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How to see
Early models
Atomic spectra
The Bohr model
Correspondence principle
Demerits…
How to see
de Broglie wavelength
The probe has to interact/scatter the object
For photons:
◦ 1 eV ~ 10-10 m - atomic physics
◦ 1 MeV ~ 10-15 m - nuclear physics
◦ 1 GeV ~ 10-20 m - particle physics
Examples of probes in atomic scale
◦ XRD
◦ Electron microscope (SEM, TEM)
Early models of atom
An atomic electron
proton
should, classically, spiral
rapidly into the nucleus
as it radiates energy due
to its acceleration
electron
The Bohr atom
Electron waves & stationary states
h
de Broglie wavelength of e : −
λ=
mv
mv 2 1 e2 e
FCentripetal = FElectric ⇒ =2 ⇒ v=
r 4πε 0 r 4πε 0 mr
h 4πε 0 r
Orbital e − wavelength: λ =
c m
This corresponds to the circumference of e − orbit: λ = 2π r
An e − can circle a nucleus only if its orbit contains
an integral number of de Broglie wavelengths
=
Condition for orbit stability: nλ 2=
π rn n 1, 2,3,
Stationary states
Bohr orbits
=
Condition for orbit stability: nλ 2=
π rn n 1, 2,3,
Angular momentum quantization (alternate approach)
h
L = I ω = (mr )(v / r ) = mvr
2
= n = n
2π
h
λ= ⇒ nλ =
2π rn
mv
nh 4πε 0 rn
= 2π rn
e m
n 2 h 2ε 0
=
Orbital radii in Bohr atom: rn = n 1, 2,3,...
π me 2
e
v=
4πε 0 mr
e2
⇒ En =
−
4πε 0 rn
me 4 1 E1
⇒ En =
− 2 2 2 = n=
1, 2,3,...
8ε 0 h n n 2
1 E1 1 1
Hydrogen spectrum : =
− 2− 2
λ hc nl nu
Correspondence principle
The greater the quantum number, the closer
quantum physics approaches classical physics
∂2 y 1 ∂2 y
Wave equation: = 2 2 (same sense of II law)
∂x 2
v ∂t
∂Ψ 2 ∂ 2 Ψ
Schrodinger equation: i =− + U Ψ (1D)
∂t 2m ∂x 2
Schrodinger’s equation
∂ 2ψ ∂ 2ψ ∂ 2ψ 2m
+ 2 + 2 + 2 ( E − U )ψ =
0 (3D)
∂x 2
∂y ∂z
e2
Electric potential energy: U= −
4πε 0 r
∂ 2 ∂ψ ∂ ∂ψ
sin θ r
2
+ sin θ sin θ
∂r ∂r ∂θ ∂θ
∂ 2ψ 2mr 2 sin 2 θ e 2
+ 2+ + E ψ =
0
∂φ 2
4πε 0 r
Separation of variables
Hydrogen atom wave fn.: ψ (r , θ , φ )= R(r )Θ(θ )Φ (φ )
∂ψ ∂R dR
Simply, if ψ = RΘΦ ⇒ = ΘΦ = ΘΦ
∂r ∂r dr
∂ψ dΘ ∂ 2ψ d 2Φ
Similarly = RΦ , =
RΘ 2
∂θ dθ ∂φ 2
dφ
Substituting above in Schrodinger’s eqn. and rearranging,
d 2 dR sin θ d dΘ
sin 2 θ r + sin θ
dr dr Θ dθ dθ
2mr 2 sin 2 θ e2 1 d 2Φ
+ + E =
−
2 4πε 0 r Φ d φ 2
1 d 2Φ
if f=
( x) g ( y ), then f=
( x) g=
( y ) const. ⇒ − =m 2
Φ dφ 2
l
Substituting for ml and rearranging, yields
1 d 2 dR 2mr 2 e 2 ml2 1 d dΘ
r + + E =
− sin θ
R dr dr 2 4πε 0 r sin 2
θ Θ sin θ dθ dθ
d 2Φ
Equation for Φ: + ml Φ =0
2
dφ 2
1 d dΘ ml2
Equation for Θ: sin θ + l (l + 1) − 2 Θ =0
sin θ dθ dθ sin θ
1 d 2 dR 2m e 2 l (l + 1)
Equation for R: r + 2 + E− R=
0
r dr dr 4πε 0 r
2
2
r
Quantum numbers
The solution of equation for Φ is given by Aeimlφ
Φ (φ ) =
2l (l + 1)
If R(r) has to be an exclusive function of r, KEorbital =
2mr 2
2
L
1 2
KEorbital = = mvorbital = 2 {L mvorbital r
2 2mr
L2 2l (l + 1)
∴ 2
=2 ⇒ Electron angular momentum L =
l (l + 1)
2mr 2mr
Magnetic quantum number
e- revolving around the nucleus ≈ minute current loop
Has a magnetic field like that of magnetic dipole
Interacts with external magnetic field B
Space quantization
Lz = ml ml = 0, ±1, ±2,..., ±l
Uncertainty principle & Lz
Why only Lz is quantized?
(n′l ′ml′)
∞
Allowed transitions: ∫
−∞
ψ n*′l ′m′ uψ nlm ≠ 0
l l
{u =
x, y , z
µ = IA = −ef π r 2 = ω r 2π f
v r=
= = 2π mfr 2
L mvr
=
L l (l + 1) e
⇒ Um =
ml B
ml 2m
cos θ =
l (l + 1)
e
Bohr magneton: µ B =
2m
ml µ B B
⇒ Um =
B e
v0 µ B =−
v1 =− v0 B
h 4π m
Normal Zeeman
v2 = v0
effect
B e
v0 µ B =+
v3 =+ v0 B
h 4π m
Anomalous Zeeman effect
The previous QM treatment could not explain both anomalous Zeeman effect and
fine structure
Two Dutch graduate students (Samuel Goudsmit & George Uhlenbeck) proposed in
1925 that
Every e- has an intrinsic angular momentum, called spin, whose magnitude is the
same for all electrons. Associated with this angular momentum is a magnetic
moment
Electron spin
11 3
Spin angular momentum: S= s ( s + 1) = + 1 =
22 2
1
S z = ms = ±
2
Classical model of a spinning electron. This model gives an
incorrect magnitude for the magnetic moment, incorrect
quantum numbers, and too many degrees of freedom. Spin
arises from relativistic dynamics.
e e
Spin magnetic moment: µS = − S µ Sz =
± ± µB
=
m 2m
Stern-Gerlach experiment
µ cos θ = µ Sz = ± µ B
⇒ ± µB B
Um =
L.S: origin of fine structure
Vector atom model
Total angular momentum: J= L + S
1
J = j ( j + 1) , j =l + s =l ±
2
jz =m j , m j =− j , − j + 1,..., j − 1, j
Precession of L, S & J
J is also space quantized
A relation for µJ
µS
µL
=2
S L
Two triangles are not similar
⇒ µ and J are not parallel
e
µ= J µL + µS = − ( L + 2S )
2m
e
= − (J + S )
2m
µ J = projection of µ on J
µ⋅J e J ⋅J + J ⋅S
= = −
L ⋅ L = (J − S ) ⋅ (J − S ) J 2m J
1
= J ⋅ J + S ⋅ S − 2J ⋅ S J ⋅ J + ( J ⋅ J + S ⋅ S − L ⋅ L)
e 2
1 = −
J ⋅ S= ( J ⋅ J + S ⋅ S − L ⋅ L) 2m J
2
A relation for µJ (contd.)
1
J ⋅ J + ( J ⋅ J + S ⋅ S − L ⋅ L)
e
µJ = − 2
2m J
1
J ( J + 1) + [ J ( J + 1) 2 + S ( S + 1) 2 − L( L + 1) 2 ]
2
e 2
= −
2m J ( J + 1)
e J ( J + 1) + S ( S + 1) − L( L + 1)
= − J ( J + 1) 1 +
2m 2 J ( J + 1)
µJ =
− µ B J ( J + 1) g J
J ( J + 1) + S ( S + 1) − L( L + 1)
gJ = 1+
2 J ( J + 1)
is the Lande g factor which is needed to calculate the relative
splitting of energy levels in weak magnetic fields
LS Coupling
How to couple angular momenta in many electron atoms
L= ∑ Li , S=
i
∑ Si ,
i
J= L + S
Hα line
Selection rule
∆l =±1