Average Particle Energy in an Ideal Gas

- the total energy of the system is found by summing up (integrating) over all particles
n(ε) at different energies ε

- with the integral

- we find

- note: - the total energy is proportional to temperature T and the number of

particles N
- the energy is independent of the specifics of the particle, e.g. its mass

- average energy per particle

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- characteristic energy per particle at room temperature T = 300 K

The Equipartition Theorem

in thermal equilibrium at temperature T the average energy ε stored in a particle with f

degrees of freedom is

- there are f = 3 independent degrees of freedom for linear motion along the x, y, z
coordinates

- in a diatomic molecule there are additionally f = 2 rotational degrees of freedom along

the two axis perpendicular to the bond axis

- any harmonic oscillator has f = 2 vibrational degrees of freedom

any independent degree of freedom per particle (e.g. position or momentum) that appears
quadratically in the total energy (Hamiltonian) of a system contributes 1/2 k T to its
average energy

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Maxwell-Boltzmann Velocity Distribution

- the velocity distribution of particles in an ideal gas can be found from the energy
distribution

- thus the number of particles with velocity in an interval dv around v is

- plot of Maxwell's velocity distribution

- rms (root-mean-squared) velocity of a molecule with

average energy of 3/2 kT (from equipartition theorem)

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Differences between most probable, average and

rms particle velocity

- rms velocity

- most probable velocity

- average velocity

note: - both the average velocity and the rms velocity are larger than the most
probable velocity

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Variation of Velocity Distribution

- velocity distribution of oxygen (O2) at

two different temperatures

- velocity distribution of hydrogen (H) at

273 K

- increase of velocity with decrease in mass

~ m-1/2 and increase of temperature ~ T1/2

- average velocity:

- example He:

de Broglie wave length

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Statistics of Quantum Particles

- bosons are indistinguishable particles with symmetric wave functions

- bosons can be in the same quantum state

- for bosons the presence of a particle in a certain quantum state increases the probability of
other particles to be found in that state

- their statistics is described by the Bose-Einstein distribution function

- for photons α = 0, generally α depends on the system parameters and is determined from
the normalization condition

- the distribution function is named after the Indian physicist Bose and after Einstein who
extended Bose's original calculation for photons to massive particles

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- fermions are indistinguishable particles with anti symmetric wave functions

- particles with anti symmetric wave function cannot be in the same state

- for fermions the presence of a particle in a certain state prevents any other particles from
being in that state

- their statistics is described by the Fermi-Dirac distribution function

- the Fermi energy is defined by

- the distribution function is named after Enrico Fermi and Paul Dirac who realized that the
exclusion principle would lead to statistics different from that for bosons or classical
particles

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Comparison of the different

distribution functions

- fBE > fMB > fFD at any temperature

- in the large kT limit all distribution

functions approach the Maxwell-
Boltzmann distribution

Fermi-Dirac distribution function in

terms of the Fermi energy εF

- consider the Fermi-Dirac distribution function in the zero temperature limit

- this allows one to draw some important conclusions about the relevance of εF for electrons in
metals

- later we will calculate the energy of free electrons in a metal and also their specific heat

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FD - Distribution function at T = 0

- all states at ε < εF are occupied f = 1

- all states at ε > εF are empty f = 0

- for a systems with N electrons the Fermi energy is determined

by filling up all states string from ε = 0 obeying the exclusion
principle until all states are filled at ε = εF

- as T is increased from zero electrons below the Fermi energy will

fill up states above the Fermi energy

- for temperatures on the order of the Fermi energy the occupation

even at low energies will be reduced and states at higher energies
will be filled
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Blackbody Radiation

- consider a thermal emitter of radiation, called a blackbody, as a cavity at temperature T

filled with photons

- considering the cavity as a box with perfectly reflecting walls, then the radiation inside the
box must be standing electromagnetic waves

- the standing waves must have wavelengths λ the half integer

multiples of which correspond to the cavity length L = j λ/2

- for a cubic cavity of dimension L3 the number j of half integer

wavelengths along each dimension x, y, z is

- for a standing wave in an arbitrary direction

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Counting the Number of Photon Modes in a Cavity

- number of modes g(λ) dλ in the cavity with wavelengths λ in

the interval dλ

- consider a vector j with length

- in the interval dj around j there is a number of combinations of jx, jy, jz that result in the
same absolute value of j and thus the same wave length

- the total number of j states with positive ji is

- as there are two different polarizations for the standing waves

- number of standing waves

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Density of Standing Waves per Volume

- the number of modes per unit volume is found by dividing by the cavity volume L3

- the number of possible modes increases quadratically with frequency and is independent of
the shape of the cavity

- from the classical equipartition theorem we expect every mode in thermal equilibrium at
temperature T to contribute an energy of kT (there are two degrees of freedom per mode that
can be described as a harmonic oscillator) to the total energy

- thus the energy density of the radiation in the cavity is

- this is the Rayleigh-Jeans formula that is accurate only for ν small in comparison to kT

- this energy density diverges (ultraviolet catastrophe) for large ν and thus must be wrong,
this problem could not be resolved with just classical physics

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Planck Radiation Law:

- as photons are bosons the Bose-Einstein distribution function should hold for describing
their statistical properties

- the energy per mode is

- the total energy density of the cavity is then

- this formula is known as the Planck law of

blackbody radiation (we will also discuss Einstein's derivation of this equation)

- it describes the radiation spectrum emitted by any body at a thermal equilibrium

temperature T (e.g. the sun, light bulbs)

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Black Body Spectrum

• fusion (H2 -> He)

• power ~ 100. 109 GW
• temperature
T ~ 6000 Kelvin
• continuous spectrum
• power on earth 1 kW/m2
• largest intensity in visible part
of the spectrum

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Spectrum of the Sun

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Wien's Displacement Law:

- find the wavelength at which the spectral density of the emitted radiation is maximum

- express the Planck law in terms of wave lengths λ

- calculate the derivative

- the result is Wien's displacement law

- shows that the wavelength of maximum radiation emission shifts to lower values as T
increases, e.g. bodies at a few thousand degrees emit visible radiation whereas bodies at room
temperature emit infrared radiation

- example: the sun

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Stefan-Boltzmann Law

- find the total energy density of a black body at temperature T

- with a universal constant a

- note that the total energy depends on the fourth power of temperature

- the energy R radiated by an object per unit time and unit area is also proportional to T4
as stated in the Stefan-Boltzmann law

- with the Stefan constant

- and the emissivity e of the blackbody which can range form 0.07 for polished steel to
0.97 for matte black paint

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