Since we cannot say exactly where an electron is, the Bohr picture
of the atom, with electrons in neat orbits, cannot be correct.
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Hydrogen Atom:
Schrödinger Equation and Quantum Numbers
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Where does the quantisation in QM come from ?
h2 ⎛ ∂ 2 ∂ ⎞ h 2 ⎛⎜ 1 ∂ ∂ 1 ∂ 2 ⎞⎟
− ⎜ r ⎟Ψ − sin θ + Ψ + V ( r ) Ψ = EΨ
2m ⎝ ∂r ∂r ⎠ 2m ⎜⎝ sin θ ∂θ ∂θ sin 2 θ ∂φ 2 ⎟⎠
1 ⎡ d 2 dR 2mr 2 ⎤
QM
Oθφ Y (θ ,φ )
⎢ r + ( E − V (r ))R ⎥ = − =λ
R ⎣ dr dr h 2
⎦ Y (θ ,φ ) Separation of variables
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Where does the quantisation in QM come from ?
1 ⎡ d 2 dR 2mr 2 ⎤
Radial equation ⎢ r + 2
( E − V (r ))R ⎥=λ
R ⎣ dr dr h ⎦
⎛ 1 ∂ ∂ 1 ∂ 2 ⎞
− ⎜⎜ sin θ + 2 ⎟Y (θ ,φ )
QM
Oθφ Y (θ ,φ ) sin θ ∂θ ∂θ sin θ ∂φ ⎠2⎟
Angular equation − = ⎝ =λ
Y (θ ,φ ) Y (θ ,φ )
∂ 2Y ∂ ∂Y
− = sin θ sin θ + λ sin 2 θY
∂φ 2 ∂θ ∂θ
1 ∂ 2Φ 1 ⎛ ∂ ∂Θ ⎞
Derive: − = ⎜ sin θ sin θ + λ sin 2
θΘ ⎟ = m 2
(again arbitrary constant)
Φ ∂φ 2 Θ ⎝ ∂θ ∂θ ⎠
∂ 2Φ(φ )
+ m 2Φ(φ ) = 0
∂φ 2
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Where does the quantisation in QM come from ?
∂ 2Φ(φ ) Φ(φ + 2π ) = Φ (φ )
+ m 2Φ(φ ) = 0 and
∂φ 2
Solutions:
Φ(φ ) = eimφ
e 2πim = 1
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Where does the quantisation in QM come from ?
with integer m
First coordinate Φ(φ ) = e imφ
(positive and negative)
angular
1 ∂ ∂Θ ⎛⎜ m 2 ⎞⎟ part
Second coordinate sin θ + λ − 2 ⎟Θ = 0
sin θ ∂θ ∂θ ⎜⎝ sin θ ⎠
angular
Results in λl = l(l + 1) with l = 0,1,2,K momentum
1 ⎡ d 2 dR 2mr 2 ⎤
Third coordinate ⎢ r + 2
( E − V (r ))R ⎥ = l(l + 1)
R ⎣ dr dr h ⎦
Differential
equation Results in quantisation of energy radial
part
2
Z2 Z 2 ⎛⎜ e 2 ⎞⎟ me
En = − 2 R∞ = − 2 ⎜
n n ⎝ 4πε 0 ⎟⎠ 2h 2
with integer n (n>0)
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Angular wave functions
h⎡ 1 ∂ ∂ 1 ∂2 ⎤
Operators: L = ⎢
2
sin θ + 2 ⎥ Angular momentum
i ⎣ sin θ ∂θ ∂θ sin θ ∂φ 2 ⎦
r
h ∂ L = ( Lx , L y , Lz )
Lz =
i ∂φ
∫ Ylm (θ ,φ ) dΩ = 1
1 3 2
Y00 = Y11 = − sin θeiφ
4π 8π Ω
∫ YlmYl 'm'dΩ = δ ll 'δ mm'
*
3
Y10 = − cosθ Ω
4π
Parity
3
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8π
sin θe −iφ Pop Υlm (θ , φ ) = Υ (π − θ , φ + π ) = (− )l Υlm (θ , φ )
The radial part: finding the ground state
1 ⎡ d 2 dR 2mr 2 ⎤
⎢ r + 2 (E − V (r ))R ⎥ = λ h2 Ze 2
R ⎣ dr dr h ⎦ Prefactor for 1/r: − =0
ma 4πε 0
trial: R (r ) = Ae −r / a
A R
R ' = − e −r / a = − Solutions for the energy
a a
A R
R" = 2 e −r / a = 2
2
2⎛
2 ⎞
h2 e ⎟ me
a a E=− = − Z ⎜⎜ ⎟
⎝ 4πε 0 ⎠ 2h
2ma 2
h2 ⎛ 1 2 ⎞ Ze 2
− ⎜ 2 − ⎟− =E
2m ⎝ a ar ⎠ 4πε 0 r
Ground state in the
Bohr model (n=1)
must hold for all values of r
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Hydrogen Atom:
Schrödinger Equation and Quantum Numbers
There are four different quantum numbers needed to
specify the state of an electron in an atom.
1. The principal quantum number n gives the total energy.
2. The orbital quantum number l gives the angular
momentum; l can take on integer values from 0 to n - 1.
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Hydrogen Atom Wave Functions
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Radial Probability Distributions
Pr =4πr2|ψ|2
Ground state
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Hydrogen Atom Wave Functions
This figure shows the three probability distributions for n = 2 and l
= 1 (the distributions for m = +1 and m = -1 are the same), as well
as the radial distribution for all n = 2 states.
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Hydrogen “Orbitals” (electron clouds)
Max Born
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Atomic Hydrogen Radial part
Z2
Enlm = − 2
R∞
n
me e 4
with R∞ =
8ε 0 h 3c
Wave functions:
r
Ψnlm (r , t ) = Rnl (r )Υlm (θ , φ )e −iEn t / h
r& 2
& * r 2
I rad ∝ er I rad ∝ ∫ψ 1 erψ 2 dτ
The atom does not radiate when it is in a stationary state !
The atom has no dipole moment
*r
μii = ∫ ψ 1 r ψ 1dτ =0
2
Intensity of spectral lines linked μ fi
Bif =
to Einstein coefficient for absorption: 6ε 0h 2
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Selection rules
Mathematical background: function of odd parity gives 0 when integrated over space
∞ ∞
In one dimension: Ψ f x Ψi = ∫ Ψ *f xΨi dx = ∫ f ( x)dx with f ( x) = Ψ *f xΨi
−∞ −∞
∞ 0 ∞ 0 ∞ ∞ ∞
∞
= 2 ∫ f ( x)dx ≠ 0 if f ( − x) = f ( x) Ψi and Ψ f opposite parity
0
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Selection rules
depend on angular behavior of the wave functions
Parity operator
r All quantum mechanical wave functions
r have a definite parity
r r
θ Ψ (− r ) = ± Ψ (r )
φ r
Ψ f r Ψi ≠ 0
r
−r If Ψf and Ψi have opposite parity
r r
Pr = −r Rule about the Ylm functions
( x , y , z ) → ( − x, − y , − z )
PYlm (θ , φ ) = (− )l Ylm (θ , φ )
(r ,θ , φ ) → (r , π − θ , φ + π )
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Hydrogen Atom:
Schrödinger Equation and Quantum Numbers
1) Quantum number n
no restrictions Balmer series
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