7.
Emission and Absorption
of Electromagnetic Radiation by Atoms
We have so far discussed primarily stationary atomic
states that are described by a stationary wave function
Ψn,l,ml ,m s or by the corresponding quantum numbers
n, l, m l , m s , which give all angular momenta l, s and
j = l + s of single electron atoms and the energies E i
photon) has to be conserved. The transition probability
therefore depends on the polarization of the emitted or
absorbed electromagnetic radiation.
In this chapter we will discuss how such transition
probabilities can be calculated from the wave functions
of the states i|, where the index i stands for all four
quantum numbers. The spatial parts of the wave functi-
ons are obtained by solving the stationary Schrödinger
equation and the spin is described by the corresponding
spin function.
For atoms with more than one electron the couplings
of the different angular momenta depends on the coup-
ling strength between them and only those states are
realized that obey the Pauli principle, which demands
that the total wave function (including the spin part)
has to be antisymmetric with regard to the exchange of
two electrons. The wave functions that fulfill this de-
mand can be written as linear combination of Slater
determinants (see Sect. 6.4).
When discussing Bohr’s atomic model we men-
tioned that atoms can undergo transitions between
different states with energies E i and E k , when a photon
with energy

ω = E k − E i (7.1)
is emitted or absorbed.
Experiments show, however, that the absorption or
emission spectrum of an atom does not contain all pos-
sible frequencies ω according to (7.1). There must be
certain “selection rules” that select from all possible
combinations E i and E k only those between which
a radiative transition can take place. Furthermore, the
intensity of the spectral lines can vary by many or-
ders of magnitude, which means that the probability of
a transition generally depends strongly on the specific
combination of the two atomic states in (7.1).
Besides the energy conservation expressed by (7.1)
also the total angular momentum of the system (atom +
of the states involved in the transition (Sect. 7.1). Also,
experimental methods for measuring such transition
probabilities are presented.
The selection rules are then discussed in Sect. 7.2
and the problem of measuring and calculating lifetimes
of emitting atomic states is covered in Sect. 7.3.
For transitions of an electron in an outer shell of the
atom the energy difference in (7.1) amounts to a few
electron volts. The transition frequency then falls into
the spectral region between the near infrared to the
near ultraviolet (1 eV corresponds to a wavelength λ
of 1.234 µm = near infrared, while 3 eV corresponds to
λ = 478 nm = blue spectral region). Since these tran-
sitions mostly give rise to emission of visible light,
the electron in the outer atomic shell is often referred
to the German word “Leucht-Elektron”, which means
“light-emitting electron.”
If an electron in an inner atomic shell is excited
into higher unoccupied states, its excitation energy can
be several keV. When it returns to its initial state, ra-
diation with short wavelengths (X-rays) are emitted.
The emission or absorption spectrum corresponding
to transitions of inner shell electrons therefore fall
between the far ultraviolet and X-ray region with wave-
lengths between 0.01−50 nm (a wavelength of 0.01 nm
corresponds to an energy of about 120 keV). The gene-
ration, absorption and detection of X-rays is discussed
in Sect. 7.4.
When measuring the frequency dependence of the
emitted or absorbed radiation intensity I(ω), it turns
out that discrete spectra are found where the intensity
peaks around certain frequencies ωik , which obeys the
energy relation (7.1), but also continuous spectra where
242 7. Emission and Absorption of Electromagnetic Radiation by Atoms

the intensity I(ω) is a smooth function of ω. However, the mode of the radiation field is increased by the same
even for discrete spectra, the intensity I(ω) of a spectral amount ∆E = hν.
line is not a delta function, but has an intensity profile The probability per second for the induced emission
with a halfwidth ∆ω, which depends on the lifetime of is analogous to (7.2) given by
the states involved, on the temperature of the atomic dPikind. em
sample and on its pressure. This subject of line profiles = Bik wν (ν) . (7.3)
dt
and line broadening will be treated in Sect. 7.5. The factor Bik is the Einstein coefficient for induced
emission.
An excited atom can also give away its excita-
7.1 Transition Probabilities tion energy spontaneously without an external radiation
field. This process is called spontaneous emission.
In this section we will discuss what a transition proba- Different from the induced emission, the spontaneous
bility means and how it depends on the wave functions photon can be emitted into an arbitrary direction, i.e.,
of the atomic states involved in a specific transition into any one of the modes of the radiation field. The
between these states. Some techniques for measuring probability per second for such a spontaneous emission
transition probabilities are presented. is
sp. em.
dPik
= Aik . (7.4)
7.1.1 Induced and Spontaneous Transitions, dt
Einstein Coefficients The factor Aik is the Einstein coefficient for sponta-
neous emission. It is solely dependent on the wave
If an atom in the state k| with energy E k is brought into functions of the states i| and k| but independent of
an electromagnetic radiation field with spectral energy the radiation field. In Fig. 7.1 all three processes are
density wν (ν) (this is the field energy per unit volume depicted schematically.
and unit frequency interval ∆ν = 1 s−1 ) it can absorb We will now look for relations between the three
a photon hν, which brings the atom into a state with Einstein coefficients.
higher energy E i = E k + hν. Consider Ni atoms in state E i and Nk atoms in
The probability per second for such an absorbing state E k within the unit volume inside a radiation field
transition with spectral energy density w(ν). Under stationary
dPkiabs conditions the number densitiesNi and Nk do not vary
= Bki wν (ν) (7.2) with time, i.e., they are constant. This means that the
dt
absorption rate must be equal to the total emission rate:
is proportional to the spectral energy density wν (ν) =
n(ν)hν of the radiation field (where n(ν) is the number Bki wν (ν)Nk = (Bik wν (ν) + Aik ) Ni . (7.5)
of photons hν per unit volume within the frequency
interval ∆ν = 1 s−1 ). The proportionality factor Bki is
the Einstein coefficient for absorption. Each absorption Ei N(E)
takes one photon from a specific mode of the radiation
field (see Sect. 3.1) and therefore decreases the number h⋅ ν h⋅ ν
of photons in this mode by one. 2 hν
The radiation field can also induce atoms in an ex- Aik Nk
cited state with energy E i to emit a photon with energy
w ν ⋅ Bki w ν ⋅ Bik
hν = E i − E k into a specific mode of the radiation field Ni
and to go into the lower state E k . This process is called
induced (or stimulated) emission. It increases by one Ek
Ek Ei E
the number of photons in this mode from which the in- a) b)
ducing photon came. Since the two photons are in the Fig. 7.1. (a) Absorption, induced emission and spontaneous
same mode, they have identical propagation directions. emission in a two-level system. (b) Thermal population
The energy of the atom is reduced by ∆E and that of distribution N(E)