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Atomic Models

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

 Plum pudding model of 1890s

 Rutherford’s experiment in 1911


Atomic spectra
Atomic spectra: the key

 Planetary model (Rutherford) 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

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

Bohr radius: a0 = 5.292 ×10−11 m ;


r1 = rn =
n 2 a0
Energy levels
mv 2 e2
E = KE + PE = −
r 4πε 0 r

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

At very high ‘n’ we have more dense


levels which are more like continuum
Bohr atom model: Demerits
 Applicable only to hydrogen and other one-
electron ions such as He+ and Li2+
 Cannot explain why some lines are more
intense than others
 Cannot explain why many lines consist of
several separate lines whose wavelengths
differ very slightly
 No light on how individual atoms interact
 Quantum mechanics was developed
(1925,1926:Schrodinger, Heisenberg, Born,
Dirac & others) to overcome these shortfalls
Quantum theory of
hydrogen atom
• Quantum mechanics: recap
• Schrodinger’s eqn. for Hydrogen atom
• Separation of variables
• Quantum numbers
• Electron probability density
• Selection rules
• Zeeman effect
Quantum mechanics: recap
 Explores probabilities instead of asserting
 Eg. Hydrogen atom: rg.s. from Bohr theory = 5.3×10-11 m
 QM  Most probable rg.s.= 5.3×10-11 m
 Wave function
 Ψ itself has no physical interpretation
 |Ψ|2 ∝ probability of finding the body (+ve, real quantity)

∫ Ψ dV =
2
Normalization: 1
−∞
x2
Px1= ∫ Ψ dx
2
Probability: x2 x1

∂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

In spherical polar coordinates, the Schrodinger’s equation becomes

∂  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

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 

=l(l + 1) (Again we have different variables on both sides)

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 ) =

Exploiting the symmetry that φ and φ + 2π identify the same


Plane, we have,
Φ (φ ) =Φ (φ + π ) ⇒ Aeimlφ = Aeiml (φ + 2π ) ⇒ m = 0, ±1, ±2, ±3,. .
The differential equation for Θ has a solution provided:
l is an integer and l ≥ ml ⇒ m = 0, ±1, ±2,..., ±l
The final solution of radial part yields,
me 4  1  E1
En =− 2 2 2  2 
= 2; n =1, 2,3,... ; n ≥ l + 1
32π ε 0   n  n

= l 0,1, 2,..., (n − 1)

Thus the principal (n), orbital (l) and magnetic (m)


quantum numbers are defined
Orbital quantum number
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 

E includes electron’s orbital kinetic energy also !!


e2
E = KEradial + KEorbital + U = KEradial + KEorbital −
4πε 0 r
1 d  2 dR  2m   2l (l + 1) 
⇒ 2 r  + 2  KEradial + KEorbital − R= 0
r dr  dr    2mr  2

 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

ml specifies the direction of L by


determining the component
of L in the field direction.

 Space quantization

Lz = ml  ml = 0, ±1, ±2,..., ±l
Uncertainty principle & Lz
Why only Lz is quantized?

L can never point any specific direction


but in cone where Lz=ml

If not the uncertainty principle will be


violated

If L were in z direction, e- is confined to


xy plane and hence ∆z = 0, ∆pz → ∞

L precesses constantly about z-axis


Electron probability density
 No definite orbits
QM view of atoms
The orbitals
Selection rules
(nlml )

(n′l ′ml′)


Allowed transitions: ∫
−∞
ψ n*′l ′m′ uψ nlm ≠ 0
l l
{u =
x, y , z

Transitions not obeying above condition are forbidden transitions

⇒ Selection rules: ∆l =±1


∆ml = 0, ±1
Interaction with magnetic field
The torque τ on a magnetic dipole in a
magnetic field of flux density B is
 
= τ µ B sin θ {r × F
=
Potential energy when θ π / 2.
U m 0=
θ θ
For other orientations U m = ∫ τ dθ = µ B ∫ sin θ dθ = − µ B cos θ
π /2 π /2

µ = IA = −ef π r 2 = ω r 2π f
v r=
= = 2π mfr 2
L mvr

Electron magnetic moment


  e 
µ = − L
 2m 
Gyromagnetic ratio
U m = − µ B cos θ
 e 
⇒ Um =
  LB cos θ
 e   2m 
µ = − L
 2m 

=
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 =

In a magnetic field, the energy of a


particular atomic state depends on ml also
Zeeman effect
In a magnetic field, the energy of a E E0 + U m
=
v =
particular atomic state depends on ml also h h
⇒ a level with unique 'n' splits into
U m = ml µ B B
different levels having different 'ml '
B
⇒ v =v0 + ml µ B
h
∆ml = 0, ±1

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
11  3
Spin angular momentum: S= s ( s + 1)  =  + 1 = 
22  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

Magnetic moment of silver atom is due to one electron


dB
Cause for deflection: Fz = µ S cos θ
dz
First proof of space quantization
Spin-orbit coupling
U m = − µ B cos θ ,

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

For many e − atoms


∆L =±1
∆J =±1
∆S = 0

More complications exist


• Relativistic effects
• Vacuum fluctuations, etc.