Consider a system consisting of a single hydrogen atom/ion, which has two possible states: unoccupied (i.e., no electron present) and occupied (i.e., one electron present, in the ground state). Calculate the ratio of the probabilities of these two states, to obtain the Saha equation, already derived in Section 5.6 Treat the electrons as a monotonic ideal gas, for the purpose of determining μ. Neglect the fact that an electron has two independent spin states.

Short Answer

Expert verified

The ratio of probabilities of unoccupied state to occupied state is kTPeνQe-1kT.

Step by step solution

01

Step 1. Formula Gibb's Factor

Formula for Gibb's Factor is given as:

G(s)=e-(ε-μ)kT

G(s)=e-(ε-μ)kT

where, μis chemical potential, εis energy occupied, kis Boltzmann's constant, Tis temperature.

02

Step 2. Ratio of Probabilities

Substitute ε=0andμ=0for unoccupied state.

G(s)=e-(0-0)kT=e0=1

Substitute ε=-1for occupied state.

role="math" localid="1647153963926" G~(s)=e-(-1-μ)kT=e(1+μ)kT

The ratio of probability of unoccupied state to occupied state is:

role="math" localid="1647154152958" G(s)G~(s)=1e(1+μ)kT

03

Step 3. Substitution in chemical potential formula

Formula for chemical potential is given as:

μ=-kT×lnVZinNνQ

Substitute VN=kTPewhere Peis partial pressure of electron gas.

role="math" localid="1647154444368" μ=-kT×lnkTZinPeνQ

For mono atomic gas, substitute Zin=1

-μkT=lnkTPeνQe-μkT=kTPeνQ
04

Step 4. Final calculation

Ratio of probability can be written as,

G(s)G~(s)=1e(1+μ)kT=e-1kT×e-μkT

Substitute e-μkT=kTPeνQin above equation,

role="math" localid="1647155185719" G(s)G~(s)=e-1kT×kTPeνQ=kTPeνQe-1kT

Hence, the ratio of probabilities of unoccupied state to occupied state is kTPeνQe-1kT .

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Most popular questions from this chapter

Consider any two internal states, s1 and s2, of an atom. Let s2 be the higher-energy state, so that Es2-Es1=ϵ for some positive constant. If the atom is currently in state s2, then there is a certain probability per unit time for it to spontaneously decay down to state s1, emitting a photon with energy e. This probability per unit time is called the Einstein A coefficient:

A = probability of spontaneous decay per unit time.

On the other hand, if the atom is currently in state s1 and we shine light on it with frequency f=ϵ/h, then there is a chance that it will absorb photon, jumping into state s2. The probability for this to occur is proportional not only to the amount of time elapsed but also to the intensity of the light, or more precisely, the energy density of the light per unit frequency, u(f). (This is the function which, when integrated over any frequency interval, gives the energy per unit volume within that frequency interval. For our atomic transition, all that matters is the value of u(f)atf=ϵ/h) The probability of absorbing a photon, per unit time per unit intensity, is called the Einstein B coefficient:

B=probability of absorption per unit timeu(f)

Finally, it is also possible for the atom to make a stimulated transition from s2down to s1, again with a probability that is proportional to the intensity of light at frequency f. (Stimulated emission is the fundamental mechanism of the laser: Light Amplification by Stimulated Emission of Radiation.) Thus we define a third coefficient, B, that is analogous to B:

B'=probability of stimulated emission per unit timeu(f)

As Einstein showed in 1917, knowing any one of these three coefficients is as good as knowing them all.

(a) Imagine a collection of many of these atoms, such that N1 of them are in state s1 and N2 are in state s2. Write down a formula for dN1/dt in terms of A, B, B', N1, N2, and u(f).

(b) Einstein's trick is to imagine that these atoms are bathed in thermal radiation, so that u(f) is the Planck spectral function. At equilibrium, N1and N2 should be constant in time, with their ratio given by a simple Boltzmann factor. Show, then, that the coefficients must be related by

B'=BandAB=8πhf3c3

In Problem 7.28you found the density of states and the chemical potential for a two-dimensional Fermi gas. Calculate the heat capacity of this gas in the limit role="math" localid="1650099524353" kTεF· Also show that the heat capacity has the expected behavior when kTεF. Sketch the heat capacity as a function of temperature.

Change variables in equation 7.83 to λ=hc/ϵ and thus derive a formula for the photon spectrum as a function of wavelength. Plot this spectrum, and find a numerical formula for the wavelength where the spectrum peaks, in terms of hc/kT. Explain why the peak does not occur at hc/(2.82kT).

Carry out the Sommerfeld expansion for the energy integral (7.54), to obtain equation 7.67. Then plug in the expansion for μto obtain the final answer, equation 7.68.

Sometimes it is useful to know the free energy of a photon gas.

(a) Calculate the (Helmholtz) free energy directly from the definition

(Express the answer in terms of T' and V.)

(b) Check the formula S=-(F/T)Vfor this system.

(c) Differentiate F with respect to V to obtain the pressure of a photon gas. Check that your result agrees with that of the previous problem.

(d) A more interesting way to calculate F is to apply the formula F=-kTlnZ separately to each mode (that is, each effective oscillator), then sum over all modes. Carry out this calculation, to obtain

F=8πV(kT)4(hc)30x2ln1-e-xdx

Integrate by parts, and check that your answer agrees with part (a).

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