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Lec12-14 Compressed PDF
Lec12-14 Compressed PDF
Atomic structure
Atomic structure: background
p̂2 1 Ze 2
Ĥ0 = −
2m 4π"0 r
! 2
"2
1 e m e2 1
En = −Ry 2 , Ry = 2
=
n 4π"0 2! 4π"0 2a0
4π#0 !2
where m is reduced mass (ca. electron mass), and a0 = e2 m .
n # Subshell(s)
1 0 1s
2 0, 1 2s 2p
3 0, 1, 2 3s 3p 3d
n 0 · · · (n − 1) ns · · ·
Atomic structure: hydrogen atom revisited
p̂2 1 Ze 2
Ĥ0 = −
2m 4π"0 r
is only the leading term in relativistic treatment (Dirac theory).
Such relativistic corrections begin to impact when the electron
becomes relativistic, i.e. v ∼ c.
Since, for Coulomb potential, 2#k.e.$ = −#p.e.$ (virial theorem),
1
2 mv 2
= #k.e.$ = −E 000 = Z 2
Ry. Using identity,
1 e2 1 1
Z Ry = mc 2 (Z α)2 ,
2
α= %
2 4π"0 !c 137
v
where α denotes the fine structure constant, we find = Zα .
c
The “real” hydrogen atom: outline
1 (p̂2 )2
Ĥ1 = −
8 m3 c 2
The relative scale of perturbation
#Ĥ1 $ p2 v2
% 2 2 = 2 % (Z α)2
#Ĥ0 $ m c c
e2 1 1
where α = 4π#0 !c % 137 .
1 (p̂2 )2
Ĥ1 = −
8 m3 c 2
2
! "4 ! "
mc Zα n 3
#Ĥ1 $n!m = − −
2 n # + 1/2 4
(b) Spin-orbit coupling
1 1
Ĥ2 = 2 2
(∂r V ) L̂ · Ŝ
2m c r
1 Ze 2
For a hydrogen-like atom, V (r ) = − 4π#0 r and
1 1 Ze 2
Ĥ2 = L̂ · Ŝ
2m2 c 2 4π"0 r 3
(b) Spin-orbit coupling: physical origin
e e 1
−µs · B = − 2
S · (p × ê (∂
r r V )) = 2
(∂r V )L · S
(mc) (mc) r
Those discontent with heuristic derviation need only wait for Dirac
formulation...
(b) Spin-orbit coupling
1 1 Ze 2
Ĥ2 = L̂ · Ŝ
2m2 c 2 4π"0 r 3
1 2 2 2 1
L̂ · Ŝ = (Ĵ − L̂ − Ŝ ) = (j(j + 1) − #(# + 1) − s(s + 1))
2 2
(b) Spin-orbit coupling
1 2 2 2 1
L̂ · Ŝ = (Ĵ − L̂ − Ŝ ) = (j(j + 1) − #(# + 1) − s(s + 1))
2 2
1 1 Ze 2
Ĥ2 = 2 2 3
L̂ · Ŝ
2m c 4π"0 r
! "4 *
1
1 Zα n j = # + 1/2
#Ĥ2 $n,j=!±1/2,mj ,! = mc 2 j
1
4 n j + 1/2 − j+1 j = # − 1/2
π!2 Ze 2 2 1 2 (Z α)4
#Ĥ3 $nj=1/2,mj !=0 = |ψn00 (0)| = mc
2m2 c 2 4π"0 2 n3
! "4 ! "
1 2 αZ 3 n
∆En,j=!±1/2,mj ,! = mc −
2 n 4 j + 1/2
independent of # and mj .
Spectroscopic notation
n 2s+1 Lj
! "4 ! "
1 2 αZ 3 n
∆En,j=!±1/2,mj ,! = mc −
2 n 4 j + 1/2
! "2
2α ! 1
#(δr)2 $ % ln , δr ∼ 10−5 a0
π mc αZ
! "4 ! "
1 2 αZ 8 1
∆ELamb % mc n× α ln δ!,0
2 n 3π αZ
Hyperfine structure
e
M = gN I
2MN
where nucleus has mass MN and gyromagnetic ratio gN .
Since nucleus has internal structure, gN is not simply 2. For proton,
sole nuclear constituent of atomic hydrogen, gp ≈ 5.56. Even
though neutron is charge neutral, gn ≈ −3.83.
µ0
Magnetic moment generates vector potential A = − 4π M × ∇(1/r )
and magnetic field
+ ,
µ0 3r(r · M) − r 2 M 8π (3)
B=∇×A= + Mδ (r)
4π r5 3
Hyperfine interaction
+ ,
2
µ0 3r(r · M) − r M 8π (3)
B=∇×A= 5
+ Mδ (r)
4π r 3
e
Ĥhyp = (L̂ + 2Ŝ) · B
2m
µ0 gN e e 8π
#Ĥhyp $n,1/2,0 = |ψn00 (0)|2 Ŝ · Î/!2
4π 2MN m 3
Hyperfine interaction
µ0 gN e e 8π
#Ĥhyp $n,1/2,0 = |ψn00 (0)|2 Ŝ · Î/!2
4π 2MN m 3
1 Z αmc 3
With |ψn00 (0)|2 = πn3 ( ! ) , we obtain
! "4
1 2 Zα 8 m
#Ĥhyp $n,1/2,0 = mc n × gN Ŝ · Î/!2
2 n 3 MN
showing scale of perturbation suppressed over fine structure by
factor m/MN ∼ 10−3 .
Finally, as with spin-orbit interaction, if we set F = I + S,
1 1 2 2 2 1
S · I = 2 (F − S − I ) = (F (F + 1) − 3/4 − I (I + 1))
!2 -2! 2
1 I F = I + 1/2
=
2 −I − 1 F = I − 1/2
Summary of atomic energy scales
. + !2 1 Ze 2
, .
1 e2
2
Ĥ = − ∇i − +
2m 4π"0 ri 4π"0 rij
i i<j
Coupling schemes:
1 LS coupling and Hund’s rules
2 jj coupling
!
.
|Ylm (θ, φ)|2 = const.
m=−!
. + !2 1 Ze 2
,
2
Ĥ0 = − ∇ − + Ui (ri )
2m i 4π"0 ri
i
. 1 e2 .
Ĥ1 = − Ui (ri )
4π"0 rij
i<j i
! " /
!2 ∇2 1 Ze 2 1 . 3 ! ! 2 e2
− − ψi + d r |ψj (r )| !
ψi (r)
2m 4π"0 r 4π"0 |r − r |
j$=i
= εi ψi (r)
. + !2 1 Ze 2
,
Ĥ0 = − ∇2i − + Ui (ri )
2m 4π"0 ri
i
. 1 e2 .
Ĥ1 = − Ui (ri )
4π"0 rij
i<j i
Hartree-Fock method
!
"
!
!
"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 H (1s) 13.6
2 He (1s)2 24.6
Can use energy sequence to 3 Li He (2s) 5.4
predict ground state electron 4 Be He (2s)2 9.3
configuration – fill levels 5 B He (2s)2 (2p) 8.3
accounting for exclusion 6 C He (2s)2 (2p)2 11.3
aufbau principle. 7 N He (2s)2 (2p)3 14.5
8 O He (2s)2 (2p)4 13.6
9 F He (2s)2 (2p)5 17.4
Sadly, there are exceptions to 10 Ne He (2s)2 (2p)6 21.6
rule: e.g. Cu (Z = 29) 11 Na Ne (3s) 5.1
expected to have configuration 12 Mg Ne (3s)2 7.6
(Ar)(4s)2 (3d)9 , actually has 14 Si Ne (3s)2 (3p)2 8.1
(Ar)(4s)1 (3d)10 . 16 S Ne (3s)2 (3p)4 10.4
18 Ar Ne (3s)2 (3p)6 15.8
19 K Ar (4s) 4.3
Periodic table
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
Since Ĥ commutes with set of total angular momenta, Ĵ2 , L̂2 , and
Ŝ2 , energy levels of multi-electron atoms are characterized by
quantum numbers L, S, J.
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
∆J ∝ J(J + 1) − (J − 1)J = 2J
(1) (2)
m! m! mL
To form symmetric total angular 1 1 2
momentum state, two electrons may 1 0 1
LS coupling – Example: carbon
E /cm−1
1
S0 20649
1
D2 10195
3
P2 43
3
P1 16
3
P0 0
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
4π"0 rij
i<j i i
2 34 5 2 34 5
Ĥ1 Ĥ2
. 1 e2 . .
Ĥ ≈ Ĥ0 + − Ui (r ) + ξi (ri )L̂i · Ŝi
i<j 4π"0 rij i i
2 34 5 2 34 5
Ĥ1 Ĥ2
(1/2, 1/2)0 (3/2, 1/2)1 (3/2, 1/2)2 (3/2, 3/2)2 (3/2, 3/2)0
in order of increasing energy.
jj coupling scheme: Example
(1/2, 1/2)0 (3/2, 1/2)1 (3/2, 1/2)2 (3/2, 3/2)2 (3/2, 3/2)0
e
ĤZeeman =− B(L̂z + 2Ŝz ) = −µB B(L̂z + 2Ŝz )/!
2mc
denotes Zeeman term.
e
ĤZeeman =− B(L̂z + 2Ŝz ) = −µB B(L̂z + 2Ŝz )/!
2mc
! "4 ! "
rel. 1 2 Zα 3 n
∆En,j = mc −
2 n 4 j + 1/2
e
ĤZeeman = − B(L̂z + 2Ŝz ) = −µB B(L̂z + 2Ŝz )/! = −µB B(Ĵz + Ŝz )/!
2mc
!mj
#n, j = # ± 1/2, mj , #|Ŝz |n, j = # ± 1/2, mj , #$ = ±
2# + 1
we obtain the following expression for the first order energy shift,
! "
Zeeman 1
∆Ej=!±1,mj ,!
= # ± 1/2, mj , #$ = µB Bmj 1±
2# + 1
i.e. all degenerate levels split by field.
e
ĤZeeman =− B(L̂z + 2Ŝz ) = −µB B(L̂z + 2Ŝz )/! = −µB B(Ĵz + Ŝz )/!
2mc
1 First we note that the operator 2L̂ · Ŝ = Ĵ2 − L̂2 − Ŝ2 is diagonal in
the basis of states, |J, MJ , L, S$.
2 Therefore, recalling that [Ŝi , Ŝj ] = i!"ijk Ŝk and [L̂i , Ŝk ] = 0, it
follows that the matrix element of the following operator vanishes,
Ŝ(L̂ · Ŝ) − (L̂ · Ŝ)Ŝ = L̂j [Ŝi , Ŝj ] = i!"ijk L̂j Ŝk ≡ −i!Ŝ × L̂
Zeeman effect: revisited
3 Moreover, since [L̂ · Ŝ, Ĵ] = 0, it follows that the matrix element of
the following operator also vanishes,
−i!(Ŝ × L̂) × Ĵ = Ŝ × Ĵ(L̂ · Ŝ) − (L̂ · Ŝ)Ŝ × Ĵ
4 If we expand left hand side, we thus find that the matrix element of
the following operator also vanishes,
L̂=Ĵ−Ŝ
(Ŝ × L̂) × Ĵ = L̂(Ŝ · Ĵ) − Ŝ(L̂ · Ĵ) = Ĵ(Ŝ · Ĵ) − ŜĴ2
∆EJ,MJ ,L,S = µB gJ MJ B