X-Ray Spectroscopy, Theory

Prasad A Naik, Centre for Advanced Technology, Indore, India

& 1999 Elsevier Ltd. All rights reserved.

This article is reproduced from the previous edition, volume 3,

pp 2487–2498, & 1999, Elsevier Ltd.

standard relation E (keV) ¼ 12.4/l (Å). In terms of energy,

Symbols the X-ray region is roughly between 125 eV and 125 keV.
E photon energy Being electromagnetic radiation, X-rays can be reflected,
gf Gaunt factor refracted, scattered, absorbed, polarized, etc. They also
I intensity show interference and diffraction effects.
I beam current There are several sources of X-rays such as a Coolidge
k Sommerfeld quantum number tube, vacuum sparks, hot-dense fusion plasmas, syn-
K deflection parameter chrotron, pinch devices, muonic atoms, beam-foil inter-
L length of magnetic structure action, stellar X-ray emitters, solar flares, etc. The X-rays
M *,m* reduced mass of muon and electron originating from all these sources can be broadly cate-
n total quantum number gorized into three main types: (1) atomic inner shell
N number of magnetic periods transitions, (2) emission by free electrons, (3) X-rays from
Ne electron density few electron systems. The basic spectroscopic aspects of
Ni ion density the various types of X-rays are discussed in this article.
P total power
r radius of Bohr orbit
R radius of electron trajectory X-Rays from Inner Shell Transitions
R Rydberg constant in Atoms
S power
Te electron temperature X-rays are produced when an electron in an outer shell of
V voltage an atom jumps to an inner shell to fill an electron vacancy.
W work function The difference in energy is emitted as an X-ray photon.
z ion charge The vacancy giving rise to such a transition can be pro-
Z atomic number duced by an energetic photon, bombardment of charged
Dx bandwidth particles (e, p, ay), or by nuclear processes such as
a fine structure constant internal conversion, K-capture, etc. If a charged particle
vn ionization potential collision or a nuclear process produces the vacancy, the
e efficiency resulting X-ray emission is called primary. If the vacancy is
c relativistic factor ¼ E/m0c2 produced by an X-ray photon, the subsequent emission is
k wavelength called secondary or fluorescence radiation.
m frequency In all these cases the singly ionized atom lowers its
h cone angle energy by emission of a photon of definite wavelength
r, s screening constants which is characteristic of the emitting atom. Hence, these
x fluorescence yield X-rays are also called characteristic X-rays.
xc electron cyclotron frequency
xp plasma frequency Characteristic X-Rays
The most energetic X-ray emission comes when a vacancy
in a K shell (n ¼ 1) is filled by an outer electron. Removal of
X-ray is the region of the electromagnetic spectrum lying a 1s electron from a neutral atom raises it to the highest
between gamma rays and extreme ultraviolet (XUV/EUV) energy state represented by 1s1s1 or 1 2S1/2 or KI. Removal
corresponding to a wavelength range of about 0.1 to 100 Å. of a 2s electron (2s2s1) gives rise to L1 state (2 2S1/2).
The radiation on the lower end of the XUV region, up to Removal of a 2p electron from a filled 2p shell (2p 5p1)
about 300 Å, is also sometimes referred to as X-ray. On the gives rise to LII(2 2p1/2) and LIII(2 2P3/2) states, respectively.
lower wavelength side, radiation of shorter wavelengths is Similarly, removal of a 3s, 3p, 3d electron from filled shells
termed X-ray if it is nonnuclear in origin. The wavelength gives rise to (3s3s1, 3p53p1, 3d 93d1) MI(3 2S1/2), MII
of the radiation is related to the photon energy by the (3 2P1/2), MIII(3 2P3/2), MIV(3 2D3/2), MV(3 2D5/2) states.

3010
 X-Ray Spectroscopy, Theory 3011

Table 1 Siegbahn notation for various inner shell X-ray transitions

Final level Initial level

Shell Optical X-ray

structure n l i notation notation K series L series M series
1 2
1s 1s 1 0 1/2 S1/2 KI

KI –: Forbidden by selection rules

2s 2s1 2 0 1/2 2
S1/2 LI – [ ]: Forbidden but observed
2p5 2p1 2 1 1/2 2
P1/2 LII a2 |: Allowed by selection rules but no name given
2p5 2p1 2 1 3/2 2
P3/2 LIII a1

LI LII LIII
1 2
3s 3s 3 0 1/2 S1/2 MI – – Z I
3p5 3p1 3 1 1/2 2
P1/2 MII b3 b4 – –
3p5 3p1 3 1 3/2 2
P3/2 MIII b1 b3 – –
3d9 3d1 3 2 3/2 2
D3/2 MIV [b5] [b10] b1 a2
3d9 3d1 3 2 5/2 2
D5/2 MV [b5] [b9] – a1

MI MII MIII MIV MI

4s 4s 1
4 0 1/2 2
S1/2 NI – – g5 b6 – | | – –
4p5 4p1 4 1 1/2 2
P1/2 NII b2(g2) g2 – – | – – x2 –
4p5 4p1 4 1 3/2 2
P3/2 NIII b2(g1) g3 – – | – – | x1
4d9 4d1 4 2 3/2 2
D3/2 NIV [b4] g1 b15 – | g2 – –
4d9 4d1 4 2 5/2 2
D5/2 NV [b4] – – b2 – – g1 – –
4f13 4f1 4 3 5/2 2
F5/2 NVI – – – – – – – b1 a2
4f13 4f1 4 3 7/2 2
F7/2 NVII – – – – – – – – a1

5s 5s1 5 0 1/2 2
S1/2 OI – g8 b7 – | | – –
5p5 5p1 5 1 1/2 2
P1/2 OII d2 g4 – – | – – | –
5p5 5p1 5 1 3/2 2
P3/2 OIII d1 g4 – – | – – | |
5d9 5d1 5 2 3/2 2
D3/2 OIV – – g6 b5 – | | – –
5d9 5d1 5 2 5/2 2
D5/2 OV – – b5 – – e – –

The selection rules applicable to optical dipole tran- formula, where s and s are screening constants. The energy
sitions also apply to X-ray transitions. The rules are of a level is given by the modified Sommerfeld formula as
DL ¼ 71, Dj ¼ 0,71. Intensity rules are also the same as
those applicable to optical transitions. The transitions T ¼ RðZ  sÞ 2 =n 2 þ Ra 2 ðZ  sÞ 4
obeying selection rules are called normal transitions. Not
ðn=k  3=4Þ=n 4 þ Oða 4 ; a 6 ; yÞ
all transitions allowed by selection rules are observed. On
the contrary, some transitions, which are not allowed by
selection rules, are sometimes observed. These are called where a is the fine structure constant, n is the total (prin-
forbidden transitions. The observed lines were initially cipal) quantum number, and k is the Sommerfeld original
given names as per their observed line intensities. The azimuthal quantum number; k ¼ 1, 2 and 3 for s, p and d
Siegbahn notation used to name various observed lines is electrons, respectively.
given in Table 1. As this nomenclature is intensity-based A pair of terms having the same n, s, L but different j
(e.g. Ka1 more intense than Ka2) and was adopted long (in the 2sþ1Lj Russel–Saunders notation) is called a spin-
before the origin of the lines was explained spectro- relativity doublet (earlier called a regular doublet).
scopically, this notation is somewhat confusing. LII  LIII, MII  MIII, MIV  MV are examples of such
Moseley’s law gives the frequency of line transition as doublets. The screening constant s (same for a doublet)
n(cm1) ¼ KR(Z  d)2, where R is the Rydberg constant, depends on s, p, d sub-levels but s is the same for a spin-
and Z is the atomic number. For example, for Ka: d ¼ 1 relativity doublet, almost independent of Z (s values:
and K ¼ 3/4, which gives n(cm1) ¼ (3/4)R(Z  1)2. LI: 2.0, LII–LIII: 3.5, MI: 6.8, MII–MIII: 8.5, MIV–MV: 13).
Similarly, for Lb1, n(cm1) ¼ (1/22  1/32) R(Z  7.4)2. A pair of terms having the same n, s and j but different
The energy levels formed by single electron removal are L values is called as screening doublet (or irregular
similar to those of a hydrogen-like atom, obtained by doublet). LI–LII, MI–MII, MIII–MIV are examples of such
replacing Z by (Z  s) and (Z  s) in the Sommerfeld screening doublets.
3012 X-Ray Spectroscopy, Theory

From the first term of the Sommerfeld formula, one is much smaller than that of a single vacancy, the intensity
obtains the screening doublet law, which states that the of satellite lines is much less than that of normal lines.
difference between the square roots of the term values of Satellite lines are denoted as a0 , a00 , a000 where the
a given doublet is constant, i.e. independent of Z. This higher number of primes implies lower intensity. If K–M
term also gives the irregular doublet law which states that (i.e. KI–MII, MIII) denotes a Kb transition, then KL–LM
the difference between term values of an irregular denotes the satellite line Kb000 which is due to an additional
(screening) doublet is a linear function of Z. vacancy in the L shell (Figure 1).
The second term of the Sommerfeld formula gives the
separation in energy for a spin-relativity doublet as pro- Hypersatellite lines
portional to the fourth power of the screened atomic This is a special case of satellite lines wherein X-rays
number, i.e. (Z  s)4. This is referred to as the regular originate from atoms with two holes in the same inner
doublet law. For example, for the LII–LIII doublet (same s), shell. A K-hypersatellite line appears when an atom has
Dn(cm1) ¼ (Ra2/16)(Z  3.5)4. initially two vacancies in its K shell. They are denoted by
superscript H. For example, KH a1,2 is a hypersatellite of
the Ka1,2 line (Figure 2). Due to the strong reduction of
Satellite Lines screening, there is a large energy difference between a
These are weaker lines appearing on the shorter wave- normal line and its hypersatellite. Hypersatellites are
length side of the normal (characteristic) lines. They were more easily observed in heavy ion collision spectra or
initially referred to as nondiagram lines because unlike the radioactive decay by K-electron capture.
normal lines, these lines did not fit conveniently in the
energy level diagrams of that time. Later, it was realized Plasma satellites
that the energies can also be predicted using energy level These are low intensity structures, which can appear on
diagrams of multiply charged ions (Figure 1). either side of a parent line. They are equally spaced and
The satellite lines are due to additional electron vacancy correspond to an energy difference of (h/2p)op, where
in a doubly ionized atom. Due to the absence of a second op is the plasma frequency given by o2p ¼ (Nee2/e0m)
electron, the energy levels shift to the higher energy side where Ne is the electron density in the conduction band
(relative to those of a singly ionized atom) due to reduced of the solid target material.
Coulomb screening. As a result, single electron transitions If an X-ray photon loses its energy in exciting a plasmon,
in such atoms (doubly ionized) are at a slightly higher one obtains a low energy plasmon satellite. On the other
energy compared to those in singly ionized atoms. As the hand, if plasmons already exist in the solid at the time of
probability of creation of two electron vacancies in an atom X-ray emission, they can lead to high energy satellites.

Figure 1 Energy diagrams for a Kb transition and Kb000 satellite transition. A() denotes the state of an atom. For example, A(MþL*)
denotes an atomic level where an M shell electron has been removed and an L shell electron is in an outer bound (excited) state. The
energy difference EKL  EK is more than EML  EM as more energy is required to remove an L shell electron in the presence of a K shell
vacancy than in the presence of an M shell vacancy. Solid downward arrows show vacancy transitions, and dashed lines with double
arrows show radiative transitions.
 X-Ray Spectroscopy, Theory 3013

Figure 2 Energy diagram for KH

a1,2 hypersatellite transition.

Auger and Allied Processes with a maximum energy hn ¼ EAuger , corresponding to zero
kinetic energy of the ejected electron (Figure 3b).
These processes compete with the radiative process in
de-excitation of the atom. Thus they influence the
energy-width of X-ray lines. Moreover, they transfer a Semi-Auger process
vacancy from one level to another and thereby affect the If, in the above radiative Auger process, the electron,
intensity of X-ray lines. Many of these processes also lead instead of being ejected out of the atom, is transferred to
to double ionization which (as discussed earlier) gives some outer bound state, then the energy of the emitted
rise to satellite lines. Some of these processes are briefly X-ray photon would be discrete having the value
described below. (EK  EL)  Eb. Here, Eb is the difference in energy
between the outer bound state and the energy level of the
electron in an atom with an L shell vacancy (Figure 3c).
Auger ionization This process is referred to as a semi-Auger process.
In this case, an inner shell vacancy is filled by an electron
from an outer shell and the excess energy, instead of being Coster–Kronig process
emitted as a photon, is consumed in ejecting a second This is a special case of Auger ionization in which the
electron (called an Auger electron) from the atom. This is vacancy transition is between two levels with the same
a radiationless process leading to double ionization. principal quantum number (i.e. within the same shell;
A transition of an electron from an L shell to a K shell Dn ¼ 0) and an electron from some outer shell (different n)
vacancy, accompanied by the ejection of an L shell elec- is ejected (e.g. LLM transition: see Figure 4).
tron, is represented as a KLL transition. The energy of the
ejected electron in a KLL transition is EAuger ¼ EK  ELL. Super Coster–Kronig process
Here EK is the energy of the atom with one electron This is an Auger transition wherein not only the vacancy
missing in the K shell and ELL is the energy of the level transition is within the same shell (Dn ¼ 0 as in a CK
formed by ejection of an L shell electron from a singly transition), but the electron is ejected from the same shell
ionized atom with an L shell electron vacancy (Figure 3a). (e.g. MMM transition: see Figure 5).

Radiative Auger process Autoionization

In this process, the Auger electron, instead of carrying away This process is similar to Auger ionization. In this case a
all the energy, receives only a part of it and the rest is emitted vacancy is created by promoting an inner shell electron
as an X-ray photon. The energy of the photon is given by to an outer bound level, instead of being ejected from the
hn ¼ EAuger  Ekin where EAuger is the energy of the electron atom. When this vacancy is filled by an outer shell
in the Auger transition involving the same three levels (e.g. electron, if the difference in energy exceeds the ioniza-
KLL), and Ekin is the kinetic energy of the ejected electron. tion potential of any electron, then that electron is
The energy spectrum of the emitted X-rays is continuous, ejected leading to a singly ionized atom (Figure 6).
3014 X-Ray Spectroscopy, Theory

Figure 3 Energy diagrams for: (a) Auger transition, (b) radiative Auger transition, and (c) semi-Auger transition.

Figure 4 Energy diagram for LLM Coster–Kronig transition.

Figure 5 Energy diagram for MMM super Coster–Kronig transition.

 X-Ray Spectroscopy, Theory 3015

Figure 6 Energy diagram for autoionization. An L shell electron is excited to an outer nl shell. Subsequently, an M shell electron fills
up the L shell vacancy. In case A, the excited electron in the nl shell leaves the atom, and in case B, another M shell electron leaves the
atom while the nl shell electron remains a spectator electron.

The differences between autoionization and Auger the square of the acceleration. Electrons, due to their
ionization are as follows: (a) Autoionization results from smaller mass, undergo higher acceleration for a given force
an electron vacancy produced by the excitation of a core and hence emit more intense radiation. The spectrum of
electron to an outer bound level, whereas Auger ioniza- the emitted radiation called Bremsstrahlung (braking
tion results from an electron vacancy created by ejecting radiation) depends on the nature and magnitude of the
a core electron from an atom. (b) Autoionization takes acceleration. We discuss here three main sources of X-ray
place in a neutral atom leading to a singly ionized atom, based on electron acceleration (deceleration), namely (i)
whereas Auger ionization takes place in a singly ionized X-ray tubes (linear acceleration, monoenergetic electrons),
atom leading to a doubly ionized atom. (ii) hot plasma sources (linear acceleration, Maxwellian
There is a quite high probability (at least for K shell distribution of energy) and (iii) synchrotron sources
ionization) of the order of 20%, that the first ionization (transverse acceleration). The X-ray spectra from these
producing the initial vacancy is simultaneously accom- differ from each other.
panied by the excitation or emission of a second electron.
If the second electron is excited to some bound state, the X-Ray Tube
process is called shake-up. If the second electron is
In this case, thermionically generated electrons are
ejected, the process is called shake-off.
accelerated by a d.c. (or pulsed) potential (V) to sev-
The Auger processes compete with radiative decay.
eral keV energy and are abruptly slowed down by
The probability of radiative decay is proportional to Z4,
impinging them on a solid target. Due to this decelera-
whereas the probability of Auger ionization is constant,
tion, Bremsstrahlung radiation is emitted. The maximum
independent of Z. The fluorescence yield (o) is defined as
emission is in the direction perpendicular to the accel-
the ratio of the number of vacancies filled by X-ray
eration. Accordingly, the target surface in an X-ray tube
emission to the total number of vacancies (filled by all
is kept at an angle to the electron beam.
processes). For K shell, oK ¼ number of K X-ray photons/
The total intensity of the X-ray emitted is given by
(number of K X-ray photon þ number of Auger elec-
IpZV2.
trons) ¼ Z 4/(Z 4 þ a), where a ¼ 1.12  106. Hence, for
The efficiency of X-ray conversion is given by e ¼ X-ray
low Z atoms, the fluorescence yield is low due to strong
power/electron beam power. Experimentally, the value of e
competition from Auger processes (for Zo33, oKo1/2).
is about 1.1  109Z(V þ 10.3Z) or B1.1  109ZV for
Because satellite lines are due to doubly ionized
large accelerating voltage. This means that the X-ray
atoms, and since Auger processes dominate for low
conversion efficiency is better for higher Z targets and at
Z atoms, satellite lines are more prominent in the spectra
higher accelerating voltages. However, even for a high-Z
of low Z atoms compared to high Z atoms.
material like tungsten (Z ¼ 74) at a voltage of 50 kV, the
efficiency is only about 0.4%. The rest of the e beam
X-Ray Emission by Free Electrons energy is spent mostly in heating the target. It is therefore
necessary to have an X-ray tube anode with a high melting
From electromagnetic theory, any accelerating charge will point in either a rotating or cooled (or both) configuration
radiate, with the intensity of emission being proportional to to prevent it from melting.
3016 X-Ray Spectroscopy, Theory

Figure 8 Bremsstrahlung emission spectrum from hot plasma.

Figure 7 Bremsstrahlung emission spectrum from an X-ray

tube. lmin, the radiation is strongly polarized in the plane
containing the X-ray and the electron beam directions.
It may be noted that if the energy of the electron
The X-ray energy distribution for a thin target is exceeds the binding energy of the inner shells of the target
given by material, the impinging electron can also knock out core
electrons from the target atoms, creating inner shell
In ¼ Io for nrnmax
vacancies, leading to emission of characteristic X-rays of
¼0 for n4nmax the target material. These X-ray lines are superimposed on
the continuous Bremsstrahlung spectrum.
where hnmax is the maximum energy of the X-ray photon,
equal to the electron beam energy. This corresponds to the Hot Plasma Sources
case where the electron loses its full energy in a single
collision. It is also referred to as the Duane–Hunt limit. These include sources such as laser-produced plasmas,
The above spectral distribution is true for a thin target tokamak plasmas, pinch plasmas, solar flares, stellar X-ray
where the electron undergoes a single collision. However, emitters, etc. In such plasmas, the electron temperature
in practice, the target is thick and the electron is scat- (corresponding to a Maxwellian velocity distribution) can
tered (decelerated) many times. As a result, the energy be a few hundreds of eV to several keV. On collision with
spectrum becomes plasma ions these energetic electrons undergo accelera-
tion/deceleration and thereby emit Bremsstrahlung
I n ¼ KZðnmax  nÞ for nrnmax radiation. Electron–electron collisions do not emit any net
radiation as the two colliding electrons undergo exactly
¼0 for n4nmax
equal and opposite accelerations. The radiation emitted by
the two electrons is therefore equal in magnitude and
The spectral distribution, in terms of X-ray wave-
opposite in phase. Hence, there is no net radiation emitted.
length, is given by (Figure 7).
For a Maxwellian velocity distribution of the electrons
in the plasma, the spectral distribution of the emitted
I l ¼ cI n =l2 BKc 2 Zðl  lmin Þ=l3 lmin for l  lmin Bremsstrahlung radiation is given by (Figure 8)
¼0 for l4lmin
I l ¼ CN e S N i z2 T e -1=2 gf expðhc=l kT e Þ=l2
i

Here lmin(Å) ¼ 124 000/V. The peak of the X-ray where Ne is the electron density, Ni is the ion density of
emission is at l D (3/2)lmin. For example, for an accel- charge i, and z is the average ion charge. The factor gf is
erating voltage of 50 kV, lmin ¼ 0.25 Å and the spectral of the order of unity and it represents a departure of
distribution has a peak at l ¼ 0.37 Å. quantum mechanical calculations from the classical
The Bremsstrahlung radiation from a thick target is results. This factor is called the Gaunt factor. The peak of
only partially polarized. However, at wavelengths near this spectrum is at lp(Å) ¼ hc/2k TeB6.2/Te(keV).
 X-Ray Spectroscopy, Theory 3017

The spectral distribution of the X-ray Bremsstrahlung electrons also emit cyclotron radiation (also called
emitted from a hot plasma is shown in Figure 8, which magnetic Bremsstrahlung) due to their gyration around
shows a strong temperature dependence of the spectrum the magnetic lines of force. The acceleration is due to the
for lolp. This fact is often used for estimation of the Lorentz force acting on the moving electrons.
electron temperature of the plasma. The radiation spectrum is a discrete line spectrum at
It may be noted that, unlike the Bremsstrahlung an electron cyclotron frequency (oc) and its harmonics:
emission from X-ray tubes, there is no short wavelength o ¼ noc, where oc ¼ eB/mD1.76  1011B (T) rad s1.
limit here as the electrons have all possible energies. Although the spectrum is independent of electron
temperature, the total power radiated is proportional to
both the electron temperature (Te) and electron density
Recombination radiation (Ne) and is given by Pc (W/m3) D 4.4  1028Ne (m3)
In addition to Bremsstrahlung radiation, a hot plasma B(T)2Te (eV).
also emits recombination radiation. This radiation is
emitted when a free electron is captured in a bound state
of an ion. If E is the kinetic energy of a free electron and Synchrotron radiation sources
wn is the ionization potential of the energy level in which In a synchrotron source, electrons move with relativistic
the electron is captured, the radiation is emitted with a speed (nBc). Although this speed is almost constant,
photon energy of hv ¼ E þ wn (Figure 9). As the free when the electron trajectory is bent using bending
electron has a continuous energy distribution, the emit- magnets, the electrons undergo transverse acceleration
ted radiation spectrum is also continuous for hv Z wn. and radiate energy. This radiation is called synchrotron
Further, since the recombination can occur in different radiation.
energy levels of the ion, the overall spectrum is quasi- The power radiated is given by
continuous showing discontinuities at energies equal to
the ionization potential energies of various levels. The S ¼ ðe 2 c=6pe0 Þg4 =R2
overall shape of the spectrum is similar to that of plasma
Bremsstrahlung radiation shown in Figure 8. where g ¼ E/m0c2 and R is the radius of the electron
Interestingly, whereas in an X-ray tube, the radiation trajectory. For an electron beam of energy E(GeV) and a
is on the longer wavelength side of the Duane–Hunt bending magnet field of B(T), the radius of the electron
limit, here the spectrum is on the shorter wavelength side trajectory is given by R ¼ 3.33 E/B m.
of the ionization potential. Since the motion of the electron is relativistic, the
radiation (emitted perpendicular to the direction of
acceleration) is highly concentrated in the direction of
Cyclotron radiation
velocity within a narrow cone of nominal angular width 1/
If the hot plasma happens to be magnetized (like the
g.
tokamak/pinch plasma, X-ray binary stars, etc.), then the
Since the radiation is emitted in the form of a
searchlight-like cone, an observer receives this radiation
for a very short time period Dt B 4R/3c g3. As a result,
the emitted radiation has a large bandwidth given by
Do ¼ 2p/Dt ¼ 3pc g3/2R. Thus the observed radiation is
a continuous spectrum over a large frequency range.
The critical frequency is defined as the frequency which
divides the synchrotron radiation power spectrum into two
equal parts. This frequency is given by oc ¼ 3cg3/2R, and
the corresponding critical energy is given by
Ec ðkeV Þ ¼ 3hcg3 =4pR ¼ 0:665 BðT Þ E 2 ðGeVÞ

Also, the critical wavelength is given by

lc ¼ 2pc=oc ¼ 4pR=3g2 ¼ 5:6 RðmÞ=E 3 ðGeVÞ
¼ 18:6=BðTÞ E 2 ðGeVÞ

The synchrotron radiation from a bending magnet is

linearly polarized when observed in the plane of the e
orbit. Out of this plane, it is elliptically polarized with
Figure 9 Energy diagram for recombination radiation. opposite helicity on either side of the plane.
3018 X-Ray Spectroscopy, Theory

Periodic magnetic structure polarization in the two halves being opposite in direction,
In order to enhance the X-ray emission from the syn- the net radiation adds up.
chrotron, periodic magnetic structures are sometimes
inserted in the linear sections of the synchrotron. This X-Rays from Few Electron Systems
makes the electron notation sinusoidal in a horizontal
plane. An important parameter characterizing the elec- X-rays from a few electron systems such as hydrogen-
tron motion is the deflection parameter (K) given by like, helium-like, lithium-like ions are observed in hot
K ¼ 93.4 lu (m) B (T), where lu is the period of the plasmas (laser produced/tokamak/Z pinch), beam-foil
magnetic structure. experiments, heavy ion collisions, solar flares, etc. Muo-
nic atoms also emit X-rays.
Undulator
For low magnetic field (K o 1) the angular excursion of Ionic X-Rays
the electron is within the nominal 1/g radiation cone. In Transitions in the highly charged ions are in the X-ray
this case, the electron beam breaks up into equally spaced region and are interesting because they are relatively
bunches and the radiation from these bunches adds simple to interpret. They are also one of the few cases in
coherently (in phase). Such a magnetic structure is called atomic physics wherein high order multipole transitions
an undulator. The emitted coherent radiation is at har- are observed.
monics of lL ¼ (1 þ 0.5 K2)lu/2g2. The relative bandwidth
of the nth harmonic is given by Dl/l ¼ 1/(nN), where N is Hydrogen-like ions
the number of magnetic periods. Along the axis, only odd These are ions having a single electron left. The energy
harmonics are observed. However, if a helical magnetic levels of these ions are exactly the same as those of the
structure is used, the radiation will be circularly polarized hydrogen atom except that they are increased by a factor
and there will be no harmonics present in the on-axis Z2, where Z is the atomic number of the ion.
radiation. The emission cone is further narrowed down to
yB1/(gON). The total radiation flux is N2 times the flux Eðn; lÞ ¼ Z 2 EH ðn; lÞ
due to a single bending magnet.
The hydrogen-like series is composed of transitions of
If such a structure is placed in an optical resonator or
the type (np)2 P3/2,1/2  (1s) 2S1/2, where n Z 2. Each
used as an amplifier for radiation of wavelength l ¼ lL,
line of the series is a doublet. The limit of this series is
then it is referred to as a free electron laser.
the highest energy X-ray line that can be emitted by a
given element.
Wiggler
Unlike the hydrogen Lyman-a doublet (Dn ¼ 0.36
If the electron excursion angle exceeds 1/g (i.e. when
cm1) which cannot be easily resolved due to Doppler
Kc1) then the magnetic structure is called a wiggler.
broadening even in moderate temperature (B104 K)
Here, the radiation from different sections of the electron
plasmas, the fine structure in high Z elements can be
trajectory (where the direction of electron motion makes
easily resolved even in high temperature (B106 K)
an angle less than 1/g with the axis) adds up incoherently.
plasmas. For example, in H-like calcium, the wavelengths
The total radiation flux is 2N times the flux due to a
of the Lya doublet are 3.018 Å and 3.24 Å, which can be
single bending magnet. The emission cone is several
easily resolved with a standard crystal spectrometer.
times larger than that of the synchrotron radiation.
The total power emitted by an undulator or wiggler is
given by Helium-like ions
These are ions with only K shell electrons left. Here,
PðkWÞ ¼ 0:633 E 2 ðGeVÞ B 2 ðTÞ LðmÞ I ðAÞ except for the ground state which is a singlet (1S0), all the
excited levels (nZ2) have both singlet and triplet states
where L is the total length ( ¼ luN) of the magnetic (Figure 10). The helium-like series is composed of
structure, and I is the beam current. transitions of the type (np 1s) 1P1  (1s2)1S0. The end
For a planar magnetic field in the vertical direction, point of the series is the ionization potential of the 1s
the on-axis radiation is polarized in the horizontal plane, electron in its (1s2)1S0 ground state.
as in the case of a bending magnet. However, unlike the
bending magnet case, for a periodic magnetic structure, Types of transitions
the off-axis radiation is also plane-polarized in the hor- The terminology for X-ray transitions in ions is the same
izontal plane. This is because the vertical component of as that of optical transitions in an atom. The three main
polarization emitted in one half is cancelled by the types of transitions observed in an ionic line spectrum
radiation in the next half (out of phase) as both have the are: (1) resonance transitions, (2) intercombination tran-
same direction of polarization. However, the horizontal sitions, and (3) satellite transitions.
 X-Ray Spectroscopy, Theory 3019

Figure 10 Energy level diagram for helium-like ions showing resonance, intercombination, and other transitions.

Resonance transitions
These are transitions from an excited state to the ground
state (Figure 10). The H-like series and He-like series
discussed earlier are resonance transitions. The oscillator
strengths of these transitions are higher than those of other
types of transition. For the same reason, these lines can be
strongly reabsorbed if they are emitted by a hot-dense
plasma. They follow the normal selection rules applicable
to optical transitions.

Intercombination transitions
These transitions are similar to resonance transitions
except that they are between states of different multi-
plicity (e.g. triplet to singlet). Corresponding to a reso-
nance transition (1s2p) 1P1  (1s2) 1S0 (which is a singlet-
singlet transition), the intercombination transition (tri-
plet-singlet) is (1s2p)3P  (1s2) 1S0 (Figure 10). These
lines appear on the lower energy side of the resonance
lines. Though 3P1  1S0 is a spin-forbidden transition, in Figure 11 Energy diagram for 2s and 2p satellite transitions in
high Z ions, the 3P1 state decays by dipole transition lithium-like ions corresponding to He-a and He-b transitions in
through mixing with 1P1 states. helium-like ions.

Satellite lines (Figure 11). The n‘l’ electron is a spectator electron. Due
These are weaker lines arising from doubly excited ions to the presence of this electron, Coulomb shielding
of higher ionization states. The satellite lines of H-like decreases, which results in the transition occurring at a
ions are due to He-like ions, those of He-like ions are slightly lower energy than that of the resonance transi-
due to Li-like ions and so on. For example, transitions in tion. Since two electrons are involved in such transitions
Li-like ions of the type 1s nln‘l’-1s 2 n‘l’ will appear as a (one active, one spectator), these lines are also referred to
satellite to 1s nl–1s2 resonance transitions in He-like ions as dielectronic satellites.
3020 X-Ray Spectroscopy, Theory

The largest separation from a parent line occurs when considerable time inside the nucleus. Consequently, the
the spectator electron is in the lowest n level (i.e. n ¼ 2), 1s level is strongly affected by the nucleus. This is cor-
when the Coulomb shielding effect is maximum. These roborated by the fact that whereas the Balmer series
satellites are referred to as 2s or 2p satellites. For (n-2) transition energies are found to be exactly
example, the 1s 2s 2p – 1s2 2s transition in Li-like ions Z2(M* /m* ) times those of the H-atom, the Lyman series
will be a 2s satellite for the 1s 2p – 1s2 (He-a) transition (n-1) transition energies are lower than expected.
in He-like ions (Figure 11). Satellites of H-like ions in
the Gabriel notation are denoted by capital letters See also: Photoelectron Spectrometers, X-Ray
A, B,yJ,y and those of He-like ions are denoted by Absorption Spectrometers, X-Ray Emission
lower case letters a, b, c,yyu, v. Spectroscopy, Applications, X-Ray Emission
Spectroscopy, Methods, X-Ray Fluorescence
Muonic X-rays Spectrometers, X-Ray Fluorescence Spectroscopy,
Applications, Zero Kinetic Energy Photoelectron
When a negatively charged particle (m, p, K meson) Spectroscopy, Theory.
replaces an electron in an atom, a mesonic atom is
formed. For example, when a m meson is brought to rest
in a target, muonic atoms of the target element are Further Reading
formed by replacement of a valence electron by m.
Agarwal BK (1991) X-ray Spectroscopy: An Introduction. Berlin:
The energy levels in a muonic atom are analogous to the Springer-Verlag.
electronic energy levels of an H-like ion except that Azaroff LV (1974) X-ray Spectroscopy. New York: McGraw-Hill.
the muon mass is higher (mmB207me). The mesonic atom Bertin EP (1975) Principles and Practice of X-ray Spectrometric
Analysis. New York: Plenum Press.
energy levels are related to those of the hydrogen atom Bonnelle C and Mande C (1982) Advances in X-ray Spectroscopy. New
by E(n,l ) ¼ Z2 (M* /m* ) EH(n,l), where M* and m* are the York: Pergamon Press.
reduced masses of m and the electron, respectively, and Craseman B (1985) Atomic Inner Shell Physics. New York: Plenum
Press.
EH(n,l ) denotes energy levels in hydrogen. The newly Herglotz HK and Birks LS (1978) X-ray Spectrometry. New York:
formed muonic atom is thus in a highly excited state and Dekker.
lowers its energy by ejecting electrons by successive Janev RK, Presnyakov LP, and Shevelko VP (1985) Physics of Highly
Charged Ions. Berlin: Springer-Verlag.
Auger processes until the principal quantum number falls Jenkins R (1976) An Introduction to X-ray Spectrometry. London:
to less than 5 (in heavy atoms). At this point, the radiative Heyden.
transition probability becomes more prominent. The Kauffman RL and Richard P (1976) X-ray region. In: Williams D (ed.)
Methods of Experimental Physics vol. 13 Part A (Spectroscopy).
energy level differences become of the order of several London: Academic Press.
keV. As a result, X-rays are emitted until the muonic Michette AG and Buckley CJ (eds.) (1993) X-ray Science and
atom reaches its ground state. Technology. London: IOP Publishing Ltd.
Thompson M, Baker MD, Christie A, and Tyson JF (1985) Auger
The average radius of the lowest (Bohr) orbit of the Electron Spectroscopy (Chemical Analysis, vol. 74). New York: Wiley
muonic atom is given by rB(m* /M* ) (aH/Z) which is Interscience.
considerably smaller than that of a normal atom. For Williams KL (1987) Introduction to X-ray Spectrometry. London: Allen
and Unwin.
example, for silver, r is 5  1015 m, which is of the order White HE (1986) Introduction to Atomic Spectroscopy. Singapore:
of the nuclear size. As a result, the muon spends McGraw-Hill Book Co.