I


1.

ATKINS,
P.W. Atkins, J. De Paula
(Atkins Physical Chemistry, 9th Edition, 2010)
, 2014

2.

, 2012

3.

PHYSICAL CHEMISTRY: A Molecular Approach

D.A. McQuarrie, J.D. Simon
University Science Books, Sausalito, California, 1997

4.

PRINCIPLES OF PHYSICAL CHEMISTRY, 2nd Edition

H. Kuhn, H.-D. Forsterling, D.H. Waldeck
John Wiley & Sons, Inc., 2000



, .., V(r),
.
,

H H1 H 2 ... H N

:
E E1 E2 ... EN

(r1,rN)

r1 , ... rN 1 r1 2 r2 N rN
,

.


, ,
, ,
.
,
, 3 r1,
r2, , r Shrdinger
.
, (He),
,
.

, .
, ,
.
,

.


-
.

ri i
, :

r1 , r2 , ...

, :

r1 , r2 , ... r1 r2 ...

,
,
, .
, , ,
.

.

 (He)

,
() .
,
1s.
1s1.
He .

2e.

1s , Z=2
,
.

image_url

1s,
He 1s2.

 Pauli
Li, Z=3, .
1s, .

, 1s,
.
Pauli:
2
, ,
spin .

spin,

() .
spin ms=+1/2 ms=-1/2,
,
spin
.

image_url

 Pauli
Pauli (1924)
- ,
.
Pauli
( spin).
, , , 13C ( spin
1/2) 35Cl ( spin 3/2).
, ( spin),
(spin 1), 12C (spin 0), ..

, Pauli :
,
( ): (2,1)= -(1,2).
,
( ): (2,1)= (1,2).

 (Li)
Li, Z=3, .
1s, .

, 1s,
.
1s,
.
,
.
,
[He].
, Li
, n=2 , ,
L.
, ,
2s 2p, [He]2s1
[He]2p1.


, 2s 2p (
)

-
Coulomb .
r ,
, ,
.

r.
,

Z Zeff .

:

Zeff Z

image_url





.
, , ,
s p , .
s
p .


, s
p.

, s
p
.

image_url


( ), s
, Zeff , p .
- , :

s pd f

(.. px, py, pz)

, .

Zeff= Z-

image_url


,

l=0 l=n-1
.

,


,

n,

l.

 (Li)
, ,
3 Li 2s 2p,
[He]2s1 [He]2p1.
2s 2p ,
Li 1s2 2s1.

,
.
Li, 2s .


(Aufbau
principle).
, Z
Z , :

1s 2s 2 p 3s 3 p 4s 3d

4 p 5s 4d

5 p 6s

2 .
,
(Z=6):

1s2 2s2 2p2

[He] 2s2 2p2

1s2 2s2 2px12py1

[He] 2s2 2px12py1

, .


, Hund:


,

(Z=6):

1s2 2s2 2px1 2py1

[He] 2s2 2px1 2py1

(Z=7):

1s2 2s2 2px1 2py1 2pz1

[He] 2s2 2px1 2py1 2pz1

(Z=8):

1s2 2s2 2px2 2py1 2pz1

[He] 2s2 2px2 2py1 2pz1

(Z=10):

1s2 2s2 2px2 2py2 2pz2

[e]

(Z=11):

1s2 2s2 2p6 3s1

[e] 3s1

image_url


s,

d

.
p ( )
s
, d
.
.. Fe (Z=26): [Ar] 3d6 4s2

5
Fe3+ : [Ar] 3d

.
.. (Z=8): [He] 2s2 2p4

2- : [He] 2s2 2p6


,
-
, I1.
, I2,
, ...
image_url

.
Li


(Zeff= 1.3 Z=3).
Be (=4)
B (=5)
, 2p
2s .


Shrdinger
.
:
1,2
2,1

Ze 2
1 ' e2
V

r
2
i
i , j 4 0 ri j
0 i

i j

rij i j.
.

.


Schrdinger D.R. Hartree
( ) V. Fock
Pauli.

(Hartree-Fock Self Consistent Field, HF-SCF).
:
1. Schrdinger ,
.
(1), (2),
2. ,
(
).
(1), (2),
3.
.
4.
.



.
,
,
.
, ( )

:

hc

,
.
,
,
.


He, 1s2.
He 1s12s1,
,
.
Hund:
H spin ()
spin ().
image_url

spin (),
spin .

( spin)
(singlet).
()


spin
spin .

spin,
(triplet).

spin spin.

image_url

spin
( ).

spin

.
()

()


:
1s12s1 He
.
, (
). , :

,
.

Coulomb
,
.
, 1s12s1 He
6421 cm-1 (0,80 eV).


He ,
:

1.
1s1nl1 ( ).

,
He+
.
2.

spin
.

, He


.

image_url

 spin -
, ,
spin .

:
spin
.
spin

spin- (spin-orbit
coupling).
spin-

.
,

spin.

el

2 e s


spin-
.

spin.
, spin ()
, .
, ,
.
image_url

image_url



j mj .
:

1
jl
2



j mj .
:

1
jl
2
:

1
jl
2
j,
l, .
l=0, j=1/2.
l=1, j=3/2 j=1/2.

 spin -
spin-
, (cm-1).

s, l, j :

El , s , j

1
hcA j j 1 l l 1 s s 1
2

,

l=0.

l=1,
spin j=3/2 j=1/2.
,
:

E3 / 2

1
hcA
2

E1/ 2 hcA

image_url

 spin -
spin- .
,
Z4.
, (
0,4 cm-1), , o Pb,
cm-1.

image_url


p
s ,
.
p :

l =1 j = 3/2, 1/2

j=3/2
j=1/2.

,
spin-.
,
589 nm (~17.000 cm-1)
Na
,
17 cm-1.

image_url


,
.
, .. 2P3/2, 3D2,
.



, L

2P


.

3/2

, J.

.

( ).


,
.

, L, :

L L 1

1/ 2

2L+1 ,

ML:

M L L, L 1,..., L
L ( )

,
Clebsch-Gordan:

L l1 l2 , l1 l2 1, ..., l1 l2


l1+l2 l1-l2
, .

.
p ,
l1=1 l2=1,
:

L 2,1, 0 D, P, S
:

L: 0 1 2 3 4 5 6

S P D F G H I
L l1 l2 , l1 l2 1, ..., l1 l2


, p2 D, P S.


.

.
,
.
,
, L l.
, [Ne]3s1 S.


,
spin S,
.
, Clebsch-Gordan:

S s1 s2 , s1 s2 1, ..., s1 s2

S=1, 0.

s=1/2,

, spin
spin
S
.
S=3/2, 1/2.

2S+1


S=0 ( , .., 1s2)
( spin).
1S.
S=s=1/2.
,
2S.

[Ne]3s1

, [Ne]3p1
2P.

, S=1 2S+1=3,
.

2S+1


, j
spin .
, ,
, J, (
).
, J=j, j=l+1/2 j=l-1/2.

, [Ne]3s1 l=0, s=1/2 , , j=1/2.

2S

1/2 .

H [Ne]3p1 l=1, s=1/2 , , j=3/2, 1/2.

,

2
2P , 2P

3/2

P1/2 .

spin-.

 Russell-Saunders
,

spin.
spin-
, .
, Russell-Saunders.

L, spin S.

J.
J Clebsch-Gordan:

J L S , L S 1, ..., L S
, 3D [Ne]2p13p1
, J=3,2,1.
, :

L=2, S=1 ,

3D , 3D , 3D .
3
2
1

 j - j
Russell-Saunders
spin- ( ).

, spin
j.
,
J.

, j j ( j

j coupling)

, p2, j 3/2 1/2

.
spin
,
j= 3/2 1/2.

j1= 3/2
j1= 3/2
j1= 1/2
j1= 1/2

j2= 3/2
j2= 1/2
j2= 3/2
j2= 1/2

J= 3, 2, 1, 0
J= 2, 1
J= 2, 1
J= 1, 0

 j - j
j j
,
Russell-Saunders.



spin-.

(Russell-Saunders)
( j-j ),

.



() .
,
Na, :

3 p1 2 P3/ 2 3s1 2 S1 / 2

3 p1 2 P1/ 2 3s1 2 S1 / 2
,
.
,
:
2

P3/ 2 2 S1/ 2

P1/ 2 2 S1/ 2
image_url


,
.

l 1
ml 0, 1

,
:

S 0
L 0, 1 , l = 1
J 0, 1 , J J ' 0
spin spin.
,

.
RussellSaunders .

 Hund
, ,
.

Friedrich Hund.

Hund

), S.

S,

L .

L S, :
,
J.

, J.


spin ,
,
.
z.
z
m
: z e ml
l

e, , e
( ) :
e

, z :

e
z
2me

m l z B m l

2 me

e
2 me

Bohr


z B ml

,
:
p

E z B
E B ml B

l=1 ml= -1, 0, +1.

, .
, :
ml=
ml=

+1

0
ml= -1

 Zeeman

image_url

.
, .

ATKINS,
P.W. Atkins, J. De Paula
(Atkins Physical Chemistry, 9th Edition, 2010)
, 2014


o
.


.


( )
.


1.0.0.


Copyright . ,
. . : 1.0. 2015.
:
https://eclass.upatras.gr/courses/CMNG2172/


Creative
Commons , 4.0 [1]
, .
.. , ...,

.
[1] http://creativecommons.org/licenses/by-nc-sa/4.0/
:

,



(.. )


, .