3 Thermal History

In this chapter, we will describe the first three minutes1 in the history of the universe, starting
from the hot and dense state following inflation. At early times, the thermodynamical proper-
ties of the universe were determined by local equilibrium. However, it are the departures from
thermal equilibrium that make life interesting. As we will see, non-equilibrium dynamics allows
massive particles to acquire cosmological abundances and therefore explains why there is some-
thing rather than nothing. Deviations from equilibrium are also crucial for understanding the
origin of the cosmic microwave background and the formation of the light chemical elements.
We will start, in §3.1, with a schematic description of the basic principles that shape the
thermal history of the universe. This provides an overview of the story that will be fleshed out
in much more detail in the rest of the chapter: in §3.2, will present equilibrium thermodynamics
in an expanding universe, while in 3.3, we will introduce the Boltzmann equation and apply it to
several examples of non-equilibrium physics. We will use units in which Boltzmann’s constant
is set equal to unity, kB ⌘ 1, so that temperature has units of energy.

3.1 The Hot Big Bang

The key to understanding the thermal history of the universe is the comparison between the
rate of interactions and the rate of expansion H. When H, then the time scale of particle
interactions is much smaller than the characteristic expansion time scale:
1 1
tc ⌘ ⌧ tH ⌘ . (3.1.1)
H
Local thermal equilibrium is then reached before the e↵ect of the expansion becomes relevant.
As the universe cools, the rate of interactions typically decreases faster than the expansion rate.
At tc ⇠ tH , the particles decouple from the thermal bath. Di↵erent particle species may have
di↵erent interaction rates and so may decouple at di↵erent times.

3.1.1 Local Thermal Equilibrium

Let us first show that the condition (3.1.1) is satisfied for Standard Model processes at temper-
atures above a few hundred GeV. We write the rate of particle interactions as 2

⌘ n v, (3.1.2)

where n is the number density of particles, is their interaction cross section, and v is the
average velocity of the particles. For T & 100 GeV, all known particles are ultra-relativistic,
1
A wonderful popular account of this part of cosmology is Weinberg’s book The First Three Minutes.
2
For a process of the form 1 + 2 $ 3 + 4, we would write the interaction rate of species 1 as 1 = n2 v, where
n2 is the density of the target species 2 and v is the average relative velocity of 1 and 2. The interaction rate of
species 2 would be 2 = n1 v. We have used the expectation that at high energies n1 ⇠ n2 ⌘ n.

36
37 3. Thermal History

and hence v ⇠ 1. Since particle masses can be ignored in this limit, the only dimensionful scale
is the temperature T . Dimensional analysis then gives n ⇠ T 3 . Interactions are mediated by
gauge bosons, which are massless above the scale of electroweak symmetry breaking. The cross
sections for the strong and electroweak interactions then have a similar dependence, which also
can be estimated using dimensional analysis 3
2
↵2
⇠ ⇠ , (3.1.3)
T2

where ↵ ⌘ gA 2 /4⇡ is the generalized structure constant associated with the gauge boson A. We

find that
↵2
= n v ⇠ T 3 ⇥ 2 = ↵2 T . (3.1.4)
T
p
We wish to compare this to the Hubble rate H ⇠ ⇢/Mpl . The same dimensional argument as
before gives ⇢ ⇠ T 4 and hence
T2
H⇠ 2 . (3.1.5)
Mpl
The ratio of (3.1.4) and (3.1.5) is
↵2 Mpl 1016 GeV
⇠ ⇠ , (3.1.6)
H T T
where we have used ↵ ⇠ 0.01 in the numerical estimate. Below T ⇠ 1016 GeV, but above 100
GeV, the condition (3.1.1) is therefore satisfied.
When particles exchange energy and momentum efficiently, they reach a state of maximum
entropy. It is a standard result of statistical mechanics that the number of particles per unit
volume in phase space—the distribution function—then takes the form 4
1
f (E) = , (3.1.7)
eE/T ±1
where the + sign is for fermions and the sign for bosons. When the temperature drops below
the mass of the particles, T ⌧ m, they become non-relativistic and their distribution function
receives an exponential suppression, f ! e m/T . This means that relativistic particles (‘radia-
tion’) dominate the density and pressure of the primordial plasma. The total energy density is
P R
therefore well approximated by summing over all relativistic particles, ⇢r / i d3 p fi (p)Ei (p).
The result can be written as (see below)
⇡2
⇢r = g? (T )T 4 , (3.1.8)
30
where g? (T ) is the number of relativistic degrees of freedom. Figure 3.1 shows the evolution
of g? (T ) assuming the particle content of the Standard Model. At early times, all particles are
relativistic and g? = 106.75. The value of g? decreases whenever the temperature of the universe
drops below the mass of a particle species and it becomes non-relativistic. Today, only photons
and (maybe) neutrinos are still relativistic and g? = 3.38.
3
Shown in eq. (3.1.3) is the Feynman diagram associated with a 2 ! 2 scattering process mediated by the
p
exchange of a gauge boson. Each vertex contributes a factor of the gauge coupling gA / ↵. The dependence of
the cross section on ↵ follows from squaring the dependence on ↵ derived from the Feynman diagram, i.e. /
p p
( ↵ ⇥ ↵)2 = ↵2 .
4
The precise formula will include the chemical potential (see below).
38 3. Thermal History

Figure 3.1: Evolution of the number of relativistic degrees of freedom assuming the Standard Model.

3.1.2 Decoupling and Freeze-Out

If equilibrium had persisted until today, the universe would be mostly photons. Any massive
particle species would be exponentially suppressed.5 To understand the world around us, it
is therefore crucial to understand the deviations from equilibrium that led to the freeze-out of
massive particles (see Fig. 3.2).

relativistic non-relativistic

freeze-out

relic density

equilibrium

1 10 100

Figure 3.2: A schematic illustration of particle freeze-out. At high temperatures, T m, the particle
abundance tracks its equilibrium value. At low temperatures, T ⌧ m, the particles freeze out and maintain
a density that is much larger than the Boltzmann-suppressed equilibrium abundance.

Below the scale of electroweak symmetry breaking, T . 100 GeV, the gauge bosons of the
weak interactions, W ± and Z, receive masses MW ⇠ MZ . The cross section associated with
5
This isn’t quite correct for baryons. Since baryon number is a symmetry of the Standard Model, the number
density of baryons can remain significant even in equilibrium.
39 3. Thermal History

processes mediated by the weak force becomes

2

⇠ ⇠ G2F T 2 , (3.1.9)

where we have introduced Fermi’s constant,6 GF ⇠ ↵/MW 2 ⇠ 1.17 ⇥ 10 5 GeV 2 . Notice that

the strength of the weak interactions now decreases as the temperature of the universe drops.
We find that ✓ ◆3
↵2 Mpl T 3 T
⇠ 4 ⇠ , (3.1.10)
H MW 1 MeV
which drops below unity at Tdec ⇠ 1 MeV. Particles that interact with the primordial plasma
only through the weak interaction therefore decouple around 1 MeV. This decoupling of weak
scale interactions has important consequences for the thermal history of the universe.

3.1.3 A Brief History of the Universe

Table 3.1 lists the key events in the thermal history of the universe:

• Baryogenesis.⇤ Relativistic quantum field theory requires the existence of anti-particles.

This poses a slight puzzle. Particles and anti-particles annihilate through processes such as
e+ + e ! + . If initially the universe was filled with equal amounts of matter and anti-
matter then we expect these annihilations to lead to a universe dominated by radiation.
However, we do observe an overabundance of matter (mostly baryons) over anti-matter in
the universe today. Models of baryogenesis try to derive the observed baryon-to-photon
ratio
nb
⌘b ⌘ ⇠ 10 9 , (3.1.11)
n
from some dynamical mechanism, i.e. without assuming a primordial matter-antimatter
asymmetry as an initial condition. Although many ideas for baryogenesis exist, none is
singled out by experimental tests. We will not have much to say about baryogenesis in
this course.

• Electroweak phase transition. At 100 GeV particles receive their masses through the
Higgs mechanism. Above we have seen how this leads to a drastic change in the strength
of the weak interaction.

• QCD phase transition. While quarks are asymptotically free (i.e. weakly interacting)
at high energies, below 150 MeV, the strong interactions between the quarks and the
gluons become important. Quarks and gluons then form bound three-quark systems,
called baryons, and quark-antiquark pairs, called mesons. These baryons and mesons are
the relevant degrees of freedom below the scale of the QCD phase transition.

• Dark matter freeze-out. Since dark matter is very weakly interacting with ordinary
matter we expect it to decouple relatively early on. In §3.3.2, we will study the example
of WIMPs—weakly interacting massive particles that freeze out around 1 MeV. We will
show that choosing natural values for the mass of the dark matter particles and their
interaction cross section with ordinary matter reproduces the observed relic dark matter
density surprisingly well.
6 2
The 1/MW comes from the low-momentum limit of the propagator of a massive gauge field.
40 3. Thermal History

Event time t redshift z temperature T

Singularity 0 1 1

43
Quantum gravity ⇠ 10 s – ⇠ 1018 GeV

Inflation & 10 34
s – –

Baryogenesis . 20 ps > 1015 > 100 GeV

EW phase transition 20 ps 1015 100 GeV

QCD phase transition 20 µs 1012 150 MeV

Dark matter freeze-out ? ? ?

Neutrino decoupling 1s 6 ⇥ 109 1 MeV

Electron-positron annihilation 6s 2 ⇥ 109 500 keV

Big Bang nucleosynthesis 3 min 4 ⇥ 108 100 keV

Matter-radiation equality 60 kyr 3400 0.75 eV

Recombination 260–380 kyr 1100–1400 0.26–0.33 eV

Photon decoupling 380 kyr 1100 0.26 eV

Reionization 100–400 Myr 10–30 2.6–7.0 meV

Dark energy-matter equality 9 Gyr 0.4 0.33 meV

Present 13.8 Gyr 0 0.24 meV

Table 3.1: Key events in the thermal history of the universe.

• Neutrino decoupling. Neutrinos only interact with the rest of the primordial plasma
through the weak interaction. The estimate in (3.1.10) therefore applies and neutrinos
decouple at 0.8 MeV.

• Electron-positron annihilation. Electrons and positrons annihilate shortly after neu-

trino decoupling. The energies of the electrons and positrons gets transferred to the
photons, but not the neutrinos. In §3.2.4, we will explain that this is the reason why the
photon temperature today is greater than the neutrino temperature.

• Big Bang nucleosynthesis. Around 3 minutes after the Big Bang, the light elements
were formed. In §3.3.4, we will study this process of Big Bang nucleosynthesis (BBN).

• Recombination. Neutral hydrogen forms through the reaction e +p+ ! H+ when the
temperature has become low enough that the reverse reaction is energetically disfavoured.
We will study recombination in §3.3.3.
41 3. Thermal History

• Photon decoupling. Before recombination the strongest coupling between the photons
and the rest of the plasma is through Thomson scattering, e + ! e + . The sharp drop
in the free electron density after recombination means that this process becomes inefficient
and the photons decouple. They have since streamed freely through the universe and are
today observed as the cosmic microwave background (CMB).
In the rest of this chapter, we will explore in detail where this knowledge about the thermal
history of the universe comes from.

3.2 Equilibrium
3.2.1 Equilibrium Thermodynamics
We have good observational evidence (from the perfect blackbody spectrum of the CMB) that the
early universe was in local thermal equilibrium.7 Moreover, we have seen above that the Standard
Model predicts thermal equilibrium above 100 GeV. To describe this state and the subsequent
evolution of the universe, we need to recall some basic facts of equilibrium thermodynamics,
suitably generalized to apply to an expanding universe.

Microscopic to Macroscopic

Statistical mechanics is the art of turning microscopic laws into an understanding of the macro-
scopic world. I will briefly review this approach for a gas of weakly interacting particles. It is
convenient to describe the system in phase space, where the gas is described by the positions
and momenta of all particles. In quantum mechanics, the momentum eigenstates of a particle
in a volume V = L3 have a discrete spectrum:

The density of states in momentum space {p} then is L3 /h3 = V /h3 , and the state density in
phase space {x, p} is
1
. (3.2.12)
h3
If the particle has g internal degrees of freedom (e.g. spin), then the density of states becomes
g g
3
= , (3.2.13)
h (2⇡)3
7
Strictly speaking, the universe can never truly be in equilibrium since the FRW spacetime doesn’t posses
a time-like Killing vector. But this is physics and not mathematics: if the expansion is slow enough, particles
have enough time to settle close to local equilibrium. (And since the universe is homogeneous, the local values of
thermodynamics quantities are also global values.)
42 3. Thermal History

where in the second equality we have used natural units with ~ = h/(2⇡) ⌘ 1. To obtain the
number density of a gas of particles we need to know how the particles are distributed amongst
the momentum eigenstates. This information is contained in the (phase space) distribution func-
tion f (x, p, t). Because of homogeneity, the distribution function should, in fact, be independent
of the position x. Moreover, isotropy requires that the momentum dependence is only in terms of
the magnitude of the momentum p ⌘ |p|. We will typically leave the time dependence implicit—
it will manifest itself in terms of the temperature dependence of the distribution functions. The
particle density in phase space is then the density of states times the distribution function
g
⇥ f (p) . (3.2.14)
(2⇡)3

The number density of particles (in real space) is found by integrating (3.2.14) over momentum,
Z
g
n = d3 p f (p) . (3.2.15)
(2⇡)3

To obtain the energy density of the gas of particles, we have to weight each momentum eigen-
state by its energy. To a good approximation, the particles in the early universe were weakly
interacting. This allows us to ignore the interaction energies between the particles and write the
energy of a particle of mass m and momentum p simply as
p
E(p) = m2 + p2 . (3.2.16)

Integrating the product of (3.2.16) and (3.2.14) over momentum then gives the energy density
Z
g
⇢ = d3 p f (p)E(p) . (3.2.17)
(2⇡)3

Similarly, we define the pressure as

Z
g p2
P = d3 p f (p) . (3.2.18)
(2⇡)3 3E

Pressure.⇤ —Let me remind you where the p2 /3E factor in (3.2.18) comes from. Consider a small area
element of size dA, with unit normal vector n̂ (see Fig. 3.3). All particles with velocity |v|, striking
this area element in the time interval between t and t + dt, were located at t = 0 in a spherical shell of
radius R = |v|t and width |v|dt. A solid angle d⌦2 of this shell defines the volume dV = R2 |v|dt d⌦2
(see the grey shaded region in Fig. 3.3). Multiplying the phase space density (3.2.14) by dV gives
the number of particles in the volume (per unit volume in momentum space) with energy E(|v|),
g
dN = f (E) ⇥ R2 |v|dt d⌦ . (3.2.19)
(2⇡)3

Not all particles in dV reach the target, only those with velocities directed to the area element.
Taking into account the isotropy of the velocity distribution, we find that the total number of
particles striking the area element dA n̂ with velocity v = |v| v̂ is

|v̂ · n̂| dA g |v · n̂|

dNA = ⇥ dN = f (E) ⇥ dA dt d⌦ , (3.2.20)
4⇡R2 (2⇡)3 4⇡
43 3. Thermal History

where v · n̂ < 0. If these particles are reflected elastically, each transfer momentum 2|p · n̂| to the
target. Hence, the contribution of particles with velocity |v| to the pressure is
Z Z
2|p · n̂| g p2 g p2
dP (|v|) = dNA = 3
f (E) ⇥ cos2 ✓ sin ✓ d✓ d = 3
⇥ f (E) , (3.2.21)
dA dt (2⇡) 2⇡E (2⇡) 3E

where we have used |v| = |p|/E and integrated over the hemisphere defined by v̂ · n̂ ⌘ cos ✓ < 0
(i.e. integrating only over particles moving towards dA—see Fig. 3.3). Integrating over energy E (or
momentum p), we obtain (3.2.18).

Figure 3.3: Pressure in a weakly interacting gas of particles.

Local Thermal Equilibrium

A system of particles is said to be in kinetic equilibrium if the particles exchange energy and
momentum efficiently. This leads to a state of maximum entropy in which the distribution
functions are given by the Fermi-Dirac and Bose-Einstein distributions
1
f (p) = , (3.2.22)
e(E(p) µ)/T ±1
where the + sign is for fermions and the sign for bosons. At low temperatures, T < E µ,
both distribution functions reduce to the Maxwell-Boltzmann distribution
(E(p) µ)/T
f (p) ⇡ e . (3.2.23)
The equilibrium distribution functions have two parameters: the temperature T and the chemical
potential µ. The chemical potential may be temperature-dependent. As the universe expands,
T and µ(T ) change in such a way that the continuity equations for the energy density ⇢ and the
particle number density n are satisfied. Each particle species i (with possibly distinct mi , µi ,
Ti ) has its own distribution function fi and hence its own ni , ⇢i , and Pi .

Chemical potential.⇤ —In thermodynamics, the chemical potential characterizes the response of a
system to a change in particle number. Specifically, it is defined as the derivative of the entropy with
respect to the number of particles, at fixed energy and fixed volume,
✓ ◆
@S
µ= T . (3.2.24)
@N U,V

The change in entropy of a system therefore is

dU + P dV µ dN
dS = , (3.2.25)
T
44 3. Thermal History

where µ dN is sometimes called the chemical work. A knowledge of the chemical potential of reacting
particles can be used to indicate which way a reaction proceeds. The second law of thermodynamics
means that particles flow to the side of the reaction with the lower total chemical potential. Chemical
equilibrium is reached when the sum of the chemical potentials of the reacting particles is equal to
the sum of the chemical potentials of the products. The rates of the forward and reverse reactions
are then equal.

If a species i is in chemical equilibrium, then its chemical potential µi is related to the chemical
potentials µj of the other species it interacts with. For example, if a species 1 interacts with
species 2, 3 and 4 via the reaction 1 + 2 $ 3 + 4, then chemical equilibrium implies

µ1 + µ2 = µ3 + µ4 . (3.2.26)

Since the number of photons is not conserved (e.g. double Compton scattering e + $ e + +
happens in equilibrium at high temperatures), we know that

µ = 0. (3.2.27)

This implies that if the chemical potential of a particle X is µX , then the chemical potential of
the corresponding anti-particle X̄ is
µX̄ = µX , (3.2.28)
To see this, just consider particle-antiparticle annihilation, X + X̄ $ + .
Thermal equilibrium is achieved for species which are both in kinetic and chemical equilibrium.
These species then share a common temperature Ti = T .8

3.2.2 Densities and Pressure

Let us now use the results from the previous section to relate the densities and pressure of a gas
of weakly interacting particles to the temperature of the universe.
At early times, the chemical potentials of all particles are so small that they can be neglected.9
Setting the chemical potential to zero, we get
Z 1
g p2
n = dp ⇥ p ⇤ , (3.2.29)
2⇡ 2 0 exp p2 + m2 /T ± 1
Z 1 p
g p2 p2 + m2
⇢ = dp ⇥p ⇤ . (3.2.30)
2⇡ 2 0 exp p2 + m2 /T ± 1

Defining x ⌘ m/T and ⇠ ⌘ p/T , this can be written as

Z 1
g 3 ⇠2
n = T I ± (x) , I ± (x) ⌘ d⇠ ⇥ p ⇤ , (3.2.31)
2⇡ 2 0 exp ⇠ 2 + x2 ± 1
Z 1 p
g 4 ⇠ 2 ⇠ 2 + x2
⇢ = T J± (x) , J± (x) ⌘ d⇠ ⇥p ⇤ . (3.2.32)
2⇡ 2 0 exp ⇠ 2 + x2 ± 1
8
This temperature is often identified with the photon temperature T — the “temperature of the universe”.
9
For electrons and protons this is a fact (see Problem Set 2), while for neutrinos it is likely true, but not
proven.
45 3. Thermal History

In general, the functions I± (x) and J± (x) have to be evaluated numerically. However, in the
(ultra)relativistic and non-relativistic limits, we can get analytical results.
The following standard integrals will be useful
Z 1
⇠n
d⇠ ⇠ = ⇣(n + 1) (n + 1) , (3.2.33)
0 e 1
Z 1
2
d⇠ ⇠ n e ⇠ = 12 12 (n + 1) , (3.2.34)
0

where ⇣(z) is the Riemann zeta-function.

Relativistic Limit

In the limit x ! 0 (m ⌧ T ), the integral in (3.2.31) reduces to

Z 1
⇠2
I± (0) = d⇠ ⇠ . (3.2.35)
0 e ±1
For bosons, this takes the form of the integral (3.2.33) with n = 2,

I (0) = 2⇣(3) , (3.2.36)

where ⇣(3) ⇡ 1.20205 · · · . To find the corresponding result for fermions, we note that
1 1 2
= ⇠ , (3.2.37)
e⇠ +1 e 1 e2⇠ 1
so that ✓ ◆3
1 3
I+ (0) = I (0) 2⇥ I (0) = I (0) . (3.2.38)
2 4
Hence, we get
(
⇣(3) 1 bosons
n = 2 gT 3 . (3.2.39)
⇡ 3
fermions
4

A similar computation for the energy density gives

(
⇡2 1 bosons
⇢= gT4 . (3.2.40)
30 7
fermions
8

Relic photons.—Using that the temperature of the CMB is T0 = 2.73 K, show that

2⇣(3) 3 3
n ,0 = T ⇡ 410 photons cm , (3.2.41)
⇡2 0
⇡2 4 34 3
⇢ ,0 = T ⇡ 4.6 ⇥ 10 g cm ) ⌦ h2 ⇡ 2.5 ⇥ 10 5
. (3.2.42)
15 0

Finally, from (3.2.18), it is easy to see that we recover the expected pressure-density relation for
a relativistic gas (i.e. ‘radiation’)
1
P = ⇢. (3.2.43)
3
46 3. Thermal History

Exercise.⇤ —For µ = 0, the numbers of particles and anti-particles are equal. To find the “net particle
number” let us restore finite µ in the relativistic limit. For fermions with µ 6= 0 and T m, show
that
Z 1 ✓ ◆
g 2 1 1
n n̄ = dp p
2⇡ 2 0 e(p µ)/T + 1 e(p+µ)/T + 1
 ⇣ ⌘ ⇣ ⌘
1 3 2 µ µ 3
= gT ⇡ + . (3.2.44)
6⇡ 2 T T

Note that this result is exact and not a truncated series.

Non-Relativistic Limit

In the limit x 1 (m T ), the integral (3.2.31) is the same for bosons and fermions
Z 1
⇠2
I± (x) ⇡ d⇠ p 2 2 . (3.2.45)
0 e ⇠ +x
Most of the contribution to the integral comes from ⇠ ⌧ x. We can therefore Taylor expand the
square root in the exponential to lowest order in ⇠,
Z 1 Z 1 Z 1
⇠2 x 2 ⇠ 2 /(2x) 3/2 x 2
I± (x) ⇡ d⇠ x+⇠2 /(2x) = e d⇠ ⇠ e = (2x) e d⇠ ⇠ 2 e ⇠ . (3.2.46)
0 e 0 0
p
The last integral is of the form of the integral (3.2.34) with n = 2. Using ( 32 ) = ⇡/2, we get
r
⇡ 3/2 x
I± (x) = x e , (3.2.47)
2
which leads to
✓ ◆3/2
mT m/T
n=g e . (3.2.48)
2⇡
As expected, massive particles are exponentially rare at low temperatures, T ⌧ m. At lowest
order in the non-relativistic limit, we have E(p) ⇡ m and the energy density is simply equal to
the mass density
⇢ ⇡ mn . (3.2.49)

p
Exercise.—Using E(p) = m2 + p2 ⇡ m + p2 /2m, show that

3
⇢ = mn + nT . (3.2.50)
2

Finally, from (3.2.18), it is easy to show that a non-relativistic gas of particles acts like pres-
sureless dust (i.e. ‘matter’)
P = nT ⌧ ⇢ = mn . (3.2.51)

Exercise.—Derive (3.2.51). Notice that this is nothing but the ideal gas law, P V = N kB T .
47 3. Thermal History

By comparing the relativistic limit (T m) and the non-relativistic limit (T ⌧ m), we see
that the number density, energy density, and pressure of a particle species fall exponentially (are
“Boltzmann suppressed”) as the temperature drops below the mass of the particle. We interpret
this as the annihilation of particles and anti-particles. At higher energies these annihilations
also occur, but they are balanced by particle-antiparticle pair production. At low temperatures,
the thermal particle energies aren’t sufficient for pair production.

Exercise.—Restoring finite µ in the non-relativistic limit, show that

✓ ◆3/2
mT
n = g e (m µ)/T , (3.2.52)
2⇡
✓ ◆3/2 ⇣µ⌘
mT
n n̄ = 2g e m/T sinh . (3.2.53)
2⇡ T

E↵ective Number of Relativistic Species

Let T be the temperature of the photon gas. The total radiation density is the sum over the
energy densities of all relativistic species

X ⇡2
⇢r = ⇢i = g? (T )T 4 , (3.2.54)
30
i

where g? (T ) is the e↵ective number of relativistic degrees of freedom at the temperature T . The
sum over particle species may receive two types of contributions:

• Relativistic species in thermal equilibrium with the photons, Ti = T mi ,

X 7 X
g?th (T ) = gi + gi . (3.2.55)
8
i=b i=f

When the temperature drops below the mass mi of a particle species, it becomes non-
relativistic and is removed from the sum in (3.2.55). Away from mass thresholds, the
thermal contribution is independent of temperature.

• Relativistic species that are not in thermal equilibrium with the photons, Ti 6= T mi ,
X ✓ ◆4 ✓ ◆4
Ti 7 X Ti
g?dec (T ) = gi + gi . (3.2.56)
T 8 T
i=b i=f

We have allowed for the decoupled species to have di↵erent temperatures Ti . This will be
relevant for neutrinos after e+ e annihilation (see §3.2.4).
48 3. Thermal History

Table 3.2: Particle content of the Standard Model.

type mass spin g

1
quarks t, t̄ 173 GeV 2 2 · 2 · 3 = 12
b, b̄ 4 GeV
c, c̄ 1 GeV
s, s̄ 100 MeV
d, s̄ 5 MeV
u, ū 2 MeV

gluons gi 0 1 8 · 2 = 16

1
leptons ⌧± 1777 MeV 2 2·2=4
±
µ 106 MeV
±
e 511 keV
1
⌫⌧ , ⌫¯⌧ < 0.6 eV 2 2·1=2
⌫µ , ⌫¯µ < 0.6 eV
⌫e , ⌫¯e < 0.6 eV

gauge bosons W+ 80 GeV 1 3

W 80 GeV
0
Z 91 GeV
0 2

Higgs boson H0 125 GeV 0 1

Figure 3.4 shows the evolution of g? (T ) assuming the Standard Model particle content (see
Table 3.2). At T & 100 GeV, all particles of the Standard Model are relativistic. Adding up
their internal degrees of freedom we get:10

gb = 28 photons (2), W ± and Z 0 (3 · 3), gluons (8 · 2), and Higgs (1)

gf = 90 quarks (6 · 12), charged leptons (3 · 4), and neutrinos (3 · 2)

and hence
7
g? = gb +
gf = 106.75 . (3.2.57)
8
As the temperature drops, various particle species become non-relativistic and annihilate. To
estimate g? at a temperature T we simply add up the contributions from all relativistic degrees
of freedom (with m ⌧ T ) and discard the rest.
Being the heaviest particles of the Standard Model, the top quarks annihilates first. At
10
Here, we have used that massless spin-1 particles (photons and gluons) have two polarizations, massive spin-1
particles (W ± , Z) have three polarizations and massive spin- 12 particles (e± , µ± , ⌧ ± and quarks) have two spin
states. We assumed that the neutrinos are purely left-handed (i.e. we only counted one helicity state). Also,
remember that fermions have anti-particles.
49 3. Thermal History

T ⇠ 16 mt ⇠ 30 GeV,11 the e↵ective number of relativistic species is reduced to g? = 106.75

7 ± 0
8 ⇥ 12 = 96.25. The Higgs boson and the gauge bosons W , Z annihilate next. This happens
roughly at the same time. At T ⇠ 10 GeV, we have g? = 96.26 (1 + 3 · 3) = 86.25. Next,
the bottom quarks annihilate (g? = 86.25 78 ⇥ 12 = 75.75), followed by the charm quarks
7
and the tau leptons (g? = 75.75 8 ⇥ (12 + 4) = 61.75). Before the strange quarks had
time to annihilate, something else happens: matter undergoes the QCD phase transition. At
T ⇠ 150 MeV, the quarks combine into baryons (protons, neutrons, ...) and mesons (pions, ...).
There are many di↵erent species of baryons and mesons, but all except the pions (⇡ ± , ⇡ 0 ) are
non-relativistic below the temperature of the QCD phase transition. Thus, the only particle
species left in large numbers are the pions, electrons, muons, neutrinos, and the photons. The
three pions (spin-0) correspond to g = 3 · 1 = 3 internal degrees of freedom. We therefore get
g? = 2 + 3 + 78 ⇥ (4 + 4 + 6) = 17.25. Next electrons and positrons annihilate. However, to
understand this process we first need to talk about entropy.

Figure 3.4: Evolution of relativistic degrees of freedom g? (T ) assuming the Standard Model particle content.
The dotted line stands for the number of e↵ective degrees of freedom in entropy g?S (T ).

3.2.3 Conservation of Entropy

To describe the evolution of the universe it is useful to track a conserved quantity. As we will
see, in cosmology entropy is more informative than energy. According to the second law of
thermodynamics, the total entropy of the universe only increases or stays constant. It is easy to
show that the entropy is conserved in equilibrium (see below). Since there are far more photons
than baryons in the universe, the entropy of the universe is dominated by the entropy of the
photon bath (at least as long as the universe is sufficiently uniform). Any entropy production
from non-equilibrium processes is therefore total insignificant relative to the total entropy. To
a good approximation we can therefore treat the expansion of the universe as adiabatic, so that
11
The transition from relativistic to non-relativistic behaviour isn’t instantaneous. About 80% of the particle-
antiparticle annihilations takes place in the interval T = m ! 16 m.
50 3. Thermal History

the total entropy stays constant even beyond equilibrium.

Exercise.—Show that the following holds for particles in equilibrium (which therefore have the cor-
responding distribution functions) and µ = 0:

@P ⇢+P
= . (3.2.58)
@T T

Consider the second law of thermodynamics: T dS = dU + P dV . Using U = ⇢V , we get

1⇣ ⇥ ⇤ ⌘
dS = d (⇢ + P )V V dP
T
1 ⇥ ⇤ V
= d (⇢ + P )V (⇢ + P ) dT
T T2

⇢+P
=d V , (3.2.59)
T

where we have used (3.2.58) in the second line. To show that entropy is conserved in equilibrium,
we consider

dS d ⇢+P
= V
dt dt T
 
V d⇢ 1 dV V dP ⇢ + P dT
= + (⇢ + P ) + . (3.2.60)
T dt V dt T dt T dt

The first term vanishes by the continuity equation, ⇢+3H(⇢+P

˙ ) = 0. (Recall that V / a3 .) The
second term vanishes by (3.2.58). This established the conservation of entropy in equilibrium.
In the following, it will be convenient to work with the entropy density, s ⌘ S/V . From
(3.2.59), we learn that
⇢+P
s= . (3.2.61)
T
Using (3.2.40) and (3.2.51), the total entropy density for a collection of di↵erent particle species is
X ⇢i + Pi 2⇡ 2
s= ⌘ g?S (T )T 3 , (3.2.62)
Ti 45
i

where we have defined the e↵ective number of degrees of freedom in entropy,

th dec
g?S (T ) = g?S (T ) + g?S (T ) . (3.2.63)

th (T ) = g th (T ). However, given that s / T 3 , for

Note that for species in thermal equilibrium g?S ? i i
decoupled species we get
X ✓ ◆3 ✓ ◆3
dec Ti 7 X Ti
g?S (T ) ⌘ gi + gi 6= g?dec (T ) . (3.2.64)
T 8 T
i=b i=f

Hence, g?S is equal to g? only when all the relativistic species are in equilibrium at the same
temperature. In the real universe, this is the case until t ⇡ 1 sec (cf. Fig. 3.4).
51 3. Thermal History

The conservation of entropy has two important consequences:

• It implies that s / a 3 . The number of particles in a comoving volume is therefore

proportional to the number density ni divided by the entropy density
ni
Ni ⌘ . (3.2.65)
s
If particles are neither produced nor destroyed, then ni / a 3 and Ni is constant. This is
case, for example, for the total baryon number after baryogenesis, nB /s ⌘ (nb nb̄ )/s.

• It implies, via eq. (3.2.62), that

1/3
g?S (T ) T 3 a3 = const. , or T / g?S a 1
. (3.2.66)

Away from particle mass thresholds g?S is approximately constant and T / a 1 , as ex-
1/3
pected. The factor of g?S accounts for the fact that whenever a particle species becomes
non-relativistic and disappears, its entropy is transferred to the other relativistic species
still present in the thermal plasma, causing T to decrease slightly less slowly than a 1 .
We will see an example in the next section (cf. Fig. 3.5).
1/3 1
Substituting T / g?S a into the Friedmann equation

1 da ⇣ ⇢r ⌘1/2 ⇡ ⇣ g? ⌘1/2 T 2
H= ' 2 ' , (3.2.67)
a dt 3Mpl 3 10 Mpl

we reproduce the usual result for a radiation dominated universe, a / t1/2 , except that
there is a change in the scaling every time g?S changes. For T / t 1/2 , we can integrate
the Friedmann equation and get the temperature as a function of time
✓ ◆1/2
T 1/4 1sec
' 1.5g? . (3.2.68)
1 MeV t

It is a useful rule of thumb that the temperature of the universe 1 second after the Big
Bang was about 1 MeV, and evolved as t 1/2 before that.

3.2.4 Neutrino Decoupling

Neutrinos are coupled to the thermal bath via weak interaction processes like

⌫e + ⌫¯e $ e+ + e ,
(3.2.69)
e + ⌫¯e $ e + ⌫¯e .

The cross section for these interactions was estimated in (3.1.9), ⇠ G2F T 2 , and hence it was
found that ⇠ G2F T 5 . As the temperature decreases, the interaction rate drops much more
rapidly that the Hubble rate H ⇠ T 2 /Mpl :
✓ ◆3
T
⇠ . (3.2.70)
H 1 MeV

We conclude that neutrinos decouple around 1 MeV. (A more accurate computation gives
Tdec ⇠ 0.8 MeV.) After decoupling, the neutrinos move freely along geodesics and preserve
52 3. Thermal History

to an excellent approximate the relativistic Fermi-Dirac distribution (even after they become
non-relativistic at later times). In §1.2.1, we showed the physical momentum of a particle scales
as p / a 1 . It is therefore convenient to define the time-independent combination q ⌘ ap, so
that the neutrino number density is
Z
3 1
n⌫ / a d3 q . (3.2.71)
exp(q/aT⌫ ) + 1

After decoupling, particle number conservation requires n⌫ / a 3 . This is only consistent with
(3.2.71) if the neutrino temperature evolves as T⌫ / a 1 . As long as the photon temperature12
T scales in the same way, we still have T⌫ = T . However, particle annihilations will cause a
deviation from T / a 1 in the photon temperature.

3.2.5 Electron-Positron Annihilation

Shortly after the neutrinos decouple, the temperature drops below the electron mass and electron-
positron annihilation occurs
e+ + e $ + . (3.2.72)
The energy density and entropy of the electrons and positrons are transferred to the photons,
but not to the decoupled neutrinos. The photons are thus “heated” (the photon temperature
does not decrease as much) relative to the neutrinos (see Fig. 3.5). To quantify this e↵ect,

neutrino decoupling

photon heating

electron-positron
annihilation

Figure 3.5: Thermal history through electron-positron annihilation. Neutrinos are decoupled and their
temperature redshifts simply as T⌫ / a 1 . The energy density of the electron-positron pairs is transferred
1/3
to the photon gas whose temperature therefore redshifts more slowly, T / g?S a 1 .

we consider the change in the e↵ective number of degrees of freedom in entropy. If we neglect
neutrinos and other decoupled species,13 we have
(
th
2 + 78 ⇥ 4 = 11
2 T & me
g?S = . (3.2.73)
2 T < me
12
For the moment we will restore the subscript on the photon temperature to highlight the di↵erence with the
neutrino temperature.
13
Obviously, entropy is separately conserved for the thermal bath and the decoupling species.
53 3. Thermal History

th (aT )3 remains constant, we find that aT increases after electron-

Since, in equilibrium, g?S
positron annihilation, T < me , by a factor (11/4)1/3 , while aT⌫ remains the same. This means
that the temperature of neutrinos is slightly lower than the photon temperature after e+ e
annihilation,
✓ ◆1/3
4
T⌫ = T . (3.2.74)
11
For T ⌧ me , the e↵ective number of relativistic species (in energy density and entropy) there-
fore is
✓ ◆4/3
7 4
g? = 2 + ⇥ 2Ne↵ = 3.36 , (3.2.75)
8 11
✓ ◆
7 4
g?S = 2 + ⇥ 2Ne↵ = 3.94 , (3.2.76)
8 11

where we have introduced the parameter Ne↵ as the e↵ective number of neutrino species in the
universe. If neutrinos decoupling was instantaneous then we have Ne↵ = 3. However, neutrino
decoupling was not quite complete when e+ e annihilation began, so some of the energy and
entropy did leak to the neutrinos. Taking this into account14 raises the e↵ective number of
neutrinos to Ne↵ = 3.046.15 Using this value in (3.2.75) and (3.2.76) explains the final values of
g? (T ) and g?S (T ) in Fig. 3.1.

3.2.6 Cosmic Neutrino Background

The relation (3.2.74) holds until the present. The cosmic neutrino background (C⌫B) there-
fore has a slightly lower temperature, T⌫,0 = 1.95 K = 0.17 meV, than the cosmic microwave
background, T0 = 2.73 K = 0.24 meV. The number density of neutrinos is
3 4
n⌫ = Ne↵ ⇥ n . (3.2.77)
4 11
Using (3.2.41), we see that this corresponds to 112 neutrinos cm 3 per flavour. The present
energy density of neutrinos depends on whether the neutrinos are relativistic or non-relativistic
today. It used to be believe that neutrinos were massless in which case we would have
✓ ◆4/3
7 4
⇢⌫ = Ne↵ ⇢ ) ⌦⌫ h2 ⇡ 1.7 ⇥ 10 5
(m⌫ = 0) . (3.2.78)
8 11

Neutrino oscillation experiments have since shown that neutrinos do have mass. The minimum
P
sum of the neutrino masses is m⌫,i > 60 meV. Massive neutrinos behave as radiation-like
16
particles in the early universe , and as matter-like particles in the late universe (see fig. 3.6).
P
On Problem Set 2, you will show that energy density of massive neutrinos, ⇢⌫ = m⌫,i n⌫,i ,
corresponds to P
2 m⌫,i
⌦⌫ h ⇡ . (3.2.79)
94 eV
14
To get the precise value of Ne↵ one also has to consider the fact that the neutrino spectrum after decoupling
deviates slightly from the Fermi-Dirac distribution. This spectral distortion arises because the energy dependence
of the weak interaction causes neutrinos in the high-energy tail to interact more strongly.
15
The Planck constraint on Ne↵ is 3.36 ± 0.34. This still leaves room for discovering that Ne↵ 6= 3.046, which
is one of the avenues in which cosmology could discover new physics beyond the Standard Model.
16
For m⌫ < 0.2 eV, neutrinos are relativistic at recombination.
54 3. Thermal History

By demanding that neutrinos don’t over close the universe, i.e. ⌦⌫ < 1, one sets a cosmological
P
upper bound on the sum of the neutrino masses, m⌫,i < 15 eV (using h = 0.7). Measurements
P
of tritium -decay, in fact, find that m⌫,i < 6 eV. Moreover, observations of the cosmic
microwave background, galaxy clustering and type Ia supernovae together put an even stronger
P
bound, m⌫,i < 1 eV. This implies that although neutrinos contribute at least 25 times the
energy density of photons, they are still a subdominant component overall, 0.001 < ⌦⌫ < 0.02.

Temperature [K]

photons
Fractional Energy Density

neutrinos

CDM

baryons

Scale Factor

Figure 3.6: Evolution of the fractional energy densities of photons, three neutrino species (one massless and
two massive – 0.05 and 0.01 eV), cold dark matter (CDM), baryons, and a cosmological constant (⇤). Notice
the change in the behaviour of the two massive neutrinos when they become non-relativistic particles.
55 3. Thermal History

3.3 Beyond Equilibrium

The formal tool to describe the evolution beyond equilibrium is the Boltzmann equation. In
this section, we first introduce the Boltzmann equation and then apply it to three important
examples: (i) the production of dark matter; (ii) the formation of the light elements during Big
Bang nucleosynthesis; and (iii) the recombination of electrons and protons into neutral hydrogen.

3.3.1 Boltzmann Equation

In the absence of interactions, the number density of a particle species i evolves as
dni ȧ
+ 3 ni = 0 . (3.3.80)
dt a
This is simply a reflection of the fact that the number of particles in a fixed physical volume (V /
a3 ) is conserved, so that the density dilutes with the expanding volume, ni / a 3 , cf. eq. (1.3.86).
To include the e↵ects of interactions we add a collision term to the r.h.s. of (3.3.80),
1 d(ni a3 )
= Ci [{nj }] . (3.3.81)
a3 dt
This is the Boltzmann equation. The form of the collision term depends on the specific inter-
actions under consideration. Interactions between three or more particles are very unlikely, so
we can limit ourselves to single-particle decays and two-particle scatterings / annihilations. For
concreteness, let us consider the following process
1+2 3+4 , (3.3.82)
i.e. particle 1 can annihilate with particle 2 to produce particles 3 and 4, or the inverse process
can produce 1 and 2. This reaction will capture all processes studied in this chapter. Suppose
we are interested in tracking the number density n1 of species 1. Obviously, the rate of change
in the abundance of species 1 is given by the di↵erence between the rates for producing and
eliminating the species. The Boltzmann equation simply formalises this statement,
1 d(n1 a3 )
= ↵ n 1 n2 + n 3 n4 . (3.3.83)
a3 dt
We understand the r.h.s. as follows: The first term, ↵n1 n2 , describes the destruction of particles
1, while that second term, + n3 n4 . Notice that the first term is proportional to n1 and n2 and
the second term is proportional to n3 and n4 . The parameter ↵ = h vi is the thermally averaged
cross section.17 The second parameter can be related to ↵ by noting that the collision term
has to vanish in (chemical) equilibrium
✓ ◆
n1 n2
= ↵, (3.3.84)
n3 n4 eq
where neq
i are the equilibrium number densities we calculated above. We therefore find
" ✓ ◆ #
1 d(n1 a3 ) n1 n2
= h vi n1 n2 n3 n4 . (3.3.85)
a3 dt n3 n4 eq

17
You will learn in the QFT and Standard Model courses how to compute cross sections for elementary
processes. In this course, we will simply use dimensional analysis to estimate the few cross sections that we will
need. The cross section may depend on the relative velocity v of particles 1 and 2. The angle brackets in ↵ = h vi
denote an average over v.
56 3. Thermal History

It is instructive to write this in terms of the number of particles in a comoving volume, as defined
in (3.2.65), Ni ⌘ ni /s. This gives
" ✓ ◆ #
d ln N1 1 N1 N2 N3 N4
= 1 , (3.3.86)
d ln a H N3 N4 eq N1 N2

where 1 ⌘ n2 h vi. The r.h.s. of (3.3.86) contains a factor describing the interaction efficiency,
1 /H, and a factor characterizing the deviation from equilibrium, [1 · · · ].
For 1 H, the natural state of the system is chemical equilibrium. Imagine that we start
with N1 N1eq (while Ni ⇠ Nieq , i = 2, 3, 4). The r.h.s. of (3.3.86) then is negative, particles
of type 1 are destroyed and N1 is reduced towards the equilibrium value N1eq . Similarly, if
N1 ⌧ N1eq , the r.h.s. of (3.3.86) is positive and N1 is driven towards N1eq . The same conclusion
applies if several species deviate from their equilibrium values. As long as the interaction rates
are large, the system quickly relaxes to a steady state where the r.h.s. of (3.3.86) vanishes and
the particles assume their equilibrium abundances.
When the reaction rate drops below the Hubble scale, 1 < H, the r.h.s. of (3.3.86) gets
suppressed and the comoving density of particles approaches a constant relic density, i.e. N1 =
const. This is illustrated in Fig. 3.2. We will see similar types of evolution when we study the
freeze-out of dark matter particles in the early universe (Fig. 3.7), neutrons in BBN (Fig. 3.9)
and electrons in recombination (Fig. 3.8).

3.3.2 Dark Matter Relics

We start with the slightly speculative topic of dark matter freeze-out. I call this speculative
because it requires us to make some assumptions about the nature of the unknown dark matter
particles. For concreteness, we will focus on the hypothesis that the dark matter is a weakly
interacting massive particle (WIMP).

Freeze-Out

WIMPs were in close contact with the rest of the cosmic plasma at high temperatures, but
then experienced freeze-out at a critical temperature Tf . The purpose of this section is to solve
the Boltzmann equation for such a particle, determining the epoch of freeze-out and its relic
abundance.
To get started we have to assume something about the WIMP interactions in the early uni-
verse. We will imagine that a heavy dark matter particle X and its antiparticle X̄ can annihilate
¯
to produce two light (essentially massless) particles ` and `,

X + X̄ $ ` + `¯ . (3.3.87)

Moreover, we assume that the light particles are tightly coupled to the cosmic plasma,18 so that
throughout they maintain their equilibrium densities, n` = neq` . Finally, we assume that there
is no initial asymmetry between X and X̄, i.e. nX = nX̄ . The Boltzmann equation (3.3.85) for
the evolution of the number of WIMPs in a comoving volume, NX ⌘ nX /s, then is

dNX h i
2 eq 2
= sh vi NX (NX ) , (3.3.88)
dt
18
This would be case case, for instance, if ` and `¯ were electrically charged.
57 3. Thermal History

eq
where NX ⌘ neq
X /s. Since most of the interesting dynamics will take place when the temperature
is of order the particle mass, T ⇠ MX , it is convenient to define a new measure of time,
MX
x⌘ . (3.3.89)
T
To write the Boltzmann equation in terms of x rather than t, we note that
✓ ◆
dx d MX 1 dT
= = x ' Hx , (3.3.90)
dt dt T T dt

where we have assumed that T / a 1 (i.e. g?S ⇡ const. ⌘ g?S (MX )) for the times relevant to
the freeze-out. We assume radiation domination so that H = H(MX )/x2 . Eq. (3.3.88) then
becomes the so-called Riccati equation,

dNX h i
2 eq 2
= NX (NX ) , (3.3.91)
dx x2

where we have defined

2⇡ 2 M 3 h vi
⌘ g?S X . (3.3.92)
45 H(MX )
We will treat as a constant (which in more fundamental theories of WIMPs is usually a good
approximation). Unfortunately, even for constant , there are no analytic solutions to (3.3.91).
Fig. 3.7 shows the result of a numerical solution for two di↵erent values of . As expected,

1 10 100

Figure 3.7: Abundance of dark matter particles as the temperature drops below the mass.

eq
at very high temperatures, x < 1, we have NX ⇡ NX ' 1. However, at low temperatures,
eq
x 1, the equilibrium abundance becomes exponentially suppressed, NX ⇠ e x . Ultimately,
X-particles will become so rare that they will not be able to find each other fast enough to
maintain the equilibrium abundance. Numerically, we find that freeze-out happens at about
xf ⇠ 10. This is when the solution of the Boltzmann equation starts to deviate significantly
from the equilibrium abundance.
1 ⌘ N (x = 1), determines the freeze-out density of dark
The final relic abundance, NX X
matter. Let us estimate its magnitude as a function of . Well after freeze-out, NX will be
58 3. Thermal History

eq eq
much larger than NX (see Fig. 3.7). Thus at late times, we can drop NX from the Boltzmann
equation,
NX 2
dNX
' (x > xf ) . (3.3.93)
dx x2
Integrating from xf , to x = 1, we find

1 1
1 f
= , (3.3.94)
NX NX xf

f f 1 (see Fig. 3.7), so a simple analytic approximation

where NX ⌘ NX (xf ). Typically, NX NX
is
1 xf
NX ' . (3.3.95)

Of course, this still depends on the unknown freeze-out time (or temperature) xf . As we see
from Fig. 3.7, a good order-of-magnitude estimate is xf ⇠ 10. The value of xf isn’t terribly
sensitive to the precise value of , namely xf ( ) / | ln |.

Exercise.—Estimate xf ( ) from (xf ) = H(xf ).

Equation (3.3.95) predicts that the freeze-out abundance NX 1 decreases as the interaction rate

increases. This makes sense intuitively: larger interactions maintain equilibrium longer, deeper
into the Boltzmann-suppressed regime. Since the estimate in (3.3.95) works quite well, we will
use it in the following.

WIMP Miracle⇤

It just remains to relate the freeze-out abundance of dark matter relics to the dark matter
density today:
⇢X,0
⌦X ⌘
⇢crit,0
MX nX,0 MX NX,0 s0 1 s0
= 2 H 2 = 3M 2 H 2 = MX NX 3M 2 H 2 . (3.3.96)
3Mpl 0 pl 0 pl 0

1.
where we have used that the number of WIMPs is conserved after freeze-out, i.e. NX,0 = NX
1 = x / and s ⌘ s(T ), we get
Substituting NX f 0 0

H(MX ) xf g?S (T0 ) T03

⌦X = 2 2 H2 , (3.3.97)
MX h vi g?S (MX ) 3Mpl 0

where we have used (3.3.92) and (3.2.62). Using (3.2.67) for H(MX ), gives
✓ ◆1/2
⇡ xf g? (MX ) g?S (T0 ) T03
⌦X = 3 H2 . (3.3.98)
9 h vi 10 g?S (MX ) Mpl 0

Finally, we substitute the measured values of T0 and H0 and use g?S (T0 ) = 3.91 and g?S (MX ) =
g? (MX ):
⇣ x ⌘ ✓ 10 ◆1/2 10 8 GeV 2
f
⌦X h2 ⇠ 0.1 . (3.3.99)
10 g? (MX ) h vi
59 3. Thermal History

This reproduces the observed dark matter density if

p p
h vi ⇠ 10 4 GeV 1 ⇠ 0.1 GF .

The fact that a thermal relic with a cross section characteristic of the weak interaction gives the
right dark matter abundance is called the WIMP miracle.

3.3.3 Recombination
An important event in the history of the early universe is the formation of the first atoms. At
temperatures above about 1 eV, the universe still consisted of a plasma of free electrons and
nuclei. Photons were tightly coupled to the electrons via Compton scattering, which in turn
strongly interacted with protons via Coulomb scattering. There was very little neutral hydrogen.
When the temperature became low enough, the electrons and nuclei combined to form neutral
atoms (recombination19 ), and the density of free electrons fell sharply. The photon mean free
path grew rapidly and became longer than the horizon distance. The photons decoupled from the
matter and the universe became transparent. Today, these photons are the cosmic microwave
background.

Saha Equilibrium

Let us start at T > 1 eV, when baryons and photons were still in equilibrium through electro-
magnetic reactions such as

e + p+ $ H + . (3.3.100)

Since T < mi , i = {e, p, H}, we have the following equilibrium abundances

✓ ◆3/2 ✓ ◆
mi T µi mi
neq
i = gi exp , (3.3.101)
2⇡ T

where µp + µe = µH (recall that µ = 0). To remove the dependence on the chemical potentials,
we consider the following ratio
✓ ◆ ✓ ◆3/2
nH gH mH 2⇡
= e(mp +me mH )/T
. (3.3.102)
ne np eq ge gp me mp T

In the prefactor, we can use mH ⇡ mp , but in the exponential the small di↵erence between mH
and mp + me is crucial: it is the binding energy of hydrogen

BH ⌘ mp + me mH = 13.6 eV . (3.3.103)

The number of internal degrees of freedom are gp = ge = 2 and gH = 4.20 Since, as far as we
know, the universe isn’t electrically charged, we have ne = np . Eq. (3.3.102) therefore becomes
✓ ◆ ✓ ◆3/2
nH 2⇡
= eBH /T . (3.3.104)
n2e eq me T
19
Don’t ask me why this is called recombination; this is the first time electrons and nuclei combined.
20
The spins of the electron and proton in a hydrogen atom can be aligned or anti-aligned, giving one singlet
state and one triplet state, so gH = 1 + 3 = 4.
60 3. Thermal History

We wish to follow the free electron fraction defined as the ratio

ne
Xe ⌘ , (3.3.105)
nb
where nb is the baryon density. We may write the baryon density as
2⇣(3) 3
nb = ⌘ b n = ⌘ b ⇥ T , (3.3.106)
⇡2
where ⌘b = 5.5 ⇥ 10 10 (⌦b h2 /0.020) is the baryon-to-photon ratio. To simplify the discussion, let
us ignore all nuclei other than protons (over 90% (by number) of the nuclei are protons). The
total baryon number density can then be approximated as nb ⇡ np + nH = ne + nH and hence
1 Xe nH
= nb . (3.3.107)
Xe2 n2e
Substituting (3.3.104) and (3.3.106), we arrive at the so-called Saha equation,
✓ ◆ ✓ ◆3/2
1 Xe 2⇣(3) 2⇡T
= ⌘ eBH /T . (3.3.108)
Xe2 eq ⇡2 me

recombination

decoupling
CMB

Boltzmann
Saha
plasma neutral hydrogen

Figure 3.8: Free electron fraction as a function of redshift.

Fig. 3.8 shows the redshift evolution of the free electron fraction as predicted both by the
Saha approximation (3.3.108) and by a more exact numerical treatment (see below). The Saha
approximation correctly identifies the onset of recombination, but it is clearly insufficient if the
aim is to determine the relic density of electrons after freeze-out.

Hydrogen Recombination

Let us define the recombination temperature Trec as the temperature where21 Xe = 10 1

in (3.3.108), i.e. when 90% of the electrons have combined with protons to form hydrogen.
We find
Trec ⇡ 0.3 eV ' 3600 K . (3.3.109)
21 1
There is nothing deep about the choice Xe (Trec ) = 10 . It is as arbitrary as it looks.
61 3. Thermal History

The reason that Trec ⌧ BH = 13.6 eV is that there are very many photons for each hydrogen
atom, ⌘b ⇠ 10 9 ⌧ 1. Even when T < BH , the high-energy tail of the photon distribution
contains photons with energy E > BH so that they can ionize a hydrogen atom.

Exercise.—Confirm the estimate in (3.3.109).

Using Trec = T0 (1 + zrec ), with T0 = 2.7 K, gives the redshift of recombination,

zrec ⇡ 1320 . (3.3.110)

Since matter-radiation equality is at zeq ' 3500, we conclude that recombination occurred
in the matter-dominated era. Using a(t) = (t/t0 )2/3 , we obtain an estimate for the time of
recombination
t0
trec = ⇠ 290 000 yrs . (3.3.111)
(1 + zrec )3/2

Photon Decoupling

Photons are most strongly coupled to the primordial plasma through their interactions with
electrons

e + $ e + , (3.3.112)

with an interaction rate given by

⇡ ne T , (3.3.113)
where T ⇡ 2 ⇥ 10 3 MeV 2 is the Thomson cross section. Since / ne , the interaction rate
decreases as the density of free electrons drops. Photons and electrons decouple roughly when
the interaction rate becomes smaller than the expansion rate,

(Tdec ) ⇠ H(Tdec ) . (3.3.114)

Writing
2⇣(3) 3
(Tdec ) = nb Xe (Tdec ) T = ⌘b T Xe (Tdec )Tdec , (3.3.115)
⇡2
✓ ◆
p Tdec 3/2
H(Tdec ) = H0 ⌦m . (3.3.116)
T0
we get p
3/2 ⇡ 2 H0 ⌦m
Xe (Tdec )Tdec ⇠ . (3.3.117)
2⇣(3) ⌘ T T 3/2
0
Using the Saha equation for Xe (Tdec ), we find

Tdec ⇠ 0.27 eV . (3.3.118)

Notice that although Tdec isn’t far from Trec , the ionization fraction decreases significantly be-
tween recombination and decoupling, Xe (Trec ) ' 0.1 ! Xe (Tdec ) ' 0.01. This shows that a large
degree of neutrality is necessary for the universe to become transparent to photon propagation.
62 3. Thermal History

Exercise.—Using (3.3.108), confirm the estimate in (3.3.118).

The redshift and time of decoupling are

zdec ⇠ 1100 , (3.3.119)

tdec ⇠ 380 000 yrs . (3.3.120)

After decoupling the photons stream freely. Observations of the cosmic microwave background
today allow us to probe the conditions at last-scattering.

Electron Freeze-Out⇤

In Fig. 3.8, we see that a residual ionisation fraction of electrons freezes out when the interactions
in (3.3.100) become inefficient. To follow the free electron fraction after freeze-out, we need to
solve the Boltzmann equation, just as we did for the dark matter freeze-out.
We apply our non-equilibrium master equation (3.3.85) to the reaction (3.3.100). To a rea-
sonably good approximation the neutral hydrogen tracks its equilibrium abundance throughout,
nH ⇡ neqH . The Boltzmann equation for the electron density can then be written as

1 d(ne a3 ) h i
= h vi n2e (neq
e ) 2
. (3.3.121)
a3 dt
Actually computing the thermally averaged recombination cross section h vi from first principles
is quite involved, but a reasonable approximation turns out to be
✓ ◆1/2
BH
h vi ' T . (3.3.122)
T

Writing ne = nb Xe and using that nb a3 = const., we find

dXe h i
= Xe2 (Xeeq )2 , (3.3.123)
dx x2

where x ⌘ BH /T . We have used the fact that the universe is matter-dominated at recombination
and defined  ✓ ◆
nb h vi 3 ⌦b h
⌘ = 3.9 ⇥ 10 . (3.3.124)
xH x=1 0.03

Exercise.—Derive eq. (3.3.123).

Notice that eq. (3.3.123) is identical to eq. (3.3.91)—the Riccati equation for dark matter freeze-
out. We can therefore immediately write down the electron freeze-out abundance, cf. eq. (3.3.95),
✓ ◆✓ ◆
1 xf 3 xf 0.03
Xe ' = 0.9 ⇥ 10 . (3.3.125)
xrec ⌦b h

Assuming that freeze-out occurs close to the time of recombination, xrec ⇡ 45, we capture the
relic electron abundance pretty well (see Fig. 3.8).
63 3. Thermal History

Exercise.—Using e (Tf ) ⇠ H(Tf ), show that the freeze-out temperature satisfies

p
⇡2 H0 ⌦m
Xe (Tf ) Tf = . (3.3.126)
2⇣(3) ⌘ T T 3/2 B 1/2
0 H

Use the Saha equation to show that Tf ⇠ 0.25 eV and hence xf ⇠ 54.

3.3.4 Big Bang Nucleosynthesis

Let us return to T ⇠ 1 MeV. Photons, electron and positrons are in equilibrium. Neutrinos
are about to decouple. Baryons are non-relativistic and therefore much fewer in number than
the relativistic species. Nevertheless, we now want to study what happened to these trace
amounts of baryonic matter. The total number of nucleons stays constant due to baryon number
conservation. This baryon number can be in the form of protons and neutrons or heavier nuclei.
Weak nuclear reactions may convert neutrons and protons into each other and strong nuclear
reactions may build nuclei from them. In this section, I want to show you how the light elements
hydrogen, helium and lithium were synthesised in the Big Bang. I won’t give a complete account
of all of the complicated details of Big Bang Nucleosynthesis (BBN). Instead, the goal of this
section will be more modest: I want to give you a theoretical understanding of a single number:
the ratio of the density of helium to hydrogen,
nHe 1
⇠ . (3.3.127)
nH 16
Figure 3.9 summarizes the four steps that will lead us from protons and neutrons to helium.
Step 0: Step 2:
Equilibrium Step 1: Neutron Decay Step 3:
Neutron Freeze-Out Helium Fusion
Fractional Abundance

equilibrium

Temperature [MeV]

Figure 3.9: Numerical results for helium production in the early universe.
64 3. Thermal History

Step 0: Equilibrium Abundances

In principle, BBN is a very complicated process involving many coupled Boltzmann equations
to track all the nuclear abundances. In practice, however, two simplifications will make our life
a lot easier:
1. No elements heavier than helium.
Essentially no elements heavier than helium are produced at appreciable levels. So the
only nuclei that we need to track are hydrogen and helium, and their isotopes: deuterium,
tritium, and 3 He.

2. Only neutrons and protons above 0.1 MeV.

Above T ⇡ 0.1 MeV only free protons and neutrons exist, while other light nuclei haven’t
been formed yet. Therefore, we can first solve for the neutron/proton ratio and then use
this abundance as input for the synthesis of deuterium, helium, etc.

Let us demonstrate that we can indeed restrict our attention to neutrons and protons above
0.1 MeV. In order to do this, we compare the equilibrium abundances of the di↵erent nuclei:

• First, we determine the relative abundances of neutrons and protons. In the early universe,
neutrons and protons are coupled by weak interactions, e.g. -decay and inverse -decay
n + ⌫ e $ p+ + e ,
(3.3.128)
n + e+ $ p+ + ⌫¯e .
Let us assume that the chemical potentials of electrons and neutrinos are negligibly small,
so that µn = µp . Using (3.3.101) for neq
i , we then have
✓ ◆ ✓ ◆
nn mn 3/2 (mn mp )/T
= e . (3.3.129)
np eq mp
The small di↵erence between the proton and neutron mass can be ignored in the first
factor, but crucially has to be kept in the exponential. Hence, we find
✓ ◆
nn
= e Q/T , (3.3.130)
np eq
where Q ⌘ mn mp = 1.30 MeV. For T 1 MeV, there are therefore as many neutrons
as protons. However, for T < 1 MeV, the neutron fraction gets smaller. If the weak
interactions would operate efficiently enough to maintain equilibrium indefinitely, then the
neutron abundance would drop to zero. Luckily, in the real world the weak interactions
are not so efficient.

• Next, we consider deuterium (an isotope of hydrogen with one proton and one neutron).
This is produced in the following reaction

n + p+ $ D + . (3.3.131)

Since µ = 0, we have µn +µp = µD . To remove the dependence on the chemical potentials

we consider ✓ ◆ ✓ ◆
nD 3 mD 2⇡ 3/2 (mD mn mp )/T
= e , (3.3.132)
nn np eq 4 mn mp T
65 3. Thermal History

where, as before, we have used (3.3.101) for neq

i (with gD = 3 and gp = gn = 2). In the
prefactor, mD can be set equal to 2mn ⇡ 2mp ⇡ 1.9 GeV, but in the exponential the small
di↵erence between mn + mp and mD is crucial: it is the binding energy of deuterium

BD ⌘ mn + mp mD = 2.22 MeV . (3.3.133)

Therefore, as long as chemical equilibrium holds the deuterium-to-proton ratio is

✓ ◆ ✓ ◆
nD 3 4⇡ 3/2 BD /T
= neq e . (3.3.134)
np eq 4 n mp T
To get an order of magnitude estimate, we approximate the neutron density by the baryon
density and write this in terms of the photon temperature and the baryon-to-photon ratio,
2⇣(3) 3
nn ⇠ nb = ⌘ b n = ⌘ b ⇥ T . (3.3.135)
⇡2
Equation (3.3.134) then becomes
✓ ◆ ✓ ◆
nD T 3/2 BD /T
⇡ ⌘b e . (3.3.136)
np eq mp
The smallness of the baryon-to-photon ratio ⌘b inhibits the production of deuterium until
the temperature drops well beneath the binding energy BD . The temperature has to drop
enough so that eBD /T can compete with ⌘b ⇠ 10 9 . The same applies to all other nuclei.
At temperatures above 0.1 MeV, then, virtually all baryons are in the form of neutrons
and protons. Around this time, deuterium and helium are produced, but the reaction rates
are by now too low to produce any heavier elements.

Step 1: Neutron Freeze-Out

The primordial ratio of neutrons to protons is of particular importance to the outcome of BBN,
since essentially all the neutrons become incorporated into 4 He. As we have seen, weak inter-
actions keep neutrons and protons in equilibrium until T ⇠ MeV. After that, we must solve
the Boltzmann equation (3.3.85) to track the neutron abundance. Since this is a bit involved, I
won’t describe it in detail (but see the box below). Instead, we will estimate the answer a bit
less rigorously.
It is convenient to define the neutron fraction as
nn
Xn ⌘ . (3.3.137)
nn + np
From the equilibrium ratio of neutrons to protons (3.3.130), we then get
e Q/T
Xneq (T ) = . (3.3.138)
1 + e Q/T
Neutrons follows this equilibrium abundance until neutrinos decouple at22 Tf ⇠ Tdec ⇠ 0.8 MeV
(see §3.2.4). At this moment, weak interaction processes such as (3.3.128) e↵ectively shut o↵.
The equilibrium abundance at that time is

Xneq (0.8 MeV) = 0.17 . (3.3.139)

22
If is fortunate that Tf ⇠ Q. This seems to be a coincidence: Q is determined by the strong and electromagnetic
interactions, while the value of Tf is fixed by the weak interaction. Imagine a world in which Tf ⌧ Q!
66 3. Thermal History

We will take this as a rough estimate for the final freeze-out abundance,
1
Xn1 ⇠ Xneq (0.8 MeV) ⇠ . (3.3.140)
6
We have converted the result to a fraction to indicate that this is only an order of magnitude
estimate.

Exact treatment⇤ .—OK, since you asked, I will show you some details of the more exact treatment.
To be clear, this box is definitely not examinable!
Using the Boltzmann equation (3.3.85), with 1 = neutron, 3 = proton, and 2, 4 = leptons (with
n` = neq
` ), we find " #
✓ ◆
1 d(nn a3 ) nn
= n nn np , (3.3.141)
a3 dt np eq

where we have defined the rate for neutron/proton conversion as n ⌘ n` h vi. Substituting (3.3.137)
and (3.3.138), we find
dXn h i
= n Xn (1 Xn )e Q/T . (3.3.142)
dt
Instead of trying to solve this for Xn as a function of time, we introduce a new evolution variable
Q
x⌘ . (3.3.143)
T
We write the l.h.s. of (3.3.142) as

dXn dx dXn x dT dXn dXn

= = = xH , (3.3.144)
dt dt dx T dt dx dx
where in the last equality we used that T / a 1 . During BBN, we have
s r
⇢ ⇡ g ? Q2 1
H= 2 = 3 , with g? = 10.75 . (3.3.145)
3Mpl 10 Mpl x2
| {z }
⌘ H1 ⇡ 1.13 s 1

Eq. (3.3.142) then becomes

dXn n ⇥ x x
⇤
= x e Xn (1 + e ) . (3.3.146)
dx H1
Finally, we need an expression for the neutron-proton conversion rate, n . You can find a sketch of
the required QFT calculation in Dodelson’s book. Here, I just cite the answer

255 12 + 6x + x2
n (x) = · , (3.3.147)
⌧n x5

where ⌧n = 886.7 ± 0.8 sec is the neutron lifetime. One can see that the conversion time n 1 is
comparable to the age of the universe at a temperature of ⇠ 1 MeV. At later times, T / t 1/2 and
3 3/2
n / T / t , so the neutron-proton conversion time n 1 / t3/2 becomes longer than the age of
the universe. Therefore we get freeze-out, i.e. the reaction rates become slow and the neutron/proton
ratio approaches a constant. Indeed, solving eq. (3.3.146) numerically, we find (see Fig. 3.9)

Xn1 ⌘ Xn (x = 1) = 0.15 . (3.3.148)

67 3. Thermal History

Step 2: Neutron Decay

At temperatures below 0.2 MeV (or t & 100 sec) the finite lifetime of the neutron becomes
important. To include neutron decay in our computation we simply multiply the freeze-out
abundance (3.3.148) by an exponential decay factor

1
Xn (t) = Xn1 e t/⌧n
= e t/⌧n
, (3.3.149)
6

where ⌧n = 886.7 ± 0.8 sec.

Step 3: Helium Fusion

At this point, the universe is mostly protons and neutron. Helium cannot form directly because
the density is too low and the time available is too short for reactions involving three or more
incoming nuclei to occur at any appreciable rate. The heavier nuclei therefore have to be built
sequentially from lighter nuclei in two-particle reactions. The first nucleus to form is therefore
deuterium,
n + p+ $ D + . (3.3.150)
Only when deuterium is available can helium be formed,

D + p+ $ 3
He + , (3.3.151)
D + 3 He $ 4
He + p+ . (3.3.152)

Since deuterium is formed directly from neutrons and protons it can follow its equilibrium
abundance as long as enough free neutrons are available. However, since the deuterium binding
energy is rather small, the deuterium abundance becomes large rather late (at T < 100 keV).
So although heavier nuclei have larger binding energies and hence would have larger equilibrium
abundances, they cannot be formed until sufficient deuterium has become available. This is the
deuterium bottleneck. Only when there is enough deuterium, can helium be produced. To get
a rough estimate for the time of nucleosynthesis, we determine the temperature Tnuc when the
deuterium fraction in equilibrium would be of order one, i.e. (nD /np )eq ⇠ 1. Using (3.3.136), I
find
Tnuc ⇠ 0.06 MeV , (3.3.153)
which via (3.2.68) with g? = 3.38 translates into
✓ ◆2
0.1MeV
tnuc = 120 sec ⇠ 330 sec. (3.3.154)
Tnuc

Comment.—From fig. 3.9, we see that a better estimate would be neq

D (Tnuc ) ' 10
3 eq
np (Tnuc ). This
gives Tnuc ' 0.07 MeV and tnuc ' 250 sec. Notice that tnuc ⌧ ⌧n , so eq. (3.3.149) won’t be very
sensitive to the estimate for tnuc .

Substituting tnuc ⇠ 330 sec into (3.3.149), we find

1
Xn (tnuc ) ⇠ . (3.3.155)
8
68 3. Thermal History

Since the binding energy of helium is larger than that of deuterium, the Boltzmann factor
eB/T favours helium over deuterium. Indeed, in Fig. 3.9 we see that helium is produced almost
immediately after deuterium. Virtually all remaining neutrons at t ⇠ tnuc then are processed
into 4 He. Since two neutrons go into one nucleus of 4 He, the final 4 He abundance is equal to
half of the neutron abundance at tnuc , i.e. nHe = 12 nn (tnuc ), or
1
nHe nHe Xn (tnuc ) 1 1
= ' 2 ⇠ Xn (tnuc ) ⇠ , (3.3.156)
nH np 1 Xn (tnuc ) 2 16
as we wished to show. Sometimes, the result is expressed as the mass fraction of helium,

4nHe 1
⇠ . (3.3.157)
nH 4

This prediction is consistent with the observed helium in the universe (see Fig. 3.10).

WMAP
Mass Fraction

4
He

D
Number relative to H

3
He

7
Li
WMAP

Figure 3.10: Theoretical predictions (colored bands) and observational constraints (grey bands).

BBN as a Probe of BSM Physics

We have arrived at a number for the final helium mass fraction, but we should remember that
this number depends on several input parameters:

• g? : the number of relativistic degrees of freedom determines the Hubble parameter during
1/2
the radiation era, H / g? , and hence a↵ects the freeze-out temperature
p 1/6
G2F Tf5 ⇠ GN g? Tf2 ! Tf / g? . (3.3.158)
69 3. Thermal History

Increasing g? increases Tf , which increases the n/p ratio at freeze-out and hence increases
the final helium abundance.

• ⌧n : a large neutron lifetime would reduce the amount of neutron decay after freeze-out
and therefore would increase the final helium abundance.

• Q: a larger mass di↵erence between neutrons and protons would decrease the n/p ratio
at freeze-out and therefore would decrease the final helium abundance.

• ⌘b : the amount of helium increases with increasing ⌘b as nucleosythesis starts earlier for
larger baryon density.

• GN : increasing the strength of gravity would increase the freeze-out temperature, Tf /

1/6
GN , and hence would increase the final helium abundance.
2/3
• GF : increasing the weak force would decrease the freeze-out temperature, Tf / GF ,
and hence would decrease the final helium abundance.

Changing the input, e.g. by new physics beyond the Standard Model (BSM) in the early universe,
would change the predictions of BBN. In this way BBN is a probe of fundamental physics.

Light Element Synthesis⇤

To determine the abundances of other light elements, the coupled Boltzmann equations have to
be solved numerically (see Fig. 3.11 for the result of such a computation). Figure 3.10 shows
that theoretical predictions for the light element abundances as a function of ⌘b (or ⌦b ).23 The
fact that we find reasonably good quantitative agreement with observations is one of the great
triumphs of the Big Bang model.
Time [min]

p
n 4
He
D
3
H
Mass Fraction

3
He
7
Li

7
Be

Figure 3.11: Numerical results for the evolution of light element abundances.

23
The shape of the curves in Fig. 3.11 is relatively easy to understood: The abundance of 4 He increases with
increasing ⌘b as nucleosythesis starts earlier for larger baryon density. D and 3 He are burnt by fusion, thus their
abundances decrease as ⌘b increases. Finally, 7 Li is destroyed by protons at low ⌘b with an efficiency that increases
with ⌘b . On the other hand, its precursor 7 Be is produced more efficiently as ⌘b increases. This explains the
valley in the curve for 7 Li.