6.

6.3.1
pressure broadening
1 n = 3 2
quantum defects

, n = 3,4,...

principal series (nP 3S) = R

2
( n + P ) 2
(3 + S )

principal D = 589.0 nm D = 589.6

1

nm D

, n = 4,5,... sharp

sharp series (nS 3P) = R

2
( n + S ) 2
(3 + P)

diffuse series (nD 3P)

diffuse

1
1
, n = 3,4,...
= R

2
2
( n + D)
(3 + P)

, n = 4,5,...

fundamental series (nF 3D) = R

2
( n + F ) 2
(3 + D)

R Rydbergs constant H Rch 13.6 eV

11 1s 2 2 s 2 2 p 6 3s1 10 L

S, P, D, F 1s 2 2 s 2 2 p 6 3s1 3S 1s 2 2s 2 2 p 6 4s1
4S1s 2 2s 2 2 p 6 3 p1 3P 1s 2 2 s 2 2 p 6 4 p1 4P
S, P, D, F, L 0,1,2,3,
L = 1 l = 1 L

inner
electrons

outer electron
6.3.2

Hartree
residual Coulomb interaction
optical exitations

eVs

6.3.3

LS

li si = LS LS coupling

Russell-Saunders coupling schemeZ <

30

l1 l2 ... = L ; s1 s2 ... = S ; L S = J .

2 S +1LJ 2S1 multiplicity 5.3.2

L +S

3d 4 p L =2 1 =3, 2,1 ; S =
3

( 2 L + 1) ( 2S +1) = ( 2 J +1)
J = L S

1
1
=1, 0 3 F2 , 3, 4 , 3 D1, 2 , 3 ,
2
2

P0 ,1.2 , 1F3 , 1D2 , 1P1

10 6 = (5 + 7 + 9) + (3 + 5 + 7) + (1 + 3 + 5) + 7 + 5 + 3 = 60

2 p3 p L =1 1 =2,1, 0 ; S =
1

1
1
=1, 0 3 D1, 2 , 3 , 3 P0 ,1, 2 , 3 S1 ,
2
2

D2 , 1P1 , 1 S 0 6 6 = 36
6 5
2!

15
2 p 2 =
2 p3 p

3
P0 ,1, 2 , 1D2 , 1 S 0 15 = (1 + 3 + 5) + 5 + 1
3 Eisberg/Resnick Appendix
P
654
= 20 = (2 + 4) + (4 + 6) + 4
2 p 3 P1 , 3 , D3 , 5 , S 3
2

2 2

2 2

3!

Hund

Hund Hunds rule
(1) S He

(2) S L
(3) L J
J
2 p3 p 3 D1 , 3 D2 , 3 D3 ; 3 P0 , 3 P1 ,
3
P2 ; 3S1 ; 1D2 ; 1P1 ;
1

S0

Land Land interval rule

LS L S

J J
E J = cJ ( J +1) E J EJ 1 = 2cJ J

D3

3
2

3
3

D2
D1

allowed transitions forbidden

transitions
1,

1 1 J =1, 0 ; L = 1 .
2 2
S =0

L =1, 0 l = +1 l = 1 L =0 ;
J =1, 0 J0 J0
Hartree LS Hund Land
Z
1

Mg
1
3s 2 S 0 ;
3s3 p 3 P2 ,1, 0 , 1 P1 ;
3s4 s 1S 0 , 3 S1 .

C
3
1
2 p 2 P0 ,1, 2 , 1D2 , S 0 ;

3s4s

2 p3s
3s3 p2
2p
3s

S0

S1

3 P1
1 2,1, 0
P1

P
3

13 P2

S
DP
SP
P0

13PP10
31 02
3 2
3 0
1

2 p3s 3 P2 ,1, 0 , 1 P1

6.3.4

jj

Z LS jj
l1 s1 = j1 , l2 s2 = j2 ,; j1 j2 .... = J
( j1 , j2 ,..) J
3 3
2 2

2 p3 p ( , )3, 2 ,1, 0 , (
p 2 (

3 1
1 3
1 1
, ) 2 ,1 , ( , ) 2 ,1 , ( , )1, 0 ,
2 2
2 2
2 2

3 3
3 1
1 1
, ) 2 , 0 , ( , ) 2,1 , ( , ) 0 . 15 = (5 + 1) + (5 + 3) + 1 .
2 2
2 2
2 2

J =1, 0 J0 J0

6.4

6.4.1 Zeeman
1896 Zeeman
normal Zeeman effect
anomalous Zeeman effect

LS

H = H 0 B

e
e
e

= L + S =
L gS
S
L + 2S

2me
2me
2me
=

J + S . LS aL S L S J

2me

= e J + S = e 1 + S J J

J

J
J

J
2m
2m
e

e
S J
eB

H0 +
1 + J B = H 0 +
H

2me
2me
J J

E = E0 + E = E0 +
g 1+

J J

1 + S J J

z
J J

eB S ( S + 1) + J ( J + 1) L( L + 1)
1 +
mJ = E0 + gB BmJ ,
2me
2 J ( J + 1)

e
S ( S + 1) + J ( J + 1) L( L + 1)
Land g-factor B
.
2me
2 J ( J + 1)

Zeeman
S0 JL, g =1 .
mJ = 1, 0

Zeeman
S 0
g 1 L

4
3P3 2 ( 3 p 3 2 ) g =
3

3P1 ( 3 p 1 ) g = 2 3S 1 ( 3s 1 ) g = 2
2
2
2
2
3

mJ = 1, 0 D1 6

D2 4 Zeeman 6 4

1 B 10 2
B
D

1
2
= E3 P3 E3S 1 , = , D = 589.0 nm
c
2
2
h
1

B = 5.79 10 5 eV/T
Paschen-Back

>10 TLS L S J
~

6.4.2

e
e
e

= L + S =
L gS
S
L + 2S ,

2me
2me
2me
H 0 +
H

e
eB

Lz + Sz ,
L + 2S B =

2me
2me

E = E0 + E E0 + ( mL + 2mS ) B B .

mL = 1, 0 mS =0
3

Lyman
D

6.5
nuclear spin

7
2

=
I
1D
J

F
Land

bI J
0.01nm

F
0

10 7 eV B 103 T10 gauss.

6.6 Stark
Stark 1913 E

m j j j1 j
j Stark
E

6.7 X
hole
X
Hartree X
X-ray levelsK 1s1 2 s 2 2 p 6 ....... K L
1s 2 2 s1 2 p 6 ....... 1s 2 2 s 2 2 p 5 ....... L
K L
L
LI , LII , LIII M
K
M l = 1 , j =1, 0 K
K K Lyman L
1

log 113.6eV4 13.6 104 eV

X

Auger

U X

92

K L
AugerAuger
effect Auger
1
2

K LL mv 2 = EK ELL K
1
2

LM mv 2 = EK ELM
Auger