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À There Is A Stable State of Minimum Energy For The Hydrogen Atom With The Lower Bound - Ry
À There Is A Stable State of Minimum Energy For The Hydrogen Atom With The Lower Bound - Ry
à The electron has the greatest probability of staying at a distance amin where the total energy is
minimal (dE/da = 0)
identical to Bohr radius a0
à There is a stable state of minimum energy for the hydrogen atom with the lower bound
Emin = - Ry*
2.2.1 Distinguishable Particles
- Definition: Distinguishable particles have wavefunctions that do not overlap in space with one
another (i. e. the interparticle distance is much greater than the de Broglie wavelength of the
particle)
à Tells us which quantum states satisfy the boundary conditions of a given system
à Represents the number of states per unit volume
à The function g(e)de depends on the dimensions of the system in question
à Sometimes thought of as a “weight function”
Open questions: - How does the macrostate form from the microstate?
- How are the microstates occupied with particles?
2.2.3 Boltzmann Distribution
Classical Statistics
- Consider an isolated system comprising a closed sub-
system with energy e in thermal contact with a heat
reservoir with energy UR
- Energy can be exchanged
- The particle number is fixed (no exchange of matter)
- The total energy of the isolated system is U0 = UR + e
from Kirkby, A Student Companion
- Closed sub-system corresponds to a particle
à canonical ensemble
- The probability that a particle has an energy between e and e + de can be derived (not shown),
and is given by (A normalization constant):
à Probability distribution that represents the average number of particles per state
à The average number of particles per state decreases exponentially with increasing energy
2.2.4 Number Density Distribution - 1
- The number density of particles n(e) with energy between e and e + de is given by:
- The total number density ntotal of particles is given by the integral over all frequencies:
- The chemical potential µ represents the change in internal energy per particle at constant entropy
+ volume (system specific parameter + does not exist in the particle conserving BD)
Tà0:
- W/o interactions between the bosons, all particles in the system fall into
the ground state Bose-Einstein condensation
- E.g. superfluidity of 4He at temperatures below ~2K
3 Axioms of Quantum Mechanics
Quantum scales:
- Wave-like quantum phenomena are apparent when the de Broglie wavelength ldB of a particle is
comparable to its dimensions or its confinement space
à As long as the postulates are not disproved by experiment, they are considered as axioms
(i. e. non-provable, true statements)
The product y*(x,t)y(x,t) is the probability density function (probability per unit distance)
- The observables of an atomic system are either discrete/ quantized eigenvalues (e.g. energy of a
bound electron) or average values of a probability distribution (e. g electron density)
- A mathematical operator is an object that acts on and modifies another mathematical object (e.g.
differential operator such as the wavevector operator, or the angular frequency operator)
- Example:
Wavevector operator and corresponding eigenvalue equation
3.1 Measurement Postulate
• Postulate 3: The measurement of a physical observable q corresponds to the expectation value
of the corresponding operator, Q:
- For example, the expectation value of a particle’s position is found by the expectation value of x = x
à The most likely outcome of a given variable is given by the expectation value of that variable
à The expectation value is the result of an infinite number of measurements on identical systems
3.1 Time-evolution Postulate
• Postulate 4: The time-evolution of the wavefunction is governed by the Schrödinger equation (TDSE)
with
- The probability that a particle is located between two points, a and b, at a time t is given by:
- The probability of finding the particle somewhere must be one à normalization condition
• An operator L with several eigenvalues l1, l2,..,ln and eigenfunctions y1,y2,..yn with the general
ansatz
• cm2 is the probability that a quantum state m with eigenvalue lm can be occupied
à Infinite plane waves do not represent wavefunctions because they are not normalizable:
à Localized plane waves are normalizable and represent wavefunctions if they satisfy the
boundary conditions at x = a and x = b:
A wave of any shape can be constructed from a linear superposition of plane waves of different
frequencies and amplitudes (the essence of Fourier analysis)
à A plane wave is the building block of all wavefunction, from which waves of other
shapes (e.g. Gaussian-shaped waves) can be constructed
3.2.2 Example 2: Probability Density /
Normalization
Consider the following functions:
( a ) y ( x, t ) = e (
i kx -wt )
(b) y ( x, t ) = sin( kx - wt ) (c) y ( x, t ) = sin( kx)
( a ) y ( x, t ) = e (
i kx -wt )
w = E / ! k = + p / ! and y *y = 1
à A wave traveling to the right (positive momentum) + constant probability density
à Generally not, only if they are confined in a finite space (e.g. potential well, exp. apparatus)
3.2.3 Example 3: Position Operator
Consider the position operator x
- Eigenvalue equation: xˆ Y ( x, t ) = x Y ( x, t )
+¥ +¥
- Expectation value: xˆ = ò Y * ( x, t ) xˆ Y ( x, t )dx = ò Y * ( x, t ) x Y ( x, t )dx
-¥ -¥
Normalize y and calculate <x> and <x2> for the following wavefunctions:
Y ( x, t ) = e (
i kx -wt )
(a)
(b) Y ( x, t ) = sin ( kx - wt )
(c) Y ( x, t ) = sin ( kx )
-l x
(d) Y ( x, t ) = Ae e - iwt with l , w , A positive real
3.2.4 Example 4: Momentum & Energy Operator
Let us consider a wavefunction that has the form of a plane wave
i
- i (wt - kx ) - ( Et - px )
y ( x, t ) = y 0 e = y 0e !
d E d
Y ( x, t ) = -iwY ( x, t ) = -i Y ( x, t ) Þ i! Y = E Y
dt ! dt
d p ! d
Y ( x, t ) = ik Y ( x, t ) = i Y ( x, t ) Þ Y = pY
dx ! i dx
For such waves we can guess the energy operator + momentum operator with the
corresponding expectation values:
d +¥ d +¥ +¥
Hˆ = Eˆ = i! E = ò Y * Eˆ Ydx = ò Y *i! Ydx = ò Y * E Ydx = E
dt -¥ -¥ dt -¥
! d +¥ +¥
* ! d
+¥
pˆ = p = ò Y pˆ Ydx = ò Y
*
Ydx = ò Y * pYdx = p
i dx -¥ -¥ i dx -¥