1.6.

3 Stability of Atoms – Estimation

Additional Material
Estimation:
- Mean radius of the hydrogen atom is a
à The distance r of the electron from the nucleus can be specified with an accuracy of
(due to the fact that the electron must surely be somewhere within the atom)
à The uncertainty of the radial component of the momentum pr becomes

à The uncertainty of the momentum p becomes

- For the mean kinetic energy of the electron applies:

- The potential energy in distance a from the nucleus is:

- For the total energy E = Ekin + Epot the inequality applies:

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 e. g. particles localized in a crystal, atoms of different elements

à All classical systems, such as ideal gases

à Indistinguishability is a quantum mechanical phenomenon (see later in this chapter)

Next step: Determine the distribution function for distinguishable particles

à classical occupation function (classical statistics)
 2.2.2 Density of States

- The number of microstates per energy interval de is represented

by the density of states g(e), which is a continuous function of
energy e :

(see later chapters in which g(e) is calculated,

e. g. electrons in a infinite square well) from Kirkby, A Student Companion

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):

Boltzmann distribution (BD)

classical occupation function

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:

à Represents the average number of particles per unit volume

à Depends on the probability that a particle has an energy e à f(e)
à Depends on the number of states available at that energy à g(e)de

- The total number density ntotal of particles is given by the integral over all frequencies:

- The normalization factor for the BD:

with the partition function Z

- The total internal energy:

 2.2.4 Number Density Distribution - 2
- The number density of particles n(e) with energy between e and e + de is given by:

The occupation function is high at e0, but

no particles occupy this energy because
the density of states equals zero

from Kirkby, A Student Companion

 2.3 Quantum Statistics
- Systems of indistinguishable particles:
• the interparticle separation is in the range of the de Broglie wavelength
• the particles have overlapping wavefunctions
• the particles can not be distinguished by any physical measurement

à Indistinguishability is a quantum phenomenon

à The particles are entangled (correlated)

- Consider an isolated system comprising an open sub-

system with NS particles and energy ES, in thermal
contact with a heat reservoir at energy UR with NR
particles
- Energy + matter can be exchanged
- The total number of particles of the isolated system
is N0 = NR + NS, and the total energy U0 = UR + ES
from Kirkby, A Student Companion
- Open sub-system corresponds to a particle
à grand canonical ensemble
 2.3.1 Quantum Occupation Functions
- The occupations functions – the Fermi-Dirac & Bose-Einstein distribution – for quantum systems
can be derived (not shown), and are given by:

Fermi-Dirac distribution (FD)

Bose-Einstein distribution (BE)

à FD for fermions, such as electrons,..

à BE for bosons, such as photons,…

- 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)

- In the limit and e >> µ both occupations approach the BD

- Link between statistical mechanics & Planck’s law of radiation:

• Independently, Planck found that the energy states are quantized + calculated the density of
states of photons + received the correct BE with µ = 0
 2.3.1 Fermi-Dirac Occupation Function

from Kirkby, A Student Companion

Tà0:
- Fermions fall into the lowest energy levels
- Fermions stack up such that the highest energy particles have an energy µ (Pauli exclusion
principle)
- The highest occupied energy level is called the Fermi energy EF
2.3.1 Bose-Einstein Occupation Function

from Kirkby, A Student Companion

Bosons do not obey the Pauli exclusion principle

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 Atomic or sub-atomic scales (i. e. <10-10 m)

Example 1: Consider an electron in a hydrogen atom:

me = 9.1 10-31 kg ~ 10-30 kg
ve ~ 0.01 c ~ 106 m s-1
pe = me v ~ 10-24 kg m s-1
le = h/ pe ~ 10-34/10-24 ~10-10 m
à Same order of magnitude as the dimensions of an atom
à Quantum mechanical treatment

Example 2: Consider a bouncing ball with momentum p = 10 kg m s-1:

ldB = h/p ~ 10-34/10 ~10-35 m << rball
à Far smaller than the ball’s dimensions (rball ~ 0.1-1 m)
à Classical treatment
 3.1 Postulates of Quantum Mechanics
The concept:
- Quantum mechanics is based on a few postulates which can not be proved or deduced

- The postulates are in good agreement with experiment

à As long as the postulates are not disproved by experiment, they are considered as axioms
(i. e. non-provable, true statements)

There are four postulates:

1. The wavefunction postulate
2. The operator postulate
3. The measurement postulate
4. The time-evolution postulate (see chapter 4)
 3.1 Wavefunction Postulate
• Postulate 1: To any quantum mechanical particle a unique complex wavefunction y(x,t) is
assigned. It defines the state of the particle (energy, momentum, position,..). The probability of
finding a particle between points x and x+dx at time t is given by:

where y*(x,t) is the complex conjugate of y(x,t).

The product y*(x,t)y(x,t) is the probability density function (probability per unit distance)

Note: Wavefunctions are complex functions

à They can not represent anything real by their nature

à They should be regarded as abstract, mathematical tools
 3.1 Operator Postulate
• Postulate 2: To every physical observable, q, there is a mathematical operator, Q, that is used
in conjunction with the wavefunction. The eigenvalue equation for a physical observable q is:

where q is the eigenvalue of Q.

- The observables are measurable quantities in classical physics

- 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

In general, the order of the operations has to be strictly kept

Measurements on quantum mechanical systems are probabilistic, not deterministic

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 TDSE is a complex partial differential wave equation

- The Hamilton operator H is the operator that represents a particle's total energy (kinetic energy +
potential energy)
- The TDSE is the quantum analog to Newton’s equation in classical mechanics

For the derivation + interpretation of the Schrödinger equation see chapter 4

 3.2 Constraints on the Wavefunction
Wavefunction and probability:

- 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

- The wavefunction must be square integrable

- Both y(x,t) and must be a continuous function of x:

à At a boundary x = a, the wavefunction + its derivation on either side must be equal

 3.2 Consequences of Postulate 3
• An operator L with only one eigenvalue l and one eigenfunction y

expectation value = eigenvalue

• 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

• If all cm , except cmo , equal to zero: (expectation value = eigenvalue)

 3.2.1 Example 1: Plane Wave
Consider a wavefunction that has the form of a plane wave (frequency w, wavevector k):

Is this a plausible wavefunction?

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)

What is the meaning and difference?

( 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

(b) y ( x, t ) = sin ( kx - wt ) w = E / ! k = + p / ! and y *y = sin 2 ( kx - wt )

à A wave traveling to the right (positive momentum) + non-constant probability density

(c) y ( x, t ) = sin ( kx ) = eiwt

2i
(
1 i( kx -wt ) i( - kx -wt )
e -e ) y *y = sin 2 ( kx )
à Superposition of wave traveling to the right and to the left: a standing wave + non-constant
probability density

Are the functions (a) and (b) normalizable?

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 !

The time and space derivations have the property:

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 -¥

The energy operator E is called Hamilton operator H