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Atomic structure
p
1
Ze
0 =
H
2m 4"0 r
Ry =
e
4"0
"2
m
e2 1
=
2
2!
4"0 2a0
4#0 !2
e2 m .
#
0
0, 1
0, 1, 2
0 (n 1)
Subshell(s)
1s
2s 2p
3s 3p 3d
ns
p
1
Ze
0 =
H
2m 4"0 r
e2 1
1
=
%
4"0 !c
137
v
where denotes the fine structure constant, we find
= Z .
c
p2 c 2
m2 c 4
p2
1 (p2 )2
= mc +
+ ,
3
2
2m 8 m c
2
H1 =
8 m3 c 2
e2 1
4#0 !c
1
137 .
1, L
2 ] = 0 and [H
1, L
z ] = 0,
Since [H
1, L
2 ]|n#! m! $ = !2 [#! (#! + 1) #(# + 1)] #n#m|H
1 |n#! m! $ = 0
#n#m|[H
1, L
z ]|n#! m! $ = !(m! m)#n#m|H
1 |n#! m! $ = 0
#n#m|[H
Therefore, the off-diagonal matrix elements vanish:
1 |n#! m! $ = 0 for # &= #!
#n#m|H
or m &= m!
H
8 m3 c 2
2mc 2
Ze 2 1
V (r ) =
4"0 r
#n#m|H1 |n#m$ =
E 2En #V (r )$n! + #V (r )$n!
2mc 2 n
1
r2
n!
Z2
= 2 3
.
a0 n (# + 1/2)
mc
2
Z
n
"4 !
n
3
# + 1/2 4
"
1 1
S
(r V ) L
2
2
2m c r
1 Ze 2
4#0 r
and
2
1
1
Ze
2 =
S
H
L
2
2
3
2m c 4"0 r
e
e 1
(p
e
(
V
))
=
(r V )L S
r r
2
2
(mc)
(mc) r
r = 1r L.
where we have used the relation p e
Additional factor of 1/2 derives from further relativistic effect
known as Thomas precession.
Those discontent with heuristic derviation need only wait for Dirac
formulation...
H
L
2m2 c 2 4"0 r 3
0, J
2 ,
Achieved by turning to basis of eigenstates of the operators, H
2 , and S
2 , where J
=L
+ S.
Since J
2 = L
2 + S
2 + 2L
S,
it
Jz , L
follows that,
1 2 2 2
1
H
L
2
2
3
2m c 4"0 r
1
2
2 vanish allowing
Once again, off-diagonal matrix elements of H
correction to be computed in first order perturbation theory.
1 !
=
2m2 c 2 2
#H2 $n,j=!1/2,mj ,!
#
# 1
"
Ze
4"0
1
r3
n!
#H2 $n,j=!1/2,mj ,!
#
# 1
"
Ze
4"0
1
= mc 2
4
Z
n
"4
n
j + 1/2
1
j
1
j+1
1
r3
n!
#>0
j = # + 1/2
j = # 1/2
#H1 $n,j=!1/2,mj ,! = mc
n
.
1
j
=
#
1/2
2
n
j+1
Combining these expressions, for # > 0, we have
1
(Z )
"
V
=
=
(r)
8m2 c 2
8m2 c 2
"0
2m2 c 2 4"0
!2 Ze 2
1 2 (Z )4
2
=
|n00 (0)| = mc
2m2 c 2 4"0
2
n3
1 2
mc
2
Z
n
"4 !
3
n
4 j + 1/2
"
Spectroscopic notation
Relativistic corrections
En,j=!1/2,mj ,!
1 2
= mc
2
Z
n
"4 !
3
n
4 j + 1/2
"
Lamb shift
Within framework of quantum electrodynamics, Coulomb
interaction is mediated by exchange of photons gauge particles.
Interaction of electron with electromagnetic field can induce a
self-interaction ! effective smearing of electron position,
#(r)2 $ %
!
mc
"2
ln
1
,
Z
r 105 a0
ELamb
1 2
% mc
2
Z
n
"4
8
1
ln
3
Z
"
!,0
Hyperfine structure
Finally, we should address the potential influence of the nuclear
spin, I, which leads to a nuclear magnetic moment,
M = gN
e
I
2MN
0
Magnetic moment generates vector potential A = 4
M (1/r )
and magnetic field
+
,
0 3r(r M) r 2 M 8
(3)
B=A=
+
M
(r)
4
r5
3
Hyperfine interaction
+
,
0 3r(r M) r M 8
(3)
B=A=
+
M
(r)
5
4
r
3
2
I/!2
#Hhyp $n,1/2,0 =
|n00 (0)|2 S
4 2MN m 3
Hyperfine interaction
0 gN e e 8
I/!2
#Hhyp $n,1/2,0 =
|n00 (0)|2 S
4 2MN m 3
With |n00 (0)|2 =
1 Z mc 3
n3 ( ! ) ,
hyp $n,1/2,0 =
#H
1 2
mc
2
we obtain
Z
n
"4
8
m 2
n gN
S I/!
3 MN
Lecture 13-14
Multi-electron atoms
Background
How can we determine energy levels of a multi-electron atom?
We could start with hydrogenic energy levels for atom of nuclear
charge Z , and start filling electrons from lowest levels, accounting
for Pauli exclusion.
Degeneracy for quantum numbers (n, #) is 2 (2# + 1). Each
energy level, n, accommodates 2 n2 electrons:
n
1
2
3
4
#
0
0, 1
0, 1, 2
0, 1, 2, 3
Degeneracy in shell
2
(1 + 3) 2 = 8
(1 + 3 + 5) 2 = 18
(1 + 3 + 5 + 7) 2 = 32
Cumulative total
2
10
28
60
Background
Multi-electron atoms
Leaving aside (for now) relativistic effects, Hamiltonian for
multi-electron atom given by
, .
2
2
. + !2
1
Ze
1
e
2
=
H
i
+
2m
4"0 ri
4"0 rij
i
i<j
jj coupling
m=!
H0 =
+ Ui (ri )
2m i
4"0 ri
i
1 =
H
.
i<j
1 e2 .
Ui (ri )
4"0 rij
i
H0 =
+ Ui (ri )
2m i
4"0 ri
i
1 =
H
.
i<j
1 e2 .
Ui (ri )
4"0 rij
i
E = #|H|$ =
d r i
i
2m
4"0 r
i
/
/
.
1
e2
3
3 !
!
!
+
d r
d r i (r)j (r )
(r
)i (r)
j
!
4"0
|r r |
i<j
3
2
E
d
r
|
(r)|
1
=0
i
i
3
2
E
d
r
|
(r)|
1
=0
i
i
i
Following variation, obtain Hartree equations,
! 2 2
"
/
2
2
!
1 Ze
1 .
e
i +
d 3 r ! |j (r! )|2
i (r)
2m
4"0 r
4"0
|r r! |
j$=i
= i i (r)
!2 2
1 Ze 2
2m
4"0 r
"
/
1 .
e2
3 !
! 2
i +
d r |j (r )|
i (r)
!
4"0
|r r |
j$=i
= i i (r)
i
2m
4"0 r
/
.
1
e2
3 ! 3
! 2
2
+
d r d r |j (r )|
|
(r)|
i
4"0
|r r! |
j$=i
.
i
1
"i
4"0
./
i<j
e2
2
d r d r |j (r )|
|
(r)|
i
|r r! |
3 !
2i
+ Ui (ri )
2m
4"0 ri
i
/
2
d 1 .
e
d 3 r ! |j (r! )|2
4 4"0
|r r! |
j$=i
.
i<j
1 e2 .
Ui (ri )
4"0 rij
i
Hartree-Fock method
An improvement on this procedure can be achieved by introducting
a trial variational state wavefunction involving a Slater determinant,
1
1
1 1 (r1 ) 1 (r2 ) 1 (r3 ) 1
1
1
1
1 1 2 (r1 ) 2 (r2 ) 2 (r3 ) 11
= 1 3 (r1 ) 3 (r2 ) 3 (r3 ) 1
1
N! 11
..
..
..
. . 11
1
.
.
.
.
where k (ri ), with i = 1, 2 N, denote the single-particle
wavefunctions for electron i, and k = (n#m! ms )
(r
)
(r)
(r)
(r
)msi ,msj
+
d 3 rj!
j
i
j
i
j
4"0 |r r! |
j$=i
1s
1
0
2
2
2s
2
0
2
4
2p
2
1
6
10
3s
3
0
2
12
3p
3
1
6
18
4s
4
0
2
20
3d
3
2
10
30
4p
4
1
6
36
5s
5
0
2
38
4d
4
2
10
48
Subshell name
Cumulative
1s
2
2s
4
2p
10
3s
12
3p
18
4s
20
3d
30
4p
36
5s
38
4d
48
!
"
!
!
"7s!
7d
! 7p
!
!
"
!6s !
6p 6d
6f
!
! !
!
"
!
!
5s 5p
5f 5g
! 5d
!
!
!
"4s!4p!
4d
4f
!
! !
! !!
!
"3s !
3p !
3d !
!
!
!
"
!
2p !!
2s !
!
"1s! !
! !
!
Periodic table
1
2
3
4
5
6
7
8
9
10
11
12
14
16
18
19
H
He
Li
Be
B
C
N
O
F
Ne
Na
Mg
Si
S
Ar
K
(1s)
(1s)2
He (2s)
He (2s)2
He (2s)2 (2p)
He (2s)2 (2p)2
He (2s)2 (2p)3
He (2s)2 (2p)4
He (2s)2 (2p)5
He (2s)2 (2p)6
Ne (3s)
Ne (3s)2
Ne (3s)2 (3p)2
Ne (3s)2 (3p)4
Ne (3s)2 (3p)6
Ar (4s)
13.6
24.6
5.4
9.3
8.3
11.3
14.5
13.6
17.4
21.6
5.1
7.6
8.1
10.4
15.8
4.3
Periodic table
Aufbau principle forms basis of Periodic table of elements:
elements with similar electron configurations in outermost shells
have similar chemical properties.
Coupling schemes
.
i<j
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
34
5
34
5 2
2
1
H
H
Coupling schemes
H
0 +
H
.
i<j
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
2
34
5
34
5
2
1
H
H
1 , H
2 , can treat H
2 as a perturbation on
For light atoms, H
0 + H
1 known as LS (or Russell-Saunders) coupling.
H
2 , H
1 , electrons
For heavy atoms (or ionized light atoms), H
become relativistic and spin-orbit interaction dominates jj
coupling.
Both scenarios are approximations real atoms do not always conform to
this comparatively simple picture.
H
0 +
H
.
i<j
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
34
5
34
5 2
2
1
H
H
.
i<j
2
1
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
34
5
34
5 2
2
1
H
H
.
i<j
2
2
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
34
5
34
5 2
2
1
H
H
.
i<j
2
3
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
2
34
5
34
5
2
1
H
H
#JmJ LS|
i (ri )L
J LS$
i
Land
e interval rule
Since separation of energies for states of different J arises from
2 (fine structure),
spin-orbit term contribution H
.
i S
i |J, mJ , L, S$
#|J, mJ , L, S|
i (ri )L
i
(L, S)
[J(J + 1) L(L + 1) S(S + 1)]
2
(1)
m!
1
1
0
(1)
m!
1
1
(2)
m!
0
1
1
(2)
m!
1
0
mL
1
0
1
mL
2
1
S0
1
D2
3
P2
3
P1
3
P0
E /cm1
20649
10195
43
16
0
D1,2,3
P0,1,2
S1
D2
P1
S0
H0 =
+ Ui (ri ) , H1 =
Ui (ri )
2m
4"0 ri
4"0 rij
i
i<j
i S
i
H2 =
(ri )L
i
H
0 +
H
.
i<j
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
2
34
5
34
5
2
1
H
H
1 , H
2 , can treat H
2 as a perturbation on
For light atoms, H
0 + H
1 known as LS (or Russell-Saunders) coupling.
H
2 , H
1 , electrons
For heavy atoms (or ionized light atoms), H
become relativistic and spin-orbit interaction dominates jj
coupling.
H
0 +
H
.
i<j
.
1 e2 .
i S
i
Ui (r ) +
i (ri )L
4"0 rij
i
i
2
34
5
34
5
2
1
H
H
jj coupling scheme
.
2
.
.
1
e
H
0 +
i S
i
H
Ui (r ) +
i (ri )L
i<j 4"0 rij
i
i
2
34
5
2
34
5
2
H
1
H
Atomic spectra
Atomic spectra result from transitions between different electronic
states of an atom via emission or absorption of photons.
In emission spectra, atom is excited by some means (e.g.
thermally through collisions), and one observes discrete spectral
lines in light emitted as atoms relax.
= |Ef Ei |
2 , so selection rules
Atomic states always eigenstates of parity and J
can be regarded as absolutely valid in electric dipole transitions.
S = 0 and MS = 0
Follows from conservation of total spin in transition.
z + 2Sz ) = B B(L
z + 2Sz )/!
HZeeman =
B(L
2mc
denotes Zeeman term.
Since we are dealing with confined electrons, we have neglected the
diamagnetic contribution to the Hamiltonian.
rel. or
Depending on scale of magnetic field, the spin-orbit term in H
the Zeeman term may dominate the spectrum of the atom.
z + 2Sz ) = B B(L
z + 2Sz )/!
HZeeman =
B(L
2mc
Previously we have seen that, to leading order, relativistic
corrections lead to fine-structure energy shift,
rel.
En,j
=
1 2
mc
2
Z
n
"4 !
3
n
4 j + 1/2
"
= # 1/2, mj , #$ = B Bmj
1
1
2# + 1
"
z + 2Sz ) = B B(L
z + 2Sz )/! = B B(Jz + Sz )/!
HZeeman =
B(L
2mc
For multi-electron atom in weak field, unperturbed states given by
|J, MJ , L, S$, where J, L, S refer to total angular momenta.
S
=J
2 L
2 S
2 is diagonal in
First we note that the operator 2L
the basis of states, |J, MJ , L, S$.
i , Sk ] = 0, it
Therefore, recalling that [Si , Sj ] = i!"ijk Sk and [L
follows that the matrix element of the following operator vanishes,
L
S)
(L
S)
S
=L
j [Si , Sj ] = i!"ijk L
j Sk i!S
L
S(
i!S
3
S,
J]
= 0, it follows that the matrix element of
Moreover, since [L
the following operator also vanishes,
L)
J
=S
J(
L
S)
(L
S)
S
J
i!(S
If we expand left hand side, we thus find that the matrix element of
the following operator also vanishes,
L=
JS
S
J)
S
J
2
(S L) J = L(S J) S(L J) = J(
J
2 $ = #J(
S
J)$.
#Sz $ = #Jz $
2J(J + 1)
As a result, we can deduce that, at first order in perturbation
theory, the energy shift arising from the Zeeman term is given by
EJ,MJ ,L,S = B B#(Jz + Sz )$/! = B gJ MJ B
where effective Land
e g-factor
J(J + 1) + S(S + 1) L(L + 1)
gJ = 1 +
2J(J + 1)
N.B. for hydrogen (S = 1/2 and J = L 1/2), we recover previous
result.
EJ,MJ ,L,S = B gJ MJ B