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# 7.

## Emission and Absorption

We have so far discussed primarily stationary atomic photon) has to be conserved. The transition probability
states that are described by a stationary wave function therefore depends on the polarization of the emitted or
Ψn,l,ml ,m s or by the corresponding quantum numbers absorbed electromagnetic radiation.
n, l, m l , m s , which give all angular momenta l, s and In this chapter we will discuss how such transition
j = l + s of single electron atoms and the energies E i probabilities can be calculated from the wave functions
of the states i|, where the index i stands for all four of the states involved in the transition (Sect. 7.1). Also,
quantum numbers. The spatial parts of the wave functi- experimental methods for measuring such transition
ons are obtained by solving the stationary Schrödinger probabilities are presented.
equation and the spin is described by the corresponding The selection rules are then discussed in Sect. 7.2
spin function. and the problem of measuring and calculating lifetimes
For atoms with more than one electron the couplings of emitting atomic states is covered in Sect. 7.3.
of the different angular momenta depends on the coup- For transitions of an electron in an outer shell of the
ling strength between them and only those states are atom the energy difference in (7.1) amounts to a few
realized that obey the Pauli principle, which demands electron volts. The transition frequency then falls into
that the total wave function (including the spin part) the spectral region between the near infrared to the
has to be antisymmetric with regard to the exchange of near ultraviolet (1 eV corresponds to a wavelength λ
two electrons. The wave functions that fulﬁll this de- of 1.234 µm = near infrared, while 3 eV corresponds to
mand can be written as linear combination of Slater λ = 478 nm = blue spectral region). Since these tran-
determinants (see Sect. 6.4). sitions mostly give rise to emission of visible light,
When discussing Bohr’s atomic model we men- the electron in the outer atomic shell is often referred
tioned that atoms can undergo transitions between to the German word “Leucht-Elektron”, which means
different states with energies E i and E k , when a photon “light-emitting electron.”
with energy If an electron in an inner atomic shell is excited
into higher unoccupied states, its excitation energy can
ω = E k − E i (7.1)
be several keV. When it returns to its initial state, ra-
is emitted or absorbed. diation with short wavelengths (X-rays) are emitted.
Experiments show, however, that the absorption or The emission or absorption spectrum corresponding
emission spectrum of an atom does not contain all pos- to transitions of inner shell electrons therefore fall
sible frequencies ω according to (7.1). There must be between the far ultraviolet and X-ray region with wave-
certain “selection rules” that select from all possible lengths between 0.01−50 nm (a wavelength of 0.01 nm
combinations E i and E k only those between which corresponds to an energy of about 120 keV). The gene-
a radiative transition can take place. Furthermore, the ration, absorption and detection of X-rays is discussed
intensity of the spectral lines can vary by many or- in Sect. 7.4.
ders of magnitude, which means that the probability of When measuring the frequency dependence of the
a transition generally depends strongly on the speciﬁc emitted or absorbed radiation intensity I(ω), it turns
combination of the two atomic states in (7.1). out that discrete spectra are found where the intensity
Besides the energy conservation expressed by (7.1) peaks around certain frequencies ωik , which obeys the
also the total angular momentum of the system (atom + 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)