introduction to quantum mechanic -...
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Introduction to Quantum
MechanicA) Radiation
B) Light is made of particles. The need for a quantification
1) Black-body radiation (1860-1901)
2) Atomic Spectroscopy (1888-) 3) Photoelectric Effect (1887-1905)
C) Wave–particle duality
1) Compton Effect (1923).
2) Electron Diffraction Davisson and Germer (1925).
3) Young's Double Slit Experiment
D) Louis de Broglie relation for a photon from relativity
E) A new mathematical tool: Wavefunctions and operators
F) Measurable physical quantities and associated operators -Correspondence principle
G) The Schrödinger Equation (1926)
H) The Uncertainty principle
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When you find this image, you may skip this part
This is less important
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The idea of duality is rooted in a debate over the nature of light and matter dating back to the 1600s, when competing theories of light were proposed by Huygens and Newton.
Christiaan HuygensDutch 1629-1695light consists of waves
Sir Isaac Newton1643 1727 light consists of particles
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Radiations, terminology
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Interferences
Constructive Interferences Destructive Interferences
in
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Phase speed or velocity
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Introducing new variables
• At the moment, let consider this just a formal change, introducing
and
we obtain
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Introducing new variables
At the moment, h is a simple constant
Later on, h will have a dimension and the p and E will be physical quantities
Then
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2 different velocities, v and vϕ
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If h is the Planck constant J.s
Then
Louis de BROGLIEFrench
(1892-1987)
Max Planck (1901)Göttingen
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- Robert Millikan (1910) showed that it was quantified.
-Rutherford (1911) showed that the negative part was diffuse while the positive part was concentrated.
Soon after theelectron discovery in 1887- J. J. Thomson (1887) Some negative part could be extracted from the atoms
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Gustav Kirchhoff (1860). The light emitted by a black body is called black-body radiation
black-body radiation
At room temperature, black bodies emit IR light, but as the temperature increases past a few hundred degrees Celsius, black bodies start to emit at visible wavelengths, from red, through orange, yellow, and white before ending up at blue, beyond which the emission includes increasing amounts of UV
RED WHITESmall ν ν ν ν Large ν ν ν ν
Shift of νννν
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black-body radiationClassical TheoryFragmentation of the surface.One large area (Small λ λ λ λ Large ν) ν) ν) ν) smaller pieces (Large λλλλ Small νννν)
Vibrations associated to the size, N2 or N3
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Kirchhoff
black-body radiation
RED WHITESmall ν ν ν ν Large ν ν ν ν
Shift of ννννRadiation is emitted when a solidafter receiving energy goes backto the most stable state (groundstate). The energy associated withthe radiation is the difference inenergy between these 2 states.When T increases, the average
E*Mean is higher and intensityincreases.E*Mean- E = kT.k is Boltzmann constant (k= 1.3810-23 Joules K-1).
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black-body radiation
Max Planck (1901)Göttingen
Why a decrease for small λλλλ ? Quantification
Numbering rungs of ladder introduces quantum numbers (here equally spaced)
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Quantum numbers
In mathematics, a naturalnumber (also called countingnumber) has two mainpurposes: they can be used forcounting ("there are 6 apples onthe table"), and they can beused for ordering ("this is the3rd largest city in the country").
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black-body radiation
Max Planck (1901)Göttingen
Why a decrease for small λλλλ ? Quantification
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black-body
radiation,
quantification
Max Planck
Steps too hard to climb Easy slope, rampPyramid nowadays Pyramid under construction
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Max Planck
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Johannes Rydberg 1888Swedish
n1 → n2 name Converges to (nm)
1 → ∞ Lyman 91
2 → ∞ Balmer 365
3 → ∞ Pashen 821
4 → ∞ Brackett 1459
5 → ∞ Pfund 2280
6 → ∞ Humphreys 3283
Atomic Spectroscopy
Absorption or Emission
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Johannes Rydberg 1888Swedish
IR
VISIBLE
UV
Atomic Spectroscopy
Absorption or Emission
Emission
-R/12
-R/22
-R/32
-R/42
-R/52
-R/62-R/72
Quantum numbers n, levels are not equally spaced R = 13.6 eV
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Photoelectric Effect (1887-1905)discovered by Hertz in 1887 and explained in 1905 by Einstein.
Vide
I
i
e
ee
Vacuum
Heinrich HERTZ (1857-1894)
Albert EINSTEIN(1879-1955)
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I
ν0ν0
ν ν
T (énergie cinétique)Kinetic energy
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Compton effect 1923playing billiards assuming λ=h/p
p
h/ λ'
h/ λ
p2/2m
hν '
hν
α
θ
Arthur Holly ComptonAmerican
1892-1962
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Davisson and Germer 1925
Clinton DavissonLester Germer
In 1927
d
θ
2d sin θ = k λ
Diffraction is similarly observed using a mono-energetic electron beam
Bragg law is verified assuming λλλλ=h/p
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Wave-particle Equivalence.
•Compton Effect (1923).•Electron Diffraction Davisson and Germer (1925)
•Young's Double Slit Experiment
In physics and chemistry, wave–particle duality is the concept that all matter and energy exhibits both wave-like and particle-like properties. A central concept of quantum mechanics, duality, addresses the inadequacy of classical concepts like "particle" and "wave" in fully describing the behavior of small-scale objects. Various interpretations of quantum mechanics attempt to explain this apparent paradox.
Wave–particle duality
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Thomas Young 1773 – 1829 English, was born into a family of Quakers.
At age 2, he could read.
At 7, he learned Latin, Greek and maths.
At 12, he spoke Hebrew, Persian and could handle
optical instruments.
At 14, he spoke Arabic, French, Italian and Spanish,
and soon the Chaldean Syriac. "H
He is a PhD to 20 years "gentleman, accomplished
flute player and minstrel (troubadour). He is
reported dancing above a rope."
He worked for an insurance company, continuing
research into the structure of the retina,
astigmatism ...
He is the rival Champollion to decipher
hieroglyphics.
He is the first to read the names of Ptolemy and
Cleopatra which led him to propose a first alphabet
of hieroglyphic scriptures (12 characters).
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Young's Double Slit Experiment
Ecran Plaque photo
F2
F1
Source
ScreenMask with 2 slits
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Young's Double Slit Experiment
This is a typical experiment showing the wave nature of light and interferences.
What happens when we decrease the light intensity ?If radiation = particles, individual photons reach one spot and there will be no interferences
If radiation ≠ particles there will be no spots on the screen
The result is ambiguousThere are spots
The superposition of all the impacts make interferences
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Young's Double Slit Experiment
Assuming a single electron each timeWhat means interference with itself ?
What is its trajectory?If it goes through F1, it should ignore the presence of F2
Ecran Plaque photo
F2
F1
Source
ScreenMask with 2 slits
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Young's Double Slit ExperimentThere is no possibility of knowing through which split the photon went!
If we measure the crossing through F1, we have to place a screen behind.Then it does not go to the final screen.
We know that it goes through F1 but we do not know where it would go after.These two questions are not compatible
Ecran Plaque photo
F2
F1
Source
ScreenMask with 2 slits
Two important differences with classical physics:
• measurement is not independent from observer
• trajectories are not defined; hν goes through F1 and F2 both! or through them with equal probabilities!
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Macroscopic world:A basket of cherriesMany of them (identical) We can see them and taste othersTaking one has negligible effectCherries are both red and good
Microscopic world:A single cherryEither we look at it without eatingIt is redOr we eat it, it is goodYou can not try both at the same timeThe cherry could not be good and red at the same time
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Slot machine “one-arm bandit”
After introducing a coin, you have
0 coin or X coins.
A measure of the profit has been
made: profit = X
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de Broglie relation from relativity
Popular expressions of relativity:m0 is the mass at rest, m in motion
E like to express E(m) as E(p) with p=mv
Ei + T + Erelativistic + P.
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de Broglie relation from relativity
Application to a photon (m0=0)
To remember
To remember
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Max Planck
Useful to remember to relate energy
and wavelength
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A New mathematical tool:
Wave functions and Operators
Each particle may be described by a wave function ΨΨΨΨ(x,y,z,t), real or complex,having a single value when position (x,y,z) and time (t) are defined.If it is not time-dependent, it is called stationary.The expression ΨΨΨΨ=Aei(pr-Et) does not represent one molecule but a flow of particles: a plane wave
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Wave functions describing one particle
To represent a single particle ΨΨΨΨ(x,y,z) that does not evolve in time, ΨΨΨΨ(x,y,z) must
be finite (0 at ∞).
In QM, a particle is not localized but has a probability to be in a given volume:dP= ΨΨΨΨ* ΨΨΨΨ dV is the probability of finding the particle in the volume dV. Around one point in space, the density of probability is dP/dV= ΨΨΨΨ* ΨΨΨΨΨΨΨΨ has the dimension of L-1/3
Integration in the whole space should give oneΨΨΨΨ is said to be normalized.
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Operators associated to physical quantities
We cannot use functions (otherwise we would end with classical mechanics)
Any physical quantity is associated with an operator.An operator O is “the recipe to transform ΨΨΨΨ into ΨΨΨΨ’ ”We write: O ΨΨΨΨ = ΨΨΨΨ’ If O ΨΨΨΨ = oΨΨΨΨ (o is a number, meaning that O does not modify ΨΨΨΨ, just a scaling factor), we say that ΨΨΨΨ is an eigenfunction of O and o is the eigenvalue.We have solved the wave equation O ΨΨΨΨ = oΨΨΨΨ by finding simultaneously ΨΨΨΨ and o that satisfy the equation.o is the measure of O for the particle in the state described by ΨΨΨΨ.
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Slot machine (one-arm bandit)
Introducing a coin, you have 0
coin or X coins.
A measure of the profit has been
made: profit = X
O is a Vending machine (cans)
Introducing a coin, you get one
can.
No measure of the gain is made
unless you sell the can (return to
coins)
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Examples of operators in mathematics : P parity
Even function : no change after x → -x Odd function : f changes sign after x → -x
y=x2 is eveny=x3 is odd
y= x2 + x3 has no parity: P(x2 + x3) = x2 - x3
Pf(x) = f(-x)
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Examples of operators in mathematics : A
y is an eigenvector; the eigenvalue is -1
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Linearity
The operators are linear:
O (aΨ1+ bΨ1) = O (aΨ1 ) + O( bΨ1)
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Normalization
An eigenfunction remains an eigenfunction when multiplied by a constant
O(λΨ)= o(λΨ) thus it is always possible to normalize a finite function
Dirac notations <ΨΨΨΨIΨΨΨΨ>
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Mean value
• If Ψ1 and Ψ2 are associated with the same eigenvalue o: O(aΨ1 +bΨ2)=o(aΨ1 +bΨ2)
• If not O(aΨ1 +bΨ2)=o1(aΨ1 )+o2(bΨ2)
we define ō = (a2o1+b2o2)/(a2+b2)
Dirac notations
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Sum, product and commutation of operators
(A+B)Ψ=AΨ+BΨ
(AB)Ψ=A(BΨ)
y1=e4x y2=x2 y3=1/x
d/dx 4 -- --
x3 3 3 3
x d/dx -- 2 -1
operators
wavefunctions
eigenvalues
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Sum, product and commutation of operators
y1=e4x y2=x2 y3=1/x
A = d/dx 4 -- --
B = x3 3 3 3
C= x d/dx -- 2 -1
not compatibleoperators
[A,C]=AC-CA≠0
[A,B]=AB-BA=0[B,C]=BC-CB=0
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Compatibility, incompatibility of operators
y1=e4x y2=x2 y3=1/x
A = d/dx 4 -- --
B = x3 3 3 3
C= x d/dx -- 2 -1
not compatibleoperators
[A,C]=AC-CA≠0
[A,B]=AB-BA=0[B,C]=BC-CB=0
When operators commute, the physical quantities may be simultaneously defined (compatibility)
When operators do not commute, the physical quantities can not be simultaneously defined (incompatibility)
compatibleoperators
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x and d/dx do not commute, are incompatible
Translation and inversion do not commute, are incompatible
A T(A)I(T(A))
I(A) AT(I(A))
vecteur de translation
O
Centre d'inversion
O
Translation vector
Inversion center
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Introducing new variables
Now it is time to give a physical meaning.
p is the momentum, E is the Energy
H=6.62 10-34 J.s
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Plane waves
This represents a (monochromatic) beam, a continuous flow of particles with the same velocity (monokinetic).
k, λ, ω, ν, p and E are perfectly definedR (position) and t (time) are not defined.ΨΨ*=A2=constant everywhere; there is no localization.
If E=constant, this is a stationary state, independent of t which is not defined.
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Niels Henrik David Bohr Danish1885-1962
Correspondence principle 1913/1920
For every physical quantity one can define an operator. The definition uses formulae from classical physics replacing quantities involved by the corresponding operators
QM is then built from classical physics in spite of demonstrating its limits
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Operators p and H
We use the expression of the plane wave which allows defining exactly p and E.
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Momentum and Energy Operators
Remember during this chapter
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Stationary state E=constant
Remember for 3 slides after
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Kinetic energy
Classical quantum operator
In 3D :
Calling the laplacian
Pierre Simon, Marquis de Laplace(1749 -1827)
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Correspondence principleangular momentum
Classical expression Quantum expression
lZ= xpy-ypx
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Erwin Rudolf Josef Alexander SchrödingerAustrian
1887 –1961
Without potential E = TWith potential E = T + V
Time-dependent Schrödinger Equation
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Schrödinger Equation for stationary states
Kinetic energyTotal energy
Potential energy
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Schrödinger Equation for stationary states
H is the hamiltonian
Sir William Rowan HamiltonIrish 1805-1865
Half penny bridge in Dublin
Remember
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Chemistry is nothing but an application of Schrödinger Equation (Dirac)
Paul Adrien Dirac 1902 – 1984Dirac’s mother was British and his father was Swiss.
< ΨI Ψ> <Ψ IOI Ψ >
Dirac notations
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Uncertainty principle
the Heisenberg uncertainty principle states that locating a particle in a small region of space makes the momentum of the particle uncertain; and conversely, that measuring the momentum of a particle precisely makes the position uncertain
We already have seen incompatible operators
Werner HeisenbergGerman1901-1976
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It is not surprising to find that quantum mechanics does not predict the position of an electron exactly. Rather, it provides only a probability as to where the electron will be found. We shall illustrate the probability aspect in terms of the system of an electron confined to motion along a line of length L. Quantum mechanical probabilities are expressed in terms of a distribution function.For a plane wave, p is defined and the position is not.With a superposition of plane waves, we introduce an uncertainty on p and we localize. Since, the sum of 2 wavefucntions is neither an eigenfunction for p nor x, we have average values.With a Gaussian function, the localization below is 1/2π
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p and x do not commute and are incompatibleFor a plane wave, p is known and x is not (Ψ*Ψ=A2 everywhere)Let’s superpose two wavesP
this introduces a delocalization for p and may be localize x
At the origin x=0 and at t=0 we want to increase the total amplitude,so the two waves Ψ1 and Ψ2 are taken in phase
At ± ∆x/2 we want to impose them out of phaseThe position is therefore known for x ± ∆x/2 the waves will have wavelengths
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Superposition of two waves
0 1 2 3 4 5-2
-1
0
1
2
a (radians)
Ψ
4.95
enveloppe
∆x/2
∆x/(2x(√2π))
Factor 1/2π a more realistic localization
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Uncertainty principle
Werner HeisenbergGerman1901-1976
A more accurate calculation localizes more(1/2ππππ the width of a gaussian) therefore one gets
x and p or E and t play symmetric roles in the plane wave expression;
Therefore, there are two main uncertainty principles