Additional Material: Relativistic Phenomena

Without attempting a systematic treatment of relativistic mechanics, we recollect basic facts:

• The speed of light is the maximal speed of propagation (in any observer frame). In
mechanics, when more energy is used for acceleration, the mass of the body increases
relative to the rest mass m0 𝑚 m0 0 v
m = m(v) = b =
1 - b12 − 𝛽
2
c
• The relativistic momentum of a massive body is still p = mv using the relativistic mass m.
The Newton equation F=dp/dt remains valid
• The total energy of a body is universally E = mc 2
• New is, that for v = 0 the energy of the body remains as E=m0c2 . The energy therefore
contains kinetic energy AND rest mass energy. We can separate E in two contributions:

E =m c =
2 2 4 m 2
0
c =
4
m0
2
( c 2
- v 2
+ v 2
) c4
1- b 2
c -v
2 2

m02 v 2 4
= m c + 2 2 c = m02 c 4 + ( mv ) c 2 = m02 c 4 + p 2 c 2
2
2 4
0 Þ E = m02c 4 + p 2c 2
c -v
• For a massless particle we obtain: p = E
• The kinetic energy T c
of a massive particle is:
T = E - m0c 2 = m02c 4 + p 2c 2 - m0c 2 = m02c 4 + m 2v 2c 2 - m0c 2 v: velocity
p: momentum
æ ö
- 1÷ » m0c 2 æç1 + 12 m2 - 1ö÷ = m0c 2
2 v2 2 v2 v2
c: speed of light
= m0c 2 ç 1 + m2 1 1
» 12 m0v 2 m/ m0 : mass/ rest mass
c2 è c2 ø 2 1- v 2 / c 2 c 2
è m0
ø m0
E: energy
1.4 Heisenberg Uncertainty Principle - 1
• As an example of a wave packet y(x,t) we choose a superposition of plane waves whose
amplitude has a gaussian distribution C(k) around k = k0 (in 1D):

w : frequency
C0, C’ : normalization constant
k0, k : wave vector
a : number
with gaussian amplitude distribution

with normalization constant

• The integration over k is analytically executable and results for t = 0:

with normalization constant

to fulfill the normalization condition

C‘

• For the probability density one then gets:

1.4 Heisenberg Uncertainty Principle - 2
• Probability density of the considered wave packet y(x,t) with gaussian amplitude
distribution C(k) around k = k0 at time t = 0:

w : frequency
C0, C’ : normalization constant
k0, k : wave vector
- For x = 0 the wave packet y(x,0) has its maximum amplitude a : number

- For x1/2 = a/2 the probability density is

à this defines usually the interval Dx as full width of the wave packet

- Analogous for the amplitude distribution: consider

à this defines the interval Dk as full width of the amplitude distribution

The product of spatial width Dx of the wave packet and the width Dk of the
wavenumber interval of the wave forming the wave packet equals one.
Dx Dk = 1
1.4 Heisenberg Uncertainty Principle - 3
Meaning for the qm description of particles:

- Use the de Broglie relation for a particle that moves in x-direction

à
- Use that the gaussian wave packet delivers the minimal product of spatial and
momentum width, thus for all other amplitude distribution applies:
à Heisenberg uncertainty relation

The product of the position uncertainty Dx of a particle (defined as spatial width

of a wave packet) and the momentum uncertainty Dpx of a particle (defined as
the width of the momentum distribution of the wave forming the wave packet) is
always bigger or equal to the reduced Planck’s constant

Annotation: The numerical value for the lower limit for the product depends on the
definition of the position uncertainty Dx and the momentum uncertainty Dpx

• Time-energy uncertainty relation:

à usage: e. g. lifetime estimate from linewidth (see chapter 4.8 SSP)
1.5 Divergence of Wave Packets - 1
- The following relationship exists between group velocity vg and particle momentum p:

- According to the uncertainty principle, the initial momentum p can not be determined more
accurately than p Dp

- This results in an uncertainty Dvg of the group velocity:

with Dx0 the original width of the wave packet

(i.e. position uncertainty of the particle)

- The uncertainty with which one can determine the location of the particle at a later time,
grows linearly with time because of the uncertainty of the particle velocity v

with Dx the width of the wave

packet, which increases with time
 1.5 Divergence of Wave Packets - 2
Remarks:
1. The area under the wave packet
remains the same, because the
normalization condition applies at
any time

2. The increase in width is the

greater, the narrower the original
width Dx0 was

from Demtröder, Experimentalphysik 3

 1.6 Quantum Structure of Atoms
Prehistory:
• An atom consists of a nucleus (charge +Ze; Rn < 10-14m) & an electron shell (charge –Ze;
V ~ 1012 -1015 x Vn)

• Atoms absorb / emit light with certain wavelengths (Kirchhoff & Bunsen 1859)
- Any wavelength that is absorbed can also occur in emission
- The absorption & emission spectrum is characteristic for each atom
- The spectral lines are not arbitrarily sharp à the atoms do not emit severe
monochromatic radiation
• For the hydrogen atom Balmer (1885) discovered an emission spectrum consisting of a series
of lines whose wavelengths lk can be described by the formula:
Rydberg constant
with n1 = 2; n2 = 3,4,5,…

• Lyman (1906) & Paschen (1908) discovered further series of lines (n1 = 1; resp. n1 = 3)

Open questions:
- What is the structure of the electron shell?
- How can the absorption & emission spectrum of atoms be explained?
- …
 1.6.1 Bohr Model
Bohr model*: An electron (mass me, velocity v) moves in a circular path with radius r around the
center S of electron and nucleus (mass mn, charge +Ze)

à System can be described by the movement of a particle of reduced mass

around the center of the Coulomb potential in the nucleus at r = 0

analogous to the planetary model of our solar system

1. Orbit radius r from the condition centripetal force = Coulomb force:

µ : reduced mass
er, : unit vector in radial direction
v : electron velocity
e : elementary charge
Z : nuclear charge number
à ldB : de Broglie wavelength

2. In a stationary state, the matter wave y of the electron corresponds to a standing wave

à Circumference must be an integer multiple of the de Broglie wavelength

* Bohr received in 1922 the Noble price in physics for the atom model
 1.6.1 Bohr Radius
- With the de Broglie wavelength dB
+ the condition
one gets for the electron velocity v: µ : reduced mass
er, : unit vector in radial direction
v : electron velocity
e : elementary charge
Z : nuclear charge number
ldB : de Broglie wavelength
n : natural number

- By inserting v in the formula for the orbital radius r, one gets a limited condition for the possible
radii of the electron:

with Bohr radius

The Bohr radius a0 is the smallest radius of the orbit of

the electron for n = 1 in the hydrogen atom (Z = 1)

à The radii r(n) for the electron orbits are limited to discrete values, i. e. they are quantized
 1.6.1 Orbital Velocity
- With the de Broglie wavelength dB
+ the condition
one gets for the electron velocity v:
µ : reduced mass
er, : unit vector in radial direction
v : electron velocity
e : elementary charge
Z : nuclear charge number
ldB : de Broglie wavelength
n : natural number
c : speed of light

with the quantized radii

+ the fine structure constant

à
 1.6.1 Quantized Energy Levels
- The kinetic energy Ekin of the electron is given by (from Fcentrifugal = FCoulomb):

Ekin equals -1/2 x the potential energy Epot of the

electron in the Coulomb field of the nucleus

- The total energy is given by:

µ : reduced mass
v : electron velocity
e : elementary charge
Z : nuclear charge number
n : natural number

- By using the expression for r, one gets the binding energy En of the electron:

with the Rydberg constant Ry* [Joule]

à The energies E(n) of the electron are limited to discrete values, i. e. they are quantized
à Quantum number n = 1,2,3,.. indicates the number of periods of the standing wave on the
circumference
1.6.2 Summary & Supplement: Bohr Model
- The atom model is semi-classical (classical movement of an electron in the Coulomb field
of the nucleus + an additional quantum condition for the stationary matter wave)
- The electron moves in a circular orbit around the nucleus with quantized radii:

- The electron orbits in the He+ ion with Z = 2 are half as large as in the hydrogen atom
- The negative total energy of the electron in each quantum orbit (defined by n) is given by:

- By absorbing light of the appropriate frequency n with , the atom

transitions to the state of higher energy Ef. Vice versa for the emission

- For the hydrogen atom (Z = 1) the lowest energy (n = 1) is given by:

Open questions:
- Why does the electron not emit energy as an accelerated charge & spirals into the nucleus?
- Why are atoms stable?
 1.6.3 Stability of Atoms
Kinetic (Ekin), potential (Epot) & total energy (E) of an electron in the Coulomb field of the nucleus:

from Demtröder, Experimentalphysik 3

Classical model: QM model:

- The electron emits energy & spirals - By means of the uncertainty relation one can
into the nucleus show that there is a stable state of minimal energy
à instable à For H-atom: the lowest state has the
energy E1 = -Ry* at the Bohr radius a0
 1.6.4 Franck-Hertz Experiment -1

from Demtröder, Experimentalphysik 3

Franck-Hertz experiment*:
- Mercury vapor tube with pressure ~10-2 mbar
- Electrons are emitted (hot cathode K) & accelerated to the
energy eU (lattice G)
- The electron collector (A) hast the voltage UA = U – DU
à electrons are decelerated after the lattice G
à electrons achieve A if their energy is at least eDU

Measurement of the electron current I(U) as a function of the acceleration voltage U at A

* J. Franck & G. Hertz received in 1925 the Noble price in physics for this discovery
 1.6.4 Franck-Hertz Experiment - 2
Observation:
- From 0 V up to 4.9 V the current increases
- Above 5 V the current decreases, goes through a
minimum & increases again up to a maximum at ~9.8 V,...

Interpretation:
- Inelastic collisions between electrons & Hg atoms

- The Hg atoms change into an energetic higher state

with Ea : excitation energy

n : number of inelastic collisions
- Due to the loss of energy such an electron can no longer
reach the collector A à I(U) decreases

from Demtröder, Experimentalphysik 3

à Atoms can only absorb energy in certain energy quanta DE
à The magnitude of DE depends on the structure of the atom
à The excited states decay after a short time (~10-8 s) by emission of a photon into lower states
à Only the lowest energy state (ground state) of an atom is stable
 1.6.5 Classical vs Quantum Physics
Classical physics: The description of the movement of particles is in principle for any time possible
if the acting forces & the initial conditions (r(0), v(0)) are known

Quantum physics: Due to the uncertainty relation is it not possible to calculate the exact time
evolution of a physical system & the initial condition (x, p) can not be specified exactly at the same
time

- Instead of specifying exact paths of individual particles, probability statements occur

- The probability of finding a particle at time t at the position x is given by where

y(x, t) denotes the matter wave (in classical physics this corresponds to the wave intensity)

- The measurement of the quantity x or p changes the state of the particle

- The position uncertainty Dx of a particle corresponds to the de Broglie wavelength dB

- Quantum phenomena occur when looking at the micro-regime of atoms & molecules
(relevant for microparticles such as electrons, protons, …but irrelevant for macroparticles of
large mass)

- Wave- particle model are not contradictory, but complementary descriptions of nature
 1.7 Summary of Chapter 1
- Many experiments point out the particle character of el.-mag. radiation (e. g. black body
radiation, photoelectric effect, Compton effect,…)
- The light quanta hu of the el.-mag. field are called photons ( , m0 = 0)

- The wave character of particles is shown by diffraction and interference experiments (e. g.
Bragg-diffraction, neutron interferometry,…)

- Matter waves show dispersion, i. e. their phase velocity vPh depends on frequency w (vPh > c)

- Particles can be described by wave packets and it applies vg = v

- The probability of finding a particle at time t at the position x in the interval dx is given through
the absolute square of the matter wave

- Position & momentum of a particle can not be measured with any accuracy at the same time
à Heisenberg uncertainty relation

- The uncertainty principle also applies to the simultaneous measurement of energy & time

- Quantization of atomic levels is experimentally confirmed by the Franck-Hertz experiment &

by line spectra in the absorption/ emission of el.-mag. radiation
 2 Statistical Mechanics
Fundamental:
- Statistical mechanics uses a microscopic approach to explain macroscopic properties
- It links together the classical world with the sub-atomic, quantum world of individual particles

Approach:
Consider a statistical ensemble, i. e. collection of macroscopically identically systems (same
values for p, T, V,…, but the microscopic properties, e. g. individual particle energy, velocity differ
from each system)

à This approach allows to determine the probabilistic microscopic properties of a system

(e. g. probability distribution of particle energies)

Side note: Statistical ensembles are mathematical idealizations (theory vs practice)

 2.1.1 Microstates & Macrostates
- The state of a particle is often specified by its energy e
à The state of a statistical ensemble can be characterized by its energy

- One distinguishes between microstate & macrostate

- Microstate: tells us which particle is in which energy level
- Macrostate: tells us the total number of particles in each energy level + the total energy of
the system (may consist of many different microstates)

Example of a possible microstate

& macrostate of a system of four
distinguishable particles

from Kirkby, A
Student Companion

The postulates of statistical mechanics describe the microstates & macrostates of a given system
2.1.2 Postulates of Statistical Mechanics
- Postulate 1: For a macrostate in equilibrium, all microstates corresponding to that
macrostate are equally probable

à If there are W different microstates to a given macrostate, then the probability of finding the
system in any one of those microstates is 1/W

- Postulate 2: The observed macrostate is the one with the most microstates W
à An important measure is the parameter W(e) for a given total energy

- Instead of the number W, often the entropy S of the system is used, and defined by:

à This definition shows that entropy can be thought of as a measure of the number of
ways of arranging quanta of energy between the particles in a system
à Entropy as a measure of “disorder” (analogous to classical thermodynamics)