![Page 1: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/1.jpg)
Quantum Physics Lecture 10
- Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection rules for transitions - Zeeman Effects, electron spin
The Hydrogen atom
Many electron atoms (Z>1)
- Periodic table of elements - Moseley’s Law
![Page 2: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/2.jpg)
Hydrogen Atom Re-visited First real test of Schroedinger Equation:
Recall Bohr model: En ∝ -1/n2, via one quantum number n (also, quantised angular momentum L via same n)
Successes: Hydrogen line emission spectra also… size & stability of atoms, Moseley’s Law for Z, etc.
Problems: Full 3D & spherical symmetry? Magnetic effects in spectra Z > 1 atoms’ spectra
Comparison with Bohr model: same expression for En via “principal” quantum number n
L = n
![Page 3: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/3.jpg)
Schroedinger Equation for H atom
Ψ r,θ ,φ( ) = R r( )Θ θ( )Φ φ( )
Express wavefunction as product (c.f 2-D box)
Leads to 3 separate equations
−
2
2mr 2
ddr
r 2dR r( )
dr
⎛
⎝⎜
⎞
⎠⎟ +
2l l +1( )2mr 2 +U r( )
⎛
⎝⎜
⎞
⎠⎟ R r( ) = ER r( )
1sinθ
ddθ
sinθdΘ θ( )
dθ
⎛
⎝⎜
⎞
⎠⎟ + l l +1( ) − ml
2
sin2θ
⎛
⎝⎜
⎞
⎠⎟ Θ θ( ) = 0
d 2Φ φ( )dφ 2 + ml
2Φ φ( ) = 0
R solutions are e-αr (× r polynomial) type, Θ are functions of cos & sin θ Φ solutions are exp(imlϕ) type, where ml is an integer
Solutions specified by three quantum numbers: n, l, ml
![Page 4: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/4.jpg)
Schroedinger Equation for H atom (cont.)
Angular momentum - is quantised Solution shows
(c.f. angular momentum in lecture 9)
Also Φ must be single valued and
Find
Note that L can be zero (unlike Bohr model) And Lz < L (unless L=0)
∵ Exists an Uncertainty relation between Lx Ly Lz
Bohr – plane, but must have Δp normal to plane… Also seen via (try it! – commutator)
But so no uncertainty between L and Lz & can know both
Φ φ( ) = Φ φ + 2π( )
Lz = ml (ml = 0,±1,± 2... ± l)
L = l l +1( )
‘Semi-classical’ vector pictures for l=2
Lx Ly − Ly Lx = Lx , Ly
⎡⎣ ⎤⎦ = iLz
L2 , Lz⎡⎣ ⎤⎦ = 0
![Page 5: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/5.jpg)
Solutions specified by three quantum numbers: n, l, ml (c.f. 3-D box, Lect. 8)
Energy Levels are En and the same as the Bohr model!
with n = 1, 2, 3, 4, ….
Solutions show l = 0, 1, 2, 3… n-1 and | ml | ≤ l Notation: s, p, d, f… for l = 0, 1, 2, 3, ….
So, possible states of electron:
Schroedinger Equation for H atom (cont.)
En = −me4
8εo2h2
1n2( )
Note: En does not depend on l, ml i.e. l, ml states are degenerate –
but holds only for H atom
![Page 6: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/6.jpg)
Electron states in hydrogen atom - orbitals
s-states - spherically symmetric
P r( )dr = ψ
24πr 2dr
Radial probability distributions (a = Bohr radius)
Note for l = n-1 (1s, 2p, 3d…) there is one maximum, at r = n2a
![Page 7: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/7.jpg)
The (ml) sub-shells combine to give spherically symmetric (l) shells - Spherical ‘harmonics’ (complete shells…)
e.g. for 2p-states, cosθ & sinθ dependence Squared (probability) & add - gives 1
Angular functions - orbitals
2p orbitals
![Page 8: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/8.jpg)
Images of orbitals….
N.B. Images (e.g. from web) are often of probability |ψ|2 rather than ψ
Recall that ψ can have negative as well as positive values. For example one lobe of the 2px orbital is +ve the other lobe -ve. Both give the same probability
![Page 9: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/9.jpg)
Transition of electrons between orbitals
Selection rules for transitions: Δl = ± 1 And Δml = 0 or ± 1 All others are ‘forbidden’
Conservation overall of angular momentum, photon has angular momentum of
l determines the magnitude of L, ml determines the direction
A non-zero magnetic field direction defines z But B field alters the energy... N.B. Magnetic dipole moment (current in loop x area of loop)
with (Bohr Magneton) e+
e- µ =
ve2πr
πr 2 mvr =
µB =
e2m
Applied B field shifts energy (dipole-field interaction) so ml states are split apart by µBB
So moment = mlµB
![Page 10: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/10.jpg)
Zeeman Effect
In non-zero magnetic field B each l-level splits into 2l+1 ml sub-levels of slightly different energy, depending on B
Spectra show three lines instead of one; only three because of further selection rule:
Δml = ± 1, 0
But…. some transitions showed more than three - anomalous
![Page 11: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/11.jpg)
Anomalous Zeeman Effect
Problem: more than 3 lines and smaller separation(s)
Solution: “electron spin”
See lecture 9 !
Electron has spin angular momentum but
Spin angular momentum S (cf L) Spin magnetic quantum number ms (cf ml)
Total combined angular momentum J
Combining L and S leads to correct number and splitting of emission lines (first seen by Irishman Thomas Preston)
J =L +S
J = j j +1( )
j = l ± 1
2
sz = ±
2 µz = − 2.000232( ) e
2msz
![Page 12: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/12.jpg)
More than 1 electron atoms…
Simple picture:
can add electrons to hydrogen-like quantum states assumes the nucleus increasing charge is shielded by inner electrons and ignores electron – electron interaction energies…. Try it anyway….
But: Pauli exclusion principle – no two electrons can occupy the same quantum state (fermions, see Lecture 9)
Two spins states possible – ‘up’ and ‘down’ ↑ or ↓
So maximum of two electrons in each state one ↑ and the other↓
±
2
![Page 13: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/13.jpg)
Many electron atoms
For Z>1, fill quantum states with max. 2 electrons each First quantum number n (c.f.Bohr energy level) Second quantum number l (angular momentum state) where 0 ≤ l ≤ (n-1) Third quantum number ml where |ml| ≤ l
![Page 14: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/14.jpg)
Many electron atoms (cont.) Examples: Helium atom Contains 2 electrons, both can be in 1s state (lowest energy)
provided one is spin up the other spin down Notation for the ground state 1s2
Lithium (Z=3)
1s shell filled (like He) Extra electron goes into 2s shell
Notation 1s2 2s1
2s orbital further out… Nuclear charge screened by 1s shell, effective charge more like H but further out So less well bound 2s electron can be lost in bonding (ionicity)
![Page 15: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/15.jpg)
n=1 - l=0 s state – 2 electrons n=2 - l=1 p state – 6 electrons …… l=2 d state – 10 electrons ……. l=3 f state – 14 electrons
Z>1 The periodic table of elements Gives the basic structure of the Periodic Table of the elements
![Page 16: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/16.jpg)
Periodic Table of Elements
For Hydrogen, s,p,d,f, states have same energy for given n (c.f. Bohr)
This Degeneracy of states is broken for Z >1 (by e-e interaction potentials) So s fills before p, before d etc., the gap increasing
as Z becomes larger.
1-7s 4-5f 3-6d 2-7p
![Page 17: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/17.jpg)
X-Ray spectra
X-Rays are emitted by impact of high energy electrons on elements
Continuous spectrum due Bremsstrahlung & other scattering processes
Molybdenum spectrum shown
λmin =
hceV
Impacting electrons cause electrons in core (lowest energy) states to be knocked out. For high Z atoms, these are very tightly bound states (K shells), so require high energies (many keV) to eject them
Spectrum shows sharp peaks, due to emission of photons by outer electrons falling to vacated core states. Energy (frequency) is characteristic of element.
N.B. Lower energy spectroscopy shows energies which often have little to do with the Z number of the atom – a problem for early atom models!
![Page 18: Quantum Physics Lecture 10 - Trinity College, Dublin · Quantum Physics Lecture 10 - Solution of Schroedinger equation - 3 quantum numbers - Probability and ‘Orbitals’ - Selection](https://reader030.vdocuments.net/reader030/viewer/2022040602/5e97bbf509e57925ba1a558b/html5/thumbnails/18.jpg)
Moseley’s Law
Moseley found that
The first time Z was spectroscopically determined…
f ∝ Z −1( )2
One other electron in K-shell, so nuclear charge screened by 1e, i.e. reduced to Z-1 Transition from n=2 to n=1 gives (Bohr model)
Which agrees very closely with Moseley’s experiment.
Actually the most important early evidence for nuclear model of atom!
ΔE =
34
Ryd Z −1( )2