
rj
to the net populat on n O
r
,
+ n
r-s,j
=2n
j
c
rj
c
sj
S
rs
to the overlap population of
r
and
s
.
Mulliken proposed a method that apportions Mulliken proposed a method that apportions
the electrons of an n-electron molecule into :
1 N t l ti i th AO 1. Net populations n
r
in the AOs;
2. Overlap populations n
r-s
for all pairs of AOs.
, ,
and
r r j r s r s j
n n n n
= =
j j
Mulliken characteristics Mulliken characteristics Mulliken characteristics Mulliken characteristics
The sum of all the net and overlap populations p p p
equals the total number of electrons in the
molecule: 2
n n n dV n dV | + = = =
} }
Gross atomic (A) population :
r r s j j
r r s s j
n n n dV n dV |
>
+ = = =
} }
1
2
A r r s
n n n
= +
p p
Mulliken charge of atom A : Z
A
=en
A
Mullikens matrix (M
rr
=n
r
and M
rs
=n
r s
) could be
( )
2
r A r s A s A e > e e
Mull ken s matr x (M
rr
n
r
and M
rs
n
r-s
) could be
divided according to atomic indexes A, B,
Then number of blocks in the A-B part of the h n num r of oc s n th part of th
matrix M defines bond order
between atoms A and B
NOTE: M
rs
= D
rs
*S
rs
Bonding Mulliken population
analysis example : C H
Bonding Mulliken population
analysis example : C H analysis example : C
2
H
2
analysis example : C
2
H
2
CC bonding. There are two orbitals composed of two g p
2p
x
and two 2p
y
atomic orbitals of the two C atoms and a
bond composed of the 1s, 2s and 2p
z
orbitals.
h G D D ( 1 ) The Gaussian output. Density matrix D
rs
(C1-C2 part)
C2\C1 1S 2S 2P
Z
2P
X
2P
Y
1S 0.04570 -0.12510 0.14378 0.00000 0.00000
2S -0.12510 0.24810 -0.28900 0.00000 0.00000
2P
Z
-0.14378 0.28900 -0.30554 0.00000 0.00000
2P
X
0.00000 0.00000 0.00000 0.75822 0.00000
2P
Y
0.00000 0.00000 0.00000 0.00000 0.75822
