Some key results for QPM. Microscopic definition of temperature. Distribution of microstates. Microscopic definition of entropy. This applies to an isolated system for which all the microstates are equally probable. Systems in contact with a heat bath. Boltzmann distribution.
Some key results for QPM
Distribution of microstates
Microscopic definition of entropy
This applies to an isolated system for which all the microstates are equally probable
This gives the normalised probability of finding the system in a state with energy Ei when in thermal equilibrium at temperature T.
Calculating thermal averages
Starting from the results
leads to a connection between the Helmholtz Free Energy and the partition function:
It follows that
We have a route for calculating these from Z
Standing wave solutions of the form
so k= (kx,ky,kz) with each component quantised:
Constant energy surface
This gives a cubic mesh with mesh size π/L .
In the case of electromagnetic radiation we have a linear “dispersion relation”, since E = ħω = ħck.
with k= E/ħc and dk= dE/ħc:
Density of single particle states (3d)
Suppose we are dealing with non-relativistic particles where
Since ħk = mv, we can define the number of states that have speeds in the range v to v+dv as:
The probability that an atom has a speed in the range v to v+dv equals the number of states in that range times the Boltzmann probability of having the corresponding energy:
Substituting the result for Z we get:
Velocity distribution for a nitrogen molecule at three temperatures
Quantum Harmonic Oscillator
The mean number of oscillators is:
The mean energy per oscillator is:
(ignoring zero point energy)
This applies to any system that can be regarded as a collection of QHOs, e.g. photons in a cavity (black body radiation), lattice vibrations, etc.
The energy density of EM radiation in a cavity in the frequency range ωtoω+dω is
= 5.6710-8 Wm-2K-4
Debye approx. for lattice vibrations
Molar heat capacity of copper compared to Debye theory
The dispersion surface ωj(k) (where j=1,2,3 labels the branches) is replaced by the simple linear dispersion ω = ck, where c is an average sound velocity.
Debye introduced a cut-off wavevector kD which is chosen so that there are exactly 3N normal modes. The cut-off in frequency is then ωD = ckD,
Systems with variable numbers of particles
The Grand (Gibbs) Distribution
This is the equivalent of the Boltzmann distribution for the situation where the number of particles in the system is not fixed.
Bose Einstein Condensation
To calculate the chemical potential for a Bose gas:
We find that μ→ 0 at a finite temperature. This leads to a macroscopic number of particles in the ground state. These particles cannot contribute to CV or the pressure, since they have zero momentum.
In real BEC systems the condensate forms a macroscopic quantum state that displays superfluidity etc.
We need N/2 k states to accommodate N fermions. The total number of fermions is the integral of the occupancy over all the states:
Ground state energy of the fermi gas
Using our result for the Fermi energy:
we find for the ground state energy:
This is called the degeneracy pressure.
It contributes to the bulk modulus of metals and is the main source of stability of white dwarf and neutron stars.
Heat capacity of fermi gas
Expect <n (ε)> << 1
In the limit where , we may ignore the 1 in the denominator, compared to the exponential. This leads to:
Classical Distribution Function:
We find that for both BE and FD gases the chemical potential becomes large and negative in the high temperature limit. This is the criterion that defines the classical limit.