atoms

Review
Photoionization and Electron–Ion Recombination in
Astrophysical Plasmas
D. John Hillier

Department of Physics and Astronomy & Pittsburgh Particle Physics, Astrophysics and Cosmology Center
(PITT PACC), University of Pittsburgh, 3941 O’Hara Street, Pittsburgh, PA 15260, USA; hillier@pitt.edu;
Tel.: +1-412-624-9000

Abstract: Photoionization and its inverse, electron–ion recombination, are key processes that influ-
ence many astrophysical plasmas (and gasses), and the diagnostics that we use to analyze the plasmas.
In this review we provide a brief overview of the importance of photoionization and recombination
in astrophysics. We highlight how the data needed for spectral analyses, and the required accuracy,
varies considerably in different astrophysical environments. We then discuss photoionization pro-
cesses, highlighting resonances in their cross-sections. Next we discuss radiative recombination, and
low and high temperature dielectronic recombination. The possible suppression of low temperature
dielectronic recombination (LTDR) and high temperature dielectronic recombination (HTDR) due to
the radiation field and high densities is discussed. Finally we discuss a few astrophysical examples to
highlight photoionization and recombination processes.

Keywords: photoionization; recombination; massive stars; Wolf–Rayet stars; local thermodynamic

equilibrium (LTE); nLTE

1. Introduction
One of the most important ways we learn about the Universe is through spectroscopy.
From spectroscopy we can typically deduce important stellar parameters such as a star’s
effective temperature,1 surface gravity (=GM∗ /R∗ 2 ) and abundances. These in turn provide
Citation: Hillier, D.J. Photoionization
insights into stellar evolution, galactic evolution, and the evolution of the Universe. To
and Electron–Ion Recombination in
perform analyses of stellar data requires atomic data, although the amount and type of
Astrophysical Plasmas. Atoms 2023,
atomic data needed varies greatly with the application. In the most extreme cases, in
11, 54. https://doi.org/10.3390/
which local thermodynamic equilibrium does not hold (discussed below), we require, for
atoms11030054
example, photoionization cross-sections, oscillator strengths for bound–bound transitions,
Academic Editors: Sultana N. Nahar line-broadening data, collisional cross-sections, autoionization rates, chemical reaction rates,
and Guillermo Hinojosa and charge exchange cross-sections. For some simple species, such as hydrogen, we have
Received: 24 January 2023
excellent atomic data while for other important species, such as Fe group elements, crucial
Revised: 3 March 2023 atomic data is lacking. Unfortunately, for many ionization stages even basic information,
Accepted: 3 March 2023 such as accurate energy levels, is also missing.2 However, invaluable work by the NIST and
Published: 9 March 2023 Imperial college atomic spectroscopy groups is helping to rectify this situation for some
important astrophysical ions (e.g., [2,3]).
In this review we discuss the importance of photoionization cross-sections for astro-
nomical applications, with an emphasis on massive stars. Such a discussion will necessarily
Copyright: © 2023 by the authors.
consider recombination processes—the inverse of photoionization processes. Before doing
Licensee MDPI, Basel, Switzerland.
so it is necessary to define some important physical and astronomical terms.
This article is an open access article
A star (or any other astrophysical object emitting radiation) is not in thermal equilib-
distributed under the terms and
rium. However, in some cases, and at some locations, it is well justified to assume that
conditions of the Creative Commons
Attribution (CC BY) license (https://
the plasma in the star is in “local” thermal equilibrium. Below the atmosphere (the thin
creativecommons.org/licenses/by/
layer that emits the radiation we observe) the material in most stars can be considered
4.0/). to be in “local” thermal equilibrium (LTE). In such cases, the state of the gas (e.g., the

Atoms 2023, 11, 54. https://doi.org/10.3390/atoms11030054 https://www.mdpi.com/journal/atoms

Atoms 2023, 11, 54 2 of 27

thermodynamical properties, the ionization state, and the populations of atomic levels) are
set by the density and electron temperature via thermodynamic arguments. The ionization
state of the gas and the level populations are determined, for example, by the Saha and
Boltzmann equations (e.g., [4]). Moreover, there is only one temperature—the electron tem-
perature, the ion temperature, the excitation temperature, and the radiation temperature
are all identical. The temperature of the gas varies with location (it must, since radiation is
propagating outwards) but the scale on which it varies does not affect the thermodynamic
state of the gas. Unfortunately, much of the radiation we observe comes from gas that is
NOT in LTE—typically referred to as nLTE or non-LTE.
At the stellar surface the assumption of LTE becomes less valid. This is not surprising—
at the stellar surface radiation is escaping from the star and there is no incident radiation (at
least for single stars), and hence the radiation density must drop from its blackbody value
by a factor of (at least) ∼2 (since there is no incident radiation—see (see [4], p. 120). Further,
because radiation can now travel significant distances, regions of different temperatures
are directly coupled, potentially making the radiation field at a given location strongly
non-Planckian.
Fortunately, in some cases the densities are high enough that collisional processes can
still strongly couple the level populations and the ionization state of the gas to the local
electron temperature, allowing us to use the Saha and Boltzmann equations to compute
level populations. In such cases the electron temperature (which will be the same as the ion
temperature) determines the state of the gas and it is this temperature that we normally
state. In general, however, the electron and radiation temperatures will be different.3
The Boltzmann equation, which relates the populations of two levels within the same
ionization state, is
gu n∗l
n∗u = exp(− Elu /kT ) (1)
gl
where n∗l and n∗u are the LTE population densities of the lower and upper states, respectively,
gl and gu are the level degeneracies, and Elu is the difference energy between the two levels
(e.g., [4]).
The Saha equation, which relates the ground state populations of two consecutive
ionization equations, is

∗ ∗ g1,i C I
n1,i = n1,i +1 Ne exp (−ψi /kT ) (2)
g1,i+1 T 3/2

where T is the electron temperature in Kelvin, C I = 2.07 × 10−16 (cgs units), Ne is the
electron density, ψi is the ionization energy, and the subscript i (i + 1) is used to denote the
ionization stage.
In many stars, and especially those with lower density gas (nebulae, stellar winds,
supernovae) the departures from LTE are significant and MUST be allowed for. Gaseous
nebulae, which typically have densities less than 106 atoms cm−3 , provide an excellent
example in which the departures from LTE are extreme. The radiation field that ionizes the
nebula typically emanates from a hot star (Teff & 25,000 K) and is strongly diluted since
the nebula is typically very distant from the star (Figure 1). The equilibrium temperature
of the gas is typically around 10,000 K (which is primarily determined by the chemical
composition of the nebula) and is insensitive to the effective temperature of the star. The
nebula, longward (i.e., at larger wavelengths) of the H I Lyman jump at 912 Å, is transparent
to most radiation. Because of the non-Planckian radiation field and the low densities,
collisions with electrons cannot drive the gas into LTE.
Atoms 2023, 11, 54 3 of 27

Figure 1. A composite image of the Helix nebula obtained using the HST and the Cerro Tololo Inter-
American Observatory in Chile. Hα+[N II] (λλ6548.1, 6583.4 Å), emission is shown in red, an average
of Hα+[N II] and [O III] (λλ4958.9, 5006.8 Å) is shown in green, and forbidden [O III] emission is
shown in blue [5]. The nebula lies at a distance of about 200 pc, and the size of the semi-major axis
is approximately 5.5 arc minutes or 66,000 AU [5]. The central star has an effective temperature
of 104,000 K, L ≈ 80 L , and R ≈ 0.028 R [6]. Using the semi-major axis as a representative size
scale, the dilution factor ( 0.25(r/R∗ )2 ) is of order 10−18 . Detailed insights into the structure and
morphology of the Helix nebula can be found in many works (e.g., [5,7]). Image credit: NASA, ESA,
C.R. O’Dell (Vanderbilt University), and M. Meixner, P. McCullough, and G. Bacon (Space Telescope
Science Institute).

When LTE no longer holds (i.e., nLTE) we are forced to solve for the ionization state
of the gas and the level populations from first principles. That is, we need to consider all
the processes, and inverse processes, that populate a given level. These processes include
photoionization and recombination, bound–bound emission and absorption, collisional
excitation and de-excitation, collisional ionization and collisional recombination, dielec-
tronic recombination and autoionization, charge exchange reactions and, in “cooler gas”
(T / 6000 K), chemical reactions, and dust chemistry.4 Determining the state of the gas is a
complicated problem. Many of the processes above depend on the radiation field which
in turn depends on the level populations. Further, the radiation field couples the gas to
regions of different temperatures. This is a highly non-linear problem and can only be
solved by iterative techniques. In many cases we can consider the population numbers to
be static (and the equations are referred to as the equations of statistical equilibrium) but
in other cases (e.g., supernovae) we may need to allow for time dependence (and solve
the kinetic equations). Another major issue is correcting for plasma effects that limit the
number of levels in atoms and ions (i.e., crudely, an atom/ion cannot be larger than the
inter-atom spacing). One approach is probabilistic and was developed in a series of papers
by Hummer, Mihalas, and Dappen [12–14], and is used, for example, in the nLTE radiative
transfer codes TLUSTY[15] and CMFGEN [16]. In this approach, levels are assigned an
occupation probability that varies smoothly with the level energy, density and temperature,
and that leads to a finite partition function.
Thus, a vast amount of atomic data is needed. Sadly, despite heroic efforts by Bob Ku-
rucz [17,18], members of the Opacity Project [19] and Iron Project [20], Sultana Nahar [21],
and many others, much of the needed data is still missing. Extensive photoionization
data is available, for example, through TOPbase [22], TIPbase [23], and NORAD [21]. As
discussed later in this article, details can matter, and it is not always obvious, a priori,
which data are essential for accurate analyses. As this paper is concerned with photoioniza-
Atoms 2023, 11, 54 4 of 27

tion/recombination, this paper does not generally elaborate on other important processes.
Information on these additional processes can be found in, e.g., [24–27].
Below we discuss photoionization and recombination as relevant to astrophysical
applications. Much of the following discussion will be based on my own experiences
in developing CMFGEN, a nLTE radiative transfer code originally designed to model hot
massive stars ( M > 20 M , Teff ≥ 20, 000 K) and their stellar winds [16,28]. The winds in
these stars are driven by radiation pressure acting on bound–bound transitions belonging,
for example, to C, N, O, Ar, and Fe (e.g., [29–31]). Since its initial development the code
has undergone considerable revisions and improvements. It has been successfully used
to model O stars (e.g., [32–36]), Wolf–Rayet (WR) stars [37,38], luminous blue variables
(e.g., [39–41]), B stars (e.g., [42]), the central stars of planetary nebulae (e.g., [43]), and A
stars. Over the last decade CMFGEN was adapted to treat time-dependent radiation transfer,
and to solve the time-dependent kinetic equations [44], and it has been used to model
spectra resulting from a variety of SN explosions (e.g., [45–48]).
The review is organized as follows: In Section 2 we briefly discuss the importance
of photoionization processes for stellar interiors and introduce the Rosseland mean opac-
ity. We then consider photoionization processes in Section 3 with an emphasis on in-
ner shell ionizations in Section 3.1. Recombination processes are discussed in Section 4
while suppression of dielectronic recombination by collisions and the radiation field is
discussed in Section 5.1 and Section 5.2 respectively. Specific examples of where photoion-
ization/recombination processes are important are then discussed—direct recombination
(Section 6.1), the Sun (Section 6.2), O stars, WR stars, luminous blue variables (LBVs),
(Section 6.3), Of and WN stars (Section 6.3.1), carbon lines in WC stars (Section 6.3.2), C II
in a [WC] star (Section 6.4), and supernovae (Section 6.5).

2. Stellar Interiors
In stellar interiors energy is transported by radiation and by convection, and in
degenerate stars by conduction. As LTE holds, photoionization processes have no direct
influence on the level populations (since the populations are determined by the Saha and
Boltzmann equations), but they do help to determine the temperature of the gas and they
do help to set the continuous radiation field that we observe. Due to the small mean-free-
path of photons, radiation transport is diffusive and in this regime a single quantity, the
Rosseland mean opacity, is required to describe the transport of radiative energy. At depth
in the star the radiation diffuses and the specific intensity (Iν ) at frequency ν is given by

µ dBν
Iν = Bν − (3)
χν dr

(e.g., [4]) where Bν is the Planck (i.e., blackbody) function given by

2hν3 1
Bν = 2
, (4)
c exp(hν/kT ) − 1

χν is the opacity, and µ is the angle between the radius and the direction of radiation
propagation. The radiative flux is simply given by

−1 dBν
Fν = . (5)
3χν dr

The negative sign in the expression for the flux arises because T, and hence Bν , decrease
with increasing r. Integrating over all frequencies yields a total radiative flux, F, given by

T 3 dT
F = −16σ (6)
3χ R dr
Atoms 2023, 11, 54 5 of 27

where σ is the Stefan–Boltzmann constant and χ R is the Rosseland mean opacity as defined by
R∞ 1
1 0 χ dBν /dT dν
= R∞ ν . (7)
0 dBν /dT dν
χR

In stellar interiors the Rosseland mean opacity is a function of density, temperature,

and composition, and is primarily determined by the most abundant species, with H, He,
C, N, O, Ne, and Fe being the most crucial. As it is a harmonic mean it can be strongly
influenced by regions of low opacity. Thus, it is crucial to take into account all opacity
sources, particularly contributions in regions of otherwise low opacity. For a given species,
the opacity is determined by photo-ionization processes, bound–bound transitions, and
free–free processes. The required cross-sections are non-trivial to compute, especially for
Fe group elements (with a partial filled 3d shell). Fortunately, because it is a broad integral,
the Rosseland mean opacity is insensitive to small random errors (e.g., bound–bound
transitions slightly offset from their correct wavelength) in the atomic data.
The computation of the Rosseland mean opacity is further complicated by the need
to account for plasma effects—atoms/ions in a star are not isolated but experience a time-
varying electric field due to their neighbors. This broadens bound–bound transitions which
enhances the Rosseland mean opacity since the influence of the line is spread over a broader
band into regions which may have lower opacity. Further, the size of the atoms/ions
(and hence the number of levels) will be truncated since atoms/ions can only occupy a
finite volume. The latter can be thought of as a lowering of the ionization potential but
more rigorous approaches, for example, use probabilistic arguments [12,49]. An extensive
discussion of some of the issues related to plasma effects on the equation of state, and
additional references, are given by [50]. Extensive efforts have been made to provide LTE
opacity libraries for stellar astrophysics that take into account different physical effects
with varying degrees of fidelity. These include the Opacity Project [51], opacities computed
using the OPAL code (e.g., [52,53]), the OPAS code [54], and a suite of codes developed at
The Los Alamos National Laboratory [55].

3. Photoionization
The photoionization rate from a level l (in an arbitrary ion of arbitrary charge) can be
written as   Z ∞ 
dnl 4π
= −nl σν Jν dν (8)
dt PR νo hν
where nl is the population density of level l, σν is the frequency dependent photoionization
cross-section (units are cm2 ), νo the threshold frequency for ionization, h is Planck’s constant,
and Jν is the mean intensity (erg cm−2 s−1 Hz−1 ). Jν is defined by

1
I
Jν = Iν dΩ (9)
4π
where dΩ is an increment in solid angle. If the radiation field is Planckian and isotropic,

Jν = Iν = Bν . (10)

The photoionization cross-sections are generally obtained from numerical calculations

—it is not feasible to measure all the cross-sections in the laboratory. Rather, laboratory
measurements are used to test the accuracy of theoretical calculations. The accuracy of the
cross-section varies greatly being dependent on both assumptions used in the modeling
and on the complexity of the model atom. For example, it is much easier to compute atomic
data for atoms/ions with a partially filled p shell than it is for the lanthanides and actinides
which have a partially filled 4f or 5f shell, respectively (e.g., [56]). The lanthanides are
believed to be created in neutron–neutron star mergers and are an important opacity source
in the outburst spectra that result from such mergers [57–62].
Atoms 2023, 11, 54 6 of 27

Typically in model atmosphere codes the rates (integrals) are evaluated using numeri-
cal quadrature. Thus    
dnl 4π
= −nl ∑ wi σi Ji (11)
dt PR i
hνi
where wi is the quadrature weight at frequency νi .
In a simple species such as hydrogen, the photoionization process is simply

H + hν → H+ + e− .

In more electron-rich species the process is more complicated since there are multiple
photoionization routes. For example, there are two direct photoionization routes from
C III(2s 2p):
C III(2s 2p1 Po ) + hν → C IV (2s2 S) + e− &
o
C III (2s 2p1 P ) + hν → C IV (2p2 Po ) + e− .
The first process occurs provided the photon energy exceeds the ionization energy of the
C III(2s 2p 1 Po ) state5 . The second process occurs when the photon energy exceeds the
sum of the ionization energy and the difference in energy between the 2s and 2p states in
C IV. Of course, photons of sufficient energy may also ionize C2+ by ejecting an inner (1s)
electron—a process of great importance when X-rays are present.
There may also be multiple indirect photoionization routes such as:

C III (2p2 1 D) + hν → C III (2p4d1 Fo ) → C IV (2s2 S) + e− .

The above produces a relatively “narrow” resonance in the photoionization cross-section—

it is narrow since the photon has to have the right energy to excite one of the 2p electrons
into the 4d state (Figure 2). The energy of this state lies above the C IV ground state. The
last step in this process is referred to as autoionization.

Figure 2. Illustration of the photoionization cross-section (in megabarn, with 1 Mb = 10−18 cm2 )
of C III 2p2 1 D. Ionization to the C IV ground state occurs via autoionizing levels such as C III 2p
4d 1 Fo . Shortward of ≈325 Å, photons have sufficient energy to ionize directly to C IV 2p 2 Po . The
data were convolved with a Gaussian profile with a full width at half maximum of ∼ 600 km s−1 (i.e.,
σ = 250.0 km s−1 ). The photoionization cross-sections for C III were computed by P. J. Storey (private
communication). In other photoionization cross-sections the resonances are often much narrower
than those shown here.

In LTE the final state arising from the photoionization process is irrelevant—only
the total opacity matters. In general, in nLTE, the final state matters, since each process
contributes to the population of a different state whose population needs to be determined
from first principles. In practice this is generally not a crucial concern for most spectral
modeling since the rates for processes connecting states within an ion are generally much
larger than the photoionization and recombination rates. However, there are cases where
the final-state-dependent cross-sections are important.
Atoms 2023, 11, 54 7 of 27

As a first example, we again consider the C III / C IV system in WR stars6 . In the

photosphere the strong C IV λλ1548, 1551 doublet (due to 1s2 2s–1s2 2p) is optically thick,
and hence the 1s2 2p state is strongly coupled to the 1s2 2s ground state through colli-
sional de-excitation and excitation (i.e., the 2p state is in LTE (computed using the local
electron temperature) with respect to the 2s state). Consequently we can treat all ion-
izations/recombinations as occurring to/from the C IV ground state. However, as the
density declines photon escape in the resonance line will lead to a decoupling of 1s2 2p
from the 1s2 2s state, in which case we should treat recombinations from the 1s2 2p state
separately from those occurring from the 1s2 2s state. Fortunately, because the 1s2 2p state
lies ≈ 8 eV above the ground state, recombinations from the 1s2 2p state are generally not
very important for the temperatures and densities appropriate to WR stars in the regime
important for spectrum formation. This may not be the case in other regimes, and for other
ions with states closer in energy to the ground state.
One crucial area where state-dependent photoionization cross-sections are important
is in X-ray fluorescence where the ejection of an inner shell electron leads to the ion being in
a highly excited state, and the emission of characteristic X-rays or the subsequent ejection of
one or more additional electrons (Auger ionization) (e.g., [68,69]). The subsequent decay of
these more highly charged ion gives rise to lines which can be detected and their strength
is dependent on the details of the autoionization processes that occurred after the inner
shell electron was ejected (e.g., [70–72]).

3.1. Inner Shell Ionization

Typically ionization from the inner shell of an ion (e.g., from the 1s2 shell in O I–O V)
is not very important for modeling stellar spectra, since very little flux will be emitted
at the relevant energies when the ionization stages are abundant. An exception occurs
when there is a significant source of X-rays, as can occur when a star has a corona or when
there is a compact object with an accretion disk. For massive stars, X-rays can arise in
shocks generated by a wind–wind collision in a binary system or in shocks generated from
instabilities in the driving of the wind by radiation pressure (e.g., [73–75]). For O stars, the
observed X-ray fluxes generated by these two processes are typically in the range of 10−5
to 10−8 L∗ (e.g., [76,77]).
With the discovery of X-ray emission from O stars it was realized that X-rays could
explain the presence of both O VI λλ1032, 1038 and N V λλ1238, 1243 P Cygni profiles7
in the UV spectra of O stars. An example P Cygni profile is shown in Figure 3. Since O
stars typically have effective temperatures of <∼ 40, 000 K, the photospheric radiation
field cannot produce sufficient O VI to explain the observed O VI profile. However, X-rays,
through Auger ionization, can produce sufficient O VI [78]. In the case of O VI, the crucial
reaction is:
O IV(1s2 2s2 2p)+ X-ray → O V(1s 2s2 2p) + e− → O VI(1s2 2s) + 2e− .
Typically two electrons are ejected (i.e, one by interaction with the photon and one
by the Auger process) in Auger ionization for CNO elements but for heavier elements
more than two electrons can be ejected (e.g., [68]). In CMFGEN we assume all inner-shell
ionizations only eject two electrons and the intermediate states are omitted.8 Many studies
have shown that inner shell ionization of X-rays can successfully explain the presence of
O VI and N V in O stars (e.g., [79,80]). Auger ionization complicates the kinetic equations
since more than two ionization stages are directly coupled.
Atoms 2023, 11, 54 8 of 27

Figure 3. The C IV λλ1548.2, 1550.8 P Cygni profile in the O4 I(n)fp star Zeta Puppis. The x-axis
was computed using v = c(λ/λo − 1.0) where λo = 1548.187. The spectrum has been normalized
by the continuum spectrum (Fc )—i.e., a smooth curve drawn through spectral regions showing no
evidence for bound–bound absorption or emission. Strong blue shifted absorption is seen, indicating
an outflowing stellar wind with a terminal velocity (V∞ ) in excess of 2600 km s−1 . The redshifted
emission primarily arises from continuum photons that were emitted in other directions, absorbed by
C IV, and subsequently scattered to the observer. The two narrow absorptions near 0 and 500 km s−1
are due to absorption by C IV in the interstellar medium.

4. Recombination
The recombination rate is given by
∗ Z ∞ 2hν3
      
dnl nl 4π
= nK σν + Jν exp(−hν/kT )dν (12)
dt RR nK νo hν c2

(e.g., [4]) where the subscript K refers to the recombining ion and the LTE population is
computed using the actual electron density. The quantity (nl /nK )∗ (for a given level) is
only a function of the electron density and temperature. When the gas is in LTE, and when
Jν = Bν , the photoionization and recombination rates (absolute values) are identical.
In my work I treat recombination as the reverse process of photoionization and hence
in CMFGEN recombination rates are computed using the photoionization cross-sections.
As noted earlier, rates are evaluated using numerical quadrature, and identical weights
are used for both the forward and reverse process. At high densities it is desirable to
treat both processes identically since small differences can cause erroneous populations
to be determined when solving the kinetic equations. At depth, where LTE conditions
apply, it is important that they identically cancel. Generally the weights are evaluated
using the trapezoidal rule—more accurate quadrature schemes are generally not feasible
because of the complex frequency dependence (and depth dependence) of the radiation
field, and because the same quadrature scheme must be used to compute the rates for both
photoionization and recombination. Care must be taken near bound-free edges, since the
integrand in the recombination rate can vary rapidly with frequency—especially true for
highly ionized states at low temperatures since the recombination rate at frequency ν scales
as exp[−h(ν − νo )/kT ].
For low densities, such as those found in H II regions, planetary nebulae, and many
collisionally ionized plasmas, recombination rates are often evaluated separately, and
treated as a distinct process. At “low” densities most transitions are optically thin, and
recombination into high states simply cascade into the ground state and metastable levels.
In a H II region, for example, the ionization of H is maintained through photoionizations
from the ground state and photoionizations from excited states can be ignored. However
transitions to the ground state can be optically thick. Consequently two limiting cases
are considered when computing H line strengths—Case A, in which all transitions are
assumed to be optically thin, and Case B, in which only the Lyman transitions are optically
thick (e.g., [25]). Under the optically thick assumption the rate of decays in a transition is
assumed to be exactly balanced by the rate of radiative excitations in the transition.
Atoms 2023, 11, 54 9 of 27

4.1. Direct Radiative Recombination

This process is taken to refer to simple recombination processes such as
H+ + e− → H(nl) + hν and
C IV(2s 2 S) + e− → C III(2s nl) + hν .
In the above n and l refer to the principal and angular momentum quantum numbers of
the electron.
The cross-sections for the processes are “smooth” and easily integrated. However,
state-of-the-art photoionization cross-sections, such as those available through TOPbase
and NORAD, often include indirect photoionization routes or resonances. When discussing
the reverse process it is often convenient to split the resonances into two classes—low tem-
perature dielectronic recombination (LTDR) resonances and high temperature dielectronic
recombination (HTDR) resonances.

4.2. Low Temperature Dielectronic Recombination (LTDR)

LTDR refers to recombination through double-excited states that lie close to, but above,
the ionization energy of the ion ground state [81,82]. It is treated separately from HTDR
since it is very species/ionization state specific—the energy levels involved in LTDR need
to be known accurately since the distance of these states from the ionization limit is a crucial
factor in determining the recombination rate. Dielectronic recombination is the inverse
process of autoionization.
We can understand the LTDR process as follows by using an example. Consider the
C III 2p 4f 1 D state (Figure 4) which can autoionize (the inverse process to dielectronic
recombination) to give C IV and a free electron. For this state the autoionization rate coeffi-
cient is large (>1013 s−1 ).9 However, the level can also undergo a “stabilizing transition”,
leading to a recombination, with the most important stabilizing transition being
2p 4d 1 Fo → 2p2 1 D + hν .
The Einstein A coefficient for this process (Aul ) is ∼ 6.2 × 109 s−1 (P. J. Storey, private com-
munication), much lower than the autoionization probability. Consequently the 2p 4f 1 Fo
state will be in LTE with respect to C IV and hence the LTDR recombination rate for this
single transition is n∗u Aul where n∗u (in cgs units) is given by

2.07 × 10−16 gu
n∗u = Ne NCIV exp (−ψl /kT ) (13)
T 3/2 gCIV

(e.g., [4]). In the above formula gu is the statistical weight for the 2p 4d 1 Fo state, gCIV
is the statistical weight of the C IV ground state (2s 2 S), Ne is the electron density, NCIV
is the ground state population of C IV, and ψl is the energy of the 2p 4d1 Fo state above
the ground state of C IV. At 104 K that single transition leads to a LTDR recombination
coefficient (defined as the (LTDR rate)/Ne /NCIV ) of 3.1 × 10−12 cm3 s−1 (P. J. Storey, pri-
vate communication) which is essentially identical to the direct recombination rate of
3.2 × 10−12 cm3 s−1 [83].
Thus, we see the following:
1. The LTDR rate is very sensitive to ψ when ψl /kT is of order unity or larger.
2. When ψl /kT << 1, the LTDR recombination rate scales as T −3/2 and thus increases
more quickly with decreasing temperature than the radiative recombination rate,
which typically scales as T −α with α ∼ 0.7. (see, e.g., [83]).
3. The LTDR process will be most important for those states with a large Einstein A
coefficient and for those states lying closest to, but above, the ion ground state.
4. The process is very dependent on the details of the atomic structure. In the above case,
the energy of the 2p 4d 1 Fo state is crucial for determining the LTDR rate. As the LTDR
autoionizing states lie well above the C III ground state, and can have large energy
Atoms 2023, 11, 54 10 of 27

widths, the energies of the states are not necessarily known. Theoretical calculations
can provide estimates, but will have difficulties for states that lie ”very close” to the
ionization limit since a small error in the energy level can make a big difference in the
recombination rate, particularly at low temperatures.
Energy
2p 2Po 2p nl 1L’

2s 2S 2p 4d 1Fo
2s nl 1L

2p2 1P
2p2 1D
2s 2p 1Po

2s2 1S

Figure 4. Simplified pseudo-Grotrian diagram for C III and C IV to help illustrate LTDR and HTDR.
Five bound C III levels are shown in black and two C IV levels are shown in red. Example HTDR
autoionizing levels (e.g., 2p 50p, 2p 50d, etc.) that converge on the C IV 2p 2 Po state are shown in
blue. One of the most important LTDR autoionizing levels is shown in orange—it has been moved up
slightly in energy to separate it more clearly from the C IV ground state—the horizontal dashed red
line is used to indicate the energy of the C IV ground state. The blue line shows a HTDR transition,
which has a wavelength approximately equal to that of the C IV resonance transitions (1548, 1551 Å),
while the dashed orange line shows a LTDR transition (at ∼412 Å). Triplet levels also experience both
LTDR and HTDR.

The LTDR rate can exceed the direct recombination rate, and in many cases plays a cru-
cial role in determining nLTE level populations, and observed line strengths
(e.g., [81,82,84]).
The LTDR process is complicated by states that are forbidden to autoionize in LS
coupling, such as the 2p 4d 3 Do state in C III or the quartet states in C II. In such cases the
populations of these levels must be determined by solving the rate equations. These levels
will be collisionally and radiatively coupled to states that can autoionize and, because of
departures from LS coupling, they can also have non-zero autoionization rates which are
larger than the radiative decay routes from the state. Thus, these levels can be an important
additional recombination channel.
In CMFGEN we handle the quartet states in C II as part of our atomic models while the
doublet autoionizing states are assumed to be in LTE with respect to the ground state of
C III and are not directly treated. Recombination through the quartet states is treated via
the line transitions connecting them to lower levels, while transitions for the autoionizing
states are treated via the photoionization cross-sections. Generally we assume the states
within a term are populated according to their statistical weights, although this will not
be valid for some levels since the autoionizing rates can depend strongly on their total
angular momentum. For example, the autoionizing probabilities for the C II 2s 2p(3 Po )
4s 4 Po j = 1/2, 3/2, and 5/2 states are 5.3 × 109 , 1.3 × 1010 , and <3 s−1 . These were obtained
from the full width at half maximum tabulated by [84]. One issue, potentially important at
high densities, is that we do not have accurate collisional cross-sections for the states not
permitted to autoionize in LS coupling.
For C III we typically assume, following [82], that all low lying states can autoionize.
LTDR is easily taken into account via the photoionization cross-sections; however, the
assumption is only necessarily valid for those states in which the autoionization rates
(greatly) exceed other processes populating/depopulating the autoionizing state.
A potential problem in nLTE calculations is that, due to difficulties of current atomic
codes to compute accurate energies, the resonances in the photoionization cross-sections
are offset from their true positions. Such offsets are probably unimportant when computing
Atoms 2023, 11, 54 11 of 27

the Rosseland mean opacity, but can be important for spectral studies. First, an inaccurate
energy will influence the location of observable resonances in stellar spectra. Second, it can
have an effect at “low” temperatures due to the scaling of the LTDR rate with temperature
(exp(−ψ/kT )/T 3/2 ). Third, complicated nLTE effects could arise. For example, a wrong
resonance wavelength can potentially cause issues if a strong resonance coincides (or now
does not coincide) with another bound–bound transition (since a strong resonance can
affect the radiation field in the transition and vice versa).
The direct inclusion of resonances in photoionization cross-sections also has other
potential issues. First, the resonances vary much more rapidly than the background cross-
section and hence a very fine frequency grid needs to be used—this is particularly true for
narrow resonances. For computational expedience, we typically sample the continuum
cross-sections in CMFGEN every 500 km s−1 (but finer near level edges). To avoid aliasing10
we smooth the cross-sections. In early versions of the atomic data the cross-sections were
smoothed to a resolution of 3000 km s−1 but in new data sets we no longer store the
smoothed cross-sections. Instead, newer cross-sections can be smoothed to the desired
resolution, set by a control parameter, when they are read in.
Second, a narrow resonance can mean that the autoionization lifetime of the upper
level may be comparable to, or even larger than, radiative transitions from the same level.
As a consequence the upper level may not be in LTE with respect to the ion and hence
the photoionization cross-section should not be used to compute the recombination rate.
When identified, such a resonance should be clipped out and the upper levels treated as a
bound state.
Third, photoionization cross-sections are usually computed in LS coupling. This
means, for example, that the multiplet structure of the resonances is not treated—a problem
more crucial when the resonances are “narrow”.

4.3. High Temperature Dielectronic Recombination (HTDR)

HTDR involves high Rydberg states [85,86] and it is very difficult to treat accu-
rately in stellar atmosphere codes. The easiest way to visualize HTDR is to discuss a
specific example.
Consider for example C III whose ground state is 2s2 1 S where we have omitted the
complete inner shell for simplicity. The states contributing to HTDR are the Rydberg
states of the form 2p nl that converge on the C IV state 2p 2 Po (Figure 4). Such states
can autoionize to give C IV 2s 2 S or the 2p electron can radiatively decay giving rise to
C III 2s nl. At “low” densities the nl electron will decay to a lower level, producing a
“real” recombination. Since the autoionization rates decay slowly with n, and since the 2p
→ 2s transition probability is approximately constant, high n values (e.g., up to n = 100)
determine the net recombination rates. Such levels are not typically included in nLTE
calculations. The process is further complicated because the autoionizing rates strongly
depend on the angular momentum—low “l” states have much higher autoionization
probabilities than do higher angular-momentum states [85,87].
At low densities the HTDR recombination will scale roughly as exp(− E/kT )/T 3/2
where E is the energy of the 2s-2p transition in C IV. Since the energy of the 2s-2p transition
is well known, and since the energy of the high Rydberg states is easily approximated,
the accuracy of the energy levels is not a crucial factor determining HTDR rates. For
some species, several Rydberg series may contribute to the HTDR rate, yielding a more
complicated temperature dependence than the simple expression provided above.
In Figure 5, the different recombination coefficients for C III are plotted. The radiative
recombination rate and the HTDR rate are from [83], while the LTDR rate is from [81].
The crucial importance of dielectronic recombination for C III is clearly demonstrated by
this figure.
Atoms 2023, 11, 54 12 of 27

Figure 5. Comparison of the recombination coefficients for normal radiative recombination, for
LTDR and for HTDR for recombination from C3+ to C2+ . Only at low temperatures (.1000 K) does
radiative recombination dominate. Above this temperature LTDR dominates until a temperature of
∼17,000 K, at which time HTDR becomes the dominant recombination mechanism.

5. Suppression of Dielectronic Recombination

5.1. Collisional Processes
The classic HTDR formula only applies at low densities. As the density rises, collisional
ionization by electrons can significantly suppress HTDR. This has been explicitly considered
for HTDR of C3+ to C2+ (i.e., C IV to C III) by [88,89]. The authors of [89] found suppression
factors of ∼0.7 at 104 , 0.4 at 106 , 0.2 at 108 , and 0.1 at 1010 cm−3 (these data were read from
Figure 1 in [90]). The reduction in the HTDR rate arises because the stabilizing transition
(2p-2s in the case of C III) from the autoionizing states leaves the electron in a high nl
state. As the electrons cascade down to lower nl states, they can be collisionally ionized
by electrons.

5.2. The Importance of the Radiation Field

The radiation field is typically regarded as unimportant in the dielectronic process,
but in stellar atmospheres and winds, the process could effectively suppress recombination,
as illustrated below. In principle, there are two suppression routes. The radiation field
can directly suppress the stabilizing transition or the radiation field can directly ionize
an electron out of the high nl state which the stabilizing transitions have left the ion in.
The latter is similar to collisional suppression, except it is the radiation field, rather than
collisions with electrons, which is reionizing the atom/ion.
For simplicity we treat the resonance as a line transition between two bound states,
with the upper level being the autoionizing level. The net recombination rate will be
given by
NR = nu Aul (1 − J̄/Slu ) (14)
where J̄ is the mean intensity in the line and is given by
Z ∞
J̄ = φ(ν) Jν dν , (15)
0

φ(ν) is the line absorption/emission profile (which, in general, is determined by the finite
lifetimes of the levels involved in the transitions, thermal motions of the atoms, and the
interaction of the radiating atom/ion with its neighbors (see [4], Chapter 9)) and Slu is the
line source function given by
 
2hν nu /gu
Slu = 2 . (16)
c nl /gl − nu /gu
Atoms 2023, 11, 54 13 of 27

In LTE nu = ( gu /gl )nl exp(−hν/kT ) and hence Slu simplifies to the Planck function. As
is readily apparent the net rate does not directly depend on the optical depth—such a
dependence only occurs indirectly through the dependence of J̄ on the optical depth.
In nebula conditions J̄/Slu is typically << 1 (since the nebula is very distant from the
star the radiation field is greatly diluted) and the contribution to the recombination rate by
this single transition is simply nu Aul . When the rates are summed over all resonances you
recover the LTDR/HDTR recombination rate. However, such a rate is typically an upper
limit since the radiation field can reduce this rate.
At depth in a stellar atmosphere J̄ ≡ Slu ≡ Bν , and thus the net LTDR and HTDR
rates are identically zero—that is, every downward transition in the stabilizing transition
is balanced by an upward transition. However, above the atmosphere the temperature
of the radiation field and the electrons are not the same. Typically J̄ will fall below Slu ;
however, in a wind J̄ can be greater than Slu in some transitions. In Figure 6 we show the
mean intensity (in the comoving frame) and the blackbody mean intensity at a temperature
of 1.6 × 104 K and a density of ∼1011 electrons cm−3 —roughly 50% of the emission in the
line referred to as C III λ2297 originates above that density. From that figure we see that
the radiation field at the wavelength of the C IV resonance transition, and at/near the
stabilizing transition, is close to a blackbody at the local electron temperature. Thus, the
radiation can act to suppress HTDR.
In Figure 7, we show the recombination and photoionization rates for n = 26 through
30 singlet states of C III (treated as a single level) for a test calculation in which we included
HTDR transitions for levels up to n = 30, and with no suppression of the recombination rate
with the angular orbital quantum number. The resulting model spectrum is almost identical
to the spectrum computed without HTDR—a consequence of the low temperatures in the
C III line-formation region and the suppression of HTDR via the radiation field in the
stabilizing transition. This result is model dependent—in practice the importance of HTDR
needs to be examined on a case-by-case basis.

Figure 6. Comparison of the mean intensity (in the comoving frame, red curve) and the blackbody
mean intensity (green dashed curve) at a temperature of 1.6 × 104 K and a density of ∼1011 electrons
cm−3 —roughly 50% of the emission in C III λ2297 originates above that density. At this density
the C IV 2s and 2p states are collisionally coupled and as a result the radiation field near the wave-
lengths of the C IV transitions at 1548, 1551 Å is also close to that of a blackbody. The blue curve is
similar to the red curve except that we used a Voigt profile for the line absorption/emission profile
(see Equation (15)), rather than the simple Doppler profile (see [4]) which is generally used when
computing the atmospheric structure and level populations. The use of a Voigt profile is crucial for
explaining the observed profile of the C IV resonance doublet at 1548, 1551 Å in WC stars [91].

The influence of the radiation field is not an issue if the resonance is included as part
of the photoionization cross-section as the influence of the radiation field is automatically
taken into account. It is also not an issue for “autoionizing” states treated as bound levels,
since the radiation field is again taken into account. However, it is a potential issue if
Atoms 2023, 11, 54 14 of 27

the LTDR or HTDR rate is included as a separate process, and the inverse process is
not included.

Figure 7. Illustration of the photoionization and recombination rates to/from a combined level
(n = 26, . . . , 30; singlet levels only) in C III. The solid curves show the rates with HTDR included, while
the dashed curves show the rates without HTDR included. At most densities the recombination and
photoionization rates agree closely in the model with HTDR. In such regions the influence of HTDR
on the ionization structure is suppressed. Towards the outer boundary the HTDR recombination rate
converges to that of a model without HTDR due to the decrease in electron temperature.

6. Astrophysical Examples
Below we discuss some examples of where photoionization data is crucial. It is
unrealistic to discuss all cases, since photoionization data is crucial in any photoionized
plasma and is crucial for nLTE analyses. For some plasmas, in which collisional processes
dominate, photoionization is less important but the inverse process (recombination) is
still critical.

6.1. Recombination Processes

The importance of photoionization/recombination processes depends critically on
the application. Here we discuss photoionized plasmas and gradually work our way up
in density.
In ionized nebulae and H II regions H and He lines are produced by recombination,
while the ionization is typically maintained via ionizations from the ground state. The
strongest metal lines (i.e., those not due to H and He), such as O III and N II, typically arise
via collisional excitation from the ground state. Metal recombination lines are much weaker,
simply because the metal abundances are typically a factor of 103 (or more) lower than
that of H. Some other lines are produced by line fluorescence, where the radiation field
in a bound–bound transition in one species gives rise to line emission in another species
(the Bowen mechanism). For example, some O III lines in planetary nebulae (gaseous
nebulae surrounding stars with effective temperatures in excess of 30,000 K) are produced
by the chance overlap of an O III line with He II Lyα [25,92]. With high signal-to-noise
spectra metal recombination lines are seen (e.g., [93,94]) and for most lines their strength is
effectively set by optically thin recombination (radiative and dielectronic) theory.
As the density increases, processes become increasingly complex. More transitions
become optically thick, affecting the cascade process and hence line strengths. Collisional
coupling between the levels also becomes more important. If the radiation field is not
too diluted, photoionization from excited states also becomes increasingly important. For
example, in O and WR stars, the ionization of He+ to He++ occurs predominantly from
the n = 2 state whose population is maintained via the intense radiation field in Lyα [95].
Similarly, the ionization of C IV is maintained from the n = 3 levels.
As the density further increases, lines become thicker and photoionization/recombination
can become more important since continuous processes at many wavelengths remain
Atoms 2023, 11, 54 15 of 27

optically thin. In hot stars the departure coefficients (=n/n∗ ) for H and He II levels typically
rise above the photosphere. Bound–bound transitions are optically thick, preventing
cascades. The radiation is diluted, hence recombinations into a level typically exceed
photoionizations from that level. Eventually, however, photon escape in lines becomes
important and the departure coefficients decrease. However, one must be careful with
generalizations—at some wavelengths (particularly in the Wien regime of the blackbody
curve) the rapid fall of the electron temperature with height above the photosphere means
that the energy density in the radiation field may initially exceed the radiation energy
density predicted by the blackbody formula for the local electron temperature.
Bound–bound processes are crucial for determining line strengths. However, it is
ultimately photoionization and recombination that determines the ionization state. In some
cases, charge exchange processes are crucial [96,97]. Particularly important are charge
exchange process of neutral H with, for example, Fe2+ and O+ . The reaction

O+ + H
O + H+
is resonant, has a total rate coefficient of order 10−9 cm3 s−1 [98], and is crucial for determin-
ing the O+ /O ratio in regions where the neutral hydrogen fraction exceeds roughly 10−3 .

6.2. The Sun

For the Sun, our nearest star, we can determine its structure in two ways. First, we can
use the observed Solar parameters (M, L, R∗ , abundances) to construct a theoretical model
of the Sun. Second, we can use helioseismology observations to constrain the internal
structure11 . Unfortunately, the structure determined from theoretical models and that
determined from the helioseismology observations are inconsistent. They can be reconciled
if the adopted opacities (for the relevant temperatures) are too low. This could arise if the
adopted O abundance is too low or alternatively it could arise from inaccuracies in the
opacities (i.e., inaccuracies in the photoionization cross-sections, oscillator strengths, etc).
The resolution of the problem is still unclear [50,99,100].

6.3. O, WR, and LBV Stars

O stars are the most luminous hydrogen-core burning stars known. They have masses
in the range 30 to ∼100 M and luminosities typically greater than 105 L . Due to nuclear
processing H is being converted to He in the core. At the same time most of the C and O
initially present have been converted to N. Mass loss, and mixing, then operate to reveal
this nuclear process at the stellar surface. During later evolution stages He is converted to
C and O, and mass loss can also reveal this material at the stellar surface.
All massive stars are losing mass in a stellar wind. In O stars and their descendants
(e.g., LBVs, WR stars) the winds are driven by radiation pressure. Due to their high
luminosities the stars are close to the Eddington limit12 . Consequently, it is relatively easy
for radiation pressure acting through bound–bound transitions to drive material off the
surface of the star via a stellar wind. Due to instabilities in the line driving, it is believed
that the winds are highly clumped (e.g., [73–75]). Additional evidence for clumping comes
from variability studies (e.g., [101,102]), from the anomalously low strength of some UV
resonance transitions relative to the level of Hα emission (e.g., [33–35]), and the weakness
of electron scattering wings associated with strong emission lines in P Cygni stars and WR
stars13 [103,104].
The wind density in massive stars varies considerably. For main sequence O stars
the winds are relatively weak and only affect a few spectral features. Their photosphere is
geometrically thin (i.e., <<radius of the star) and, in principle, can be modeled using plane-
parallel model atmospheres (i.e., the curvature of the star’s atmosphere can be ignored),
although the wind may still have an influence at some wavelengths. As the stars evolve,
the wind density tends to arise and become increasingly important, and the use of a plane-
parallel atmosphere is no longer valid. Indeed, in WR stars, the wind is so dense that
Atoms 2023, 11, 54 16 of 27

spectrum formation occurs in the stellar wind and nLTE spherical models that treat the
wind are essential.

6.3.1. N III and N IV lines in Of and WN stars

Of stars are evolved O stars that show emission in N III and He II λ4686 [105,106]. First
computations of model atmospheres suggested that the N III lines are driven into emission
by LTDR [107]. However, more recent work that includes line blanketing (by lines of iron
group elements) and winds reduces the importance of dielectronic recombination, and
continuum fluorescence acting through UV resonance transitions plays a crucial role [108].14
WN stars, which are a type of WR star, are evolved O stars which show abundances
which have been influenced by the CNO nuclear burning cycle—H is depleted (in many it
is absent), He is enhanced, and much of the C and O has been converted to N. In a WN star
such as HD 50896, several N IV lines are seen. The formation of these lines is complex, but
typically their strength is determined by a combination of dielectronic recombination and
continuum fluorescence [110]; while the models used by [110] did not include iron group
elements, more recent models with iron-group elements confirm the importance of LTDR
for WN stars. In Figure 8, we illustrate the influence of LTDR on several N IV emission
lines for a model appropriate to an early-type WN star (such as HD 50896).

Figure 8. Illustration of the influence of LTDR on the strength of several N IV emission lines. The
model in red is the full calculation, while for the blue spectrum we omitted LTDR transitions in the
calculation of the nLTE populations. A N IV transition at 1718 Å is also influenced by LTDR. For
these calculations we used smooth N IV photoionization cross-sections and the LTDR data of [81,82].
Calculations using the opacity photoionization cross-sections of [111], that were obtained from [22],
yield a spectrum very similar to that shown in red. The model has a luminosity of 3 × 105 L , a radius
(at a Rosseland optical depth of 2/3) of 2.9 R , an effective temperature of ∼78,000 K, a mass-loss rate
of Ṁ = 1.5 × 10−5 M yr−1 , and a volume filling factor (which characterizes the degree of clumping
in the wind) of 0.1.

6.3.2. Carbon in WC stars

WC stars are the evolved descendants of WN stars. Due to extensive mass loss, and
nuclear processing in the interior of the star, their atmospheres are devoid of H, and are
primarily composed of He, C and O (with similar mass fractions). Due to their dense stellar
winds, and high C and O abundance, emission lines of He, C, and O dominate the spectrum.
In the optical region, most of these arise from recombination, although optical depth effects
greatly complicate line formation [91].
Below we discuss the spectrum of the WC4-type star, BAT99-9, which has recently
been discussed by [37]. In most ways its spectrum, and parameters, are typical of other
WC4 stars in the Large Magellanic Cloud (LMC). However, it does differ in one important
aspect—it still exhibits one N V and two N IV emission lines. Nitrogen is expected to
disappear rapidly as a star transitions from WN to WC because N in the interior of the star
is converted to 22 Ne.
Atoms 2023, 11, 54 17 of 27

The electron temperature structure and wind velocity of a model for the LMC WC4
star, BAT99-9, is shown in Figure 9. The non-Planckian nature of the radiation field at two
depths in the wind is illustrated in Figure 10.

Figure 9. Illustration of the electron temperature (blue) and velocity structure (red) in the model for
the WC4-type star, BAT99-9. The model has log L/L = 5.48, an effective temperature of 84,000 K,
and a mass-loss rate of 1.4 × 10−5 M yr−1 .

Figure 10. An illustration of the radiation field in a WC4 star at a depth where V (r ) = 0.67 × V∞
( Ne = 1.7 × 1013 cm−3 ) (top panel) and at a depth V (r ) = 0.934 × V∞ ( Ne = 1.2 × 1011 cm−3 ) (lower
panel). Shown also is the blackbody spectrum at the local electron temperatures (Te = 4.90 × 104 K
and Te = 1.61 × 104 K). In the top panel (where V (r ) = 0.67 × V∞ ) we also illustrate the blackbody
spectrum at the effective temperature (Te = 8.19 × 104 K) that has been normalized to match the
model spectrum at 5.0 µm. As readily apparent, the local radiation field is very different from that
defined by the blackbody at the local electron temperature or that defined by the effective temperature.
Consequently, and because of the low electron densities, the ionization state of the gas, and the level
populations, are far from their LTE values. Due to the strong departures from LTE accurate atomic
data is crucial for determining the state of the gas and hence for predicting the stellar spectrum.

A characteristic of WC stars is the stratified ionization structure—as we move farther

out in the wind the ionization decreases. The complex ionization structure for C and O is
illustrated in Figure 11. Because of stratified ionization structure many different species
need to be included to model the spectrum. In BAT99-9 we see emission from four stages of
Atoms 2023, 11, 54 18 of 27

O (O III through O VI). To understand driving at the base of the wind additional ionization
stages are needed—in some models we include Fe IV through Fe XVII.

Figure 11. Illustration of the stratified ionization structure in the WC4 star, BAT99-9. On the top axis
we show the Rosseland optical depth (left plot) and the electron density in units of electrons per cm3
(right plot). The top scales are not linear. As we move out in the wind, the ionization decreases. This
variation is verified by the emission profile line widths—O VI lines are narrower than O III lines.

The stratified ionization structure is a consequence of several factors. First, the winds
of WR stars are not transparent. For example, the He II Lyman continuum (shortward
of 228 Å) is optically thick. Further, the transparency is a strong function of wavelength.
Second, as we move out in the wind the radiation field becomes diluted. Third, the intense
radiation field in some spectra bands can pump low lying levels. Because of this, and
because of the high densities which reduce cascades, ionizations from excited states can
play an important role in determining the ionization state of the gas.
In Figure 12 we illustrate the photoionization rate, normalized by the total recombi-
nation rate to all (included) levels. The normalization was primarily chosen to emphasize
the important process in the line formation region. In the inner regions of these dense
winds photoionizations and recombinations to each level will be in detailed balance. As we
move out in the wind the photoionization from most levels will decrease due to dilution of
the radiation, although for some levels the photoionization and recombination rates may
maintain equality if the continua are optically thick. For C III we see that three levels, in
order of importance, control the ionization—2s 2p 3 Po , 2s2 1 S, and 2s 2p 1 Po . On the other
hand, for C IV it is the n = 3 levels (3s, 3p, and 3d) that help to determine the C IV/C V
ionization ration. The ionization eventually shifts because the radiation is becoming diluted
(as 1/r2 ) and the populations of the n= 3 levels are also declining. One reason for the
difference in behavior of C III and C IV is there is often a rapid decline in the strength of
the radiation field shortward of ∼228 Å.
The presence of multiple ionization stages in the wind results in emission from mul-
tiple ionization stages. For example, in the case of BAT99-9 we see emission from two
ionization stages of carbon (C III & C IV)15 and four ionization stages of oxygen (O III
through O VI) with the characteristic line width (after allowance for blending and for the
formation mechanism) decreasing as the ionization increases. The origin of one O and two
C lines is shown in Figure 13—it shows that a given emission line originates over a range
of radii and that lower ionization features form farther out in the wind.
Atoms 2023, 11, 54 19 of 27

Figure 12. Illustration of the model photoionization rates for the WC4 star, BAT99-9. For illustration
purposes, the rates for the 3l states have been combined in the right plot.

Figure 13. Illustration of where O VI λ3811, C IV λ5471, and C III λ2297 originate in the wind.
R
ζ d ln r is proportional to the emission. High excitation lines originate in the inner denser wind,
while lower excitation lines originate in the outer wind.

6.4. C II in [WC] Stars

The LMC star J060819.93-715737.4 (hereafter J0608) has an exquisite C II spectrum—
over 150 lines can be identified in the optical [112,113]. It is classified as a [WC11] star
with the [] denoting that it is associated with a low mass star (<a fewM ) rather than
the product of the evolution of a massive star.16 The star is probably devoid of H (the
observed spectrum exhibits H emission but these probably arise in circumstellar material
and not in the stellar wind) and the C abundance is substantially enhanced (atmospheric
mass fractions of He and C are approximately 0.4 and 0.6, respectively); while the rich C II
spectrum is predominately produced by recombination, it cannot be explained by classical
optically thin cascades—optical depth effects play a crucial role in determining the relative
C II line strengths.
The spectrum of J0608 is similar to the [WC11] star CPD–56o 8032 whose spectrum has
been extensively discussed and analyzed [114–117]. Those studies show the importance of
LTDR in producing the spectrum and identify several optical lines that arise from autoion-
izing levels. The spectrum of J0608 has slightly lower ionization than CPD–56o 8032 and
has a lower terminal wind speed, and as a consequence provides a more ideal object by
which to explore the C II spectrum.
A small section of the rich C II spectrum is shown in Figure 14. The authors of [113]
argue that some of the lines are formed via fluorescence processes, but our own modeling
suggests that the spectrum can be explained by allowing for the optical depth effects and
by allowing for a transition from ionized to neutral carbon in the outer wind. The latter
truncates the emission of the strongest C III lines.
Atoms 2023, 11, 54 20 of 27

Figure 14. A small section of the spectrum of the WC 11 star J0608 (blue) which was obtained
by Nidia Morrell (private communication). A model fit (in red) is shown and model lines are
identified. The broad feature near 5115 Å (the first unidentified feature) is due to a resonance in the
C II free–free (i.e., Bremsstrahlung) cross-section. It arises from the 2s 2p(3 Po )3d 2 Po − 2s 2p(3 Po )4f 2 D
transition [117–119]. Both these states are autoionizing.

In Figure 14, we also show a free–free resonance (λ∼ 5115 Å) previously identified in
CPD–56o 8032 [117]. The observations were obtained with a resolution of ≈ 7 km s−1 and
hence the line is resolved. In CMFGEN the resonance is treated as a free–free resonance since
both levels involved in the transition are autoionizing (with A∼1011 s−1 ; [117]). In the case
of this free–free resonance it was trivial to omit it from a “continuum” calculation. The latter
is needed so we can rectify the spectrum (i.e., normalize the continuum to unity). However,
this is not the case for bound-free resonances that appear in the photoionization cross-
sections. Such resonances can appear in the computed continuum, distorting an otherwise
smooth spectrum. These resonances riddle the UV continuum spectrum. However, in
practice they are difficult to discern because of the rich forest of bound–bound transitions
which mask the continuum spectrum.

6.5. Supernovae
Supernovae are fascinating objects. They represent the end points of evolution for
many stars and are an important source of metals (astronomical jargon for all elements more
massive than He) in the Universe. Broadly speaking there are two classes of supernovae
—those arising from the core collapse of a massive star (e.g., [120]) and those arising from
the thermonuclear detonation of a white dwarf (WD) star (a compact object of stellar origin
with a mass less than ∼1.4 M that is supported by electron-degeneracy pressure). The
latter class is designated as a Type Ia SN and, while we know that it involves a WD, we do
not know in what type of binary system the explosion occurs.
An extensive discussion of the possible progenitors of Type Ia SNe is given by [121].
Type Ia SN could arise when the WD accretes hydrogen-rich material from a “normal” star
(e.g., a red supergiant or a main sequence star). As a WD accretes mass its radius shrinks
(assuming it does not eject the accreted mass via a surface explosion in an event called a
nova, which is believed to occur in many systems). As it approaches the Chandrasekhar
mass of 1.414 M (the upper mass limit or a WD star) it will undergo a thermonuclear
explosion. Another possibility is that the WD star accretes He rich material from a WD
companion. This material undergoes a surface thermonuclear explosion which triggers
an inward propagating shock that triggers the detonation of the accreting WD. A third
possibility involves collisions and mergers of two WD stars. In the first scenario the
exploding WD has a mass of 1.4 M , while in the other two cases the mass of the exploding
WD is (typically) less than 1.4 M . The different scenarios predict different chemical
compositions for the ejecta and thus determining the chemical composition of the ejecta
offers a potential means of determining the nature of exploding WD.
Atoms 2023, 11, 54 21 of 27

At late times (say 200 days) the spectra of Type Ia supernovae ejecta are dominated
by emission lines of Fe, although lines due to Ni, Ca, and S are also present. One issue
with current models of the ejecta is that they fail to yield an iron spectrum in agreement
with observation (e.g., [45,122]). Basically, the Fe II lines are too weak relative to Fe III
(Figure 15) and this limits our ability to interpret ejecta observations. Is the issue related
to a problem in the ejecta explosion models, is it due to the ejecta being clumped (which
enhances recombination and hence lowers the ionization), is it due to issues with the iron
atomic data, is it due to problems treating the thermalization of high-energy electrons [122],
or are we missing additional physics? Unfortunately in these systems the iron atomic data
is of crucial importance, since Fe II/ Fe III is of order unity and the lines of both species
probably form in the same region. Thus, a factor of 2 error in the Fe II recombination
rate will make a factor of 2 error in the Fe II/ Fe III ionization fraction and will change
the relative line strengths (which are produced via collisional excitations) by a factor of 2.
Fortunately, for Fe II and Fe III, HTDR is unimportant at the relevant temperatures, as can
be gleaned from the rates provided by [123]. Nebular spectra of Type Ia SNe 2

Figure
Figure1. Comparison
15. Illustration
of SUB1of anda CHAN
small models
section of the spectrum
to SN2011fe. Flux valuesofforaSN2011fe
Ia SN showing the influence
have been scaled of7clumping
by 4.225 × 10 to account for models at 1
Then, all flux values were scaled by the same value that is of order unity. Data from SN2011fe are shown in brown and are 204.5 d post B-band maximum
which enhances recombination and hence reduces the ionization state of the gas. In the unclumped
two most striking discrepancies between the models and observations are as follows: (i) the [Fe III] lines are too strong relative to the [Fe II] lines (espe
inmodel,
the unclumped f = 1, Fe
with models), (ii) lines
and III near 5000ofÅthe
the overprediction are[Catoo strong.
II] doublet Increasing
near the clumping
7300 Å (especially The data were ftaken
(i.e., decreasing
in model CHAN). ) from the
Supernova
lowers theArchive and collectedthus
ionization, from improving
Yaron & Gal-Yamthe(2012) and Mazzali
agreement. et al. (2015).the emission feature near 7400 Å (a
However,
blend of Fe II, Ni II, and Ca II lines) is worse. The shape of the feature near 5000 Å is also sensitive to
we discuss the effects on iron features, nickel features, and IMEs, clumping in CMFGEN differs from that of a concentric shell-
the adopted
respectively. Fe IIwe
Finally, photoionization
summarize our work cross-sections
in Section 4. and updated calculations
structure, which iscould also improve
susceptible the fit. effects ac
to radiative-transfer
a shell and requires a large number of depth points to resolv
7. Conclusions shells.
2 TECHNIQUE The clumping factor scales many variables, such as dens
Accurate photoionization cross-sections are essential for many areas of astrophysics.
(scaled by 1/f) and the emissivities and opacities (calculated u
2.1
The Ejecta models quality varies greatly with the application.
required The biggest
the populations needs
in the clumps are scaled
and then at “in- by f). This m
termediate”
This research uses densities where
two hydrodynamic nLTE
models is relevant,
of Wilk et al. (2018), clumping
and where formalismdensity
complex leaves theand massradiation
column density unchan
DDC10
processes(CHAN) and SCH5p5
directly (SUB1).
affect levelDDC10 is a MCh (1.40
populations. M"is
This case forhasmany
) the CMFGEN incorporated this clumping
astrophysical method since Hilli
phenom-
model from Blondin et al. (2013). Model SCH5p5 is a sub-MCh Miller (1999) first applied it to massive stars.
ena associated with, for example, stellar winds, accretion At adisks, andof supernovae
time-step ejecta. (∼ + 200 d
216.5 d post-explosion
(1.04 M" ) from Blondin et al. (2017), but we have scaled the density
56
by 0.98 (see Wilk et al. 2018) in order to have the same Ni. Both maximum), we re-solved the relativistic radiative-transfer equ
Funding:
CHAN Partial
and SUB1 havesupport
the same 56for the
Ni at work
0.62 was provided
M" . However, CHAN by NASA for our theory
models SUB1
grant and CHAN using a clumping
80NSSC20K0524 and factor (
has a stable
STScI GrantironNocore, whereas SUB1 does not. STScI
HST-AR-16131.001-A. We useisCMFGEN
operated by 0.33,
the0.25, and 0.10 (values
Association partially motivated
of Universities for Re-by modellin
tosearch
solve intheAstronomy,
spherically symmetric, time-dependent, relativistic radiation-driven winds in massive stars; see, e.g. Hillier & M
Inc., under NASA contract NAS 5-26555.
radiative transfer equation allowing for non-LTE processes. We 1999; Najarro 2001; Bouret et al. 2003; Puls et al. 2003).
take
Data these two models atStatement:
Availability 216.5 d post-explosion
CMFGENfrom , and Wilk
theetatomic
al. range used
data of values
byisCMFGEN
also consistent
, arewith what hasatbeen inferre
available
(2018). Table 1 lists the initial (accessed
masses for each model as well as2023).
the clumps in planetary nebulae (Boffi & Stanghellini 1994; Stasi
www.pitt.edu/~hillier on 1 February This site also contains some older O star
mass abundance of calcium, iron, cobalt, 58 Ni plus 60 Ni, and 56 Ni. et al. 2004; Ruiz et al. 2011). Since the previous time-step
models. Data from supernova calculations can be downloaded from Zenodo or requested
not computed using clumping in the models, we from thescaled the in
We see CHAN has more than twice the amount of stable nickel –
appropriate
58 60author. A grid of spectra are available from the
M( Ni) + M( Ni) – than SUB1 as well as almost a factor of 2 Pollux data base [124]. A large grid of
input populations by 1/f between successive ionizations. This si
more
CMFGEN spectra models has been constructed and is being made
calcium. scaling available
is adequate[125,126].
since time-dependent
Hillier willeffects
alsohave a negli
provide CMFGEN models upon request. influence on the spectrum.

2.2 Numerical treatment

3 R E S U LT S
Our original radiative-transfer calculations for our models did not
include the effects of clumping. Therefore, to treat clumping in To highlight the drop in ionization due to clumping for nor
our models, we make some simple assumptions with CMFGEN. We type SNe Ia, the optical spectrum of SN2011fe is plotted ag
assume that the clumps are ‘small’ (i.e. smaller than a mean-free the synthetic spectra of models SUB1 and CHAN for clum
path) and occupy a fraction, f, of the total volume. f is known as the values f = 1.00, 0.33, 0.25, and 0.10 in Fig. 1. For non-clum
volume-filling factor, and can be defined as f = #ρ$2 /#ρ 2 $, where models, [Fe III] lines are too strong while [Fe II] lines are too w
Atoms 2023, 11, 54 22 of 27

Acknowledgments: The author would like to thank P. J. Storey for extensive discussions on atomic
data, and for supplying atomic data on C II and C III that was directly used in this review. He would
also like to thank the numerous workers who have undertaken extensive atomic data calculations
and made their work freely available on the internet. A special thanks to Nidia Morrell who obtained
the high resolution spectrum of J0608. The invaluable comments made by the referees are also greatly
appreciated. This paper has made use of NASA’s Astrophysics Data System Bibliographic Services.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:

ADS Astrophysics Data System

ESA European Space Agency
HST Hubble Space Telescope
LTE Local thermodynamic equilibrium
nLTE Non-local thermodynamic equilibrium
LTDR Low temperature dielectronic recombination
HTDR High temperature dielectronic recombination
LBV Luminous blue variable
LS coupling Total orbital angular momentum (L) is coupled with the total spin (S)
NASA National Aeronautics and Space Administration
SN Supernova
WD White dwarf
WR star Wolf–Rayet star
WN Wolf–Rayet star belonging to the nitrogen sequence
WC Wolf–Rayet star belonging to the carbon sequence

Notes
1 The effective temperature of the star is defined by the relation L = 4πR2∗ σSB Teff 4 where L is the stellar luminosity (energy emitted
per second), σSB the Stefan–Boltzmann constant, and R∗ is the radius of the star.
2 The meaning of “accurate” is highly context dependent. Atomic data calculations can, in some cases, give energy levels accurate
to 1% and for some purposes this is sufficient. However, for spectral modeling such energy levels cannot be used to compute
transition wavelengths—a 1% shift (which will be potentially larger if the levels are close in energy) will move a line far from its
correct location, influencing spectral synthesis calculations. Moreover, in non-LTE a wrong wavelength will influence how a line
interacts with neighboring transitions. In O supergiants two weak Fe IV lines, that overlap with He I λ304, influence the strength
of He I singlet transitions in the optical and accurate wavelengths (and oscillator strengths) of these Fe IV lines are crucial for
understanding the He I singlet transitions [1].
3 Strictly speaking, a radiation temperature is only well defined if the radiation field is Planckian. However, astronomers often use
color temperatures, defined by fitting a scaled blackbody ratio to the flux at two wavelengths, to characterize the nature of the
radiation field in some pass band. In nLTE, astronomers may also use the excitation temperature to characterize the excitation or
ionization state of a gas. In general these will not be the same as the local electron temperature, and will vary with level and
ionization stage (though possibly in a systematic way).
4 The Sun’s atmosphere is cool and dense enough for molecules to form and 50 molecular species have been identified [8]. In
the solar spectrum, spectral features due, for example, to CO, SiO, H2 , OH, CH, C2 , and CN, have been identified [8,9]. Dust
formation in red giants and supergiants is common but not well understood [10], and in some cases may be associated with
non-equilibrium chemistry [11].
5 Throughout the article we neglect full shells when providing the electron configuration. We use the principal quantum number
(n), orbital angular momentum number (l = 0, . . . , n − 1 = s, p, d, f, g . . . ), and spin (±1/2) to describe the state of an electron.
Thus, 2p indicates an electron with n = 2 and l = 1. LS-coupling (in which the orbital angular momenta are coupled and the
electron spins are coupled) is used to provide the term designation. A term designation has the format 2S+1 Lx where S is the sum
of the (valence) electron spins, L is the total orbital angular momentum, and “o” is used to indicate that the arithmetic sum of the
electron orbital angular momenta is odd (o) or even (in which case e is omitted by convention). An excellent primer on atomic
spectroscopy is provided by [63] .
6 WR stars are a class of massive stars that evolved from O stars (stars with initial masses & 15 M ). They are experiencing mass
loss via a stellar wind (induced by radiation pressure acting through bound–bound transitions) with a mass-loss rate typically in
excess of 10−5 M yr−1 and a terminal wind speed of ∼1000 to 3500 km s−1 [64,65]. In many WR stars the wind is sufficiently
Atoms 2023, 11, 54 23 of 27

dense that the entire spectrum we observe originates in the wind—the hydrostatic core of the star is not seen. There are two main
WR classes: WN stars exhibit N and He (and sometimes H) emission lines, and exhibit enhanced N and He at the stellar surface
due to the CNO cycle (the main H-fusion chain in massive stars). WC stars exhibit emission lines of He, C, and O, with a C
abundance comparable to that of He (e.g., [66,67]). They have lost all of their hydrogen envelope, with the enhanced C abundance
arising from the triple alpha process (3 4 He→12 C).
7 A P Cygni profile is formed when continuum radiation is absorbed and scattered by outflowing material. Outflowing gas along
the line of sight absorbs continuum radiation and scatters it out of the line of sight, producing blue-shifted absorption. Radiation
absorbed in other directions can be scattered into the line of sight and, for a spherically symmetric expanding gas, the combination
with the blue-shifted absorption will give rise to red-shifted emission.
8 The ejecta of Type Ia SNe are composed primarily of intermediate mass elements (Ca, Si) and iron group (Fe, Ni, Co) elements. In
such ejecta we may need to treat Auger ionization more rigorously since it could potentially affect the ionization state of the gas
and the thermalization of non-thermal electrons. The non-thermal electrons are initially produced via Compton scattering of
gamma-ray photons produced from decay of radioactive 56 Ni and 56 Co. In this case inner shell ionization will most likely occur
via non-thermal electrons. However the subsequent Auger ionization and fluorescence are independent of how the K-shell hole
was created.
9 From AUTOSTRUCTURE calculations made by a collaboration of researchers at Auburn University, Rollins College, the University of
Strathclyde, and other universities. Tables produced by N. R. Badnell and are available at Atomic Data from AUTOSTRUCTURE.
10 A signal processing term that refers to the distortion of data due to sampling which is too coarse. In the present case a narrow but
strong resonance could be missed in the photoionization cross-section when the frequency sampling is too coarse. Alternatively,
its influence could be artificially enhanced if it is not fully resolved.
11 The Sun is simultaneously oscillating in thousands of different vibration modes. The frequency and strength of these modes
depends on the internal structure of the Sun (e.g., the depth of the convection, the sound speed).
12 At the Eddington limit the force arising from the scattering of radiation by free electrons matches the gravitational force.
13 The strength of most emission lines in WR stars is proportional to the density squared. Thus, a clumped wind can yield the same
line strengths for a lower mass-loss rate (i.e., for a lower average density). On the other hand electron scattering line wings arise
from Thomson scattering of line photons by free electrons and hence scale with density. Thus, the strength of electron scattering
wings relative to their neighboring emission line can act as a global diagnostic of clumping. In WR stars the wings are offset to
the red from their originating transition because of the large outflow velocities.
14 In this process a strong transition (typically in the UV) absorbs continuum photons, a process whose efficiency is enhanced by the
velocity field which allows the UV transitions to intercept more continuum radiation. In many cases the absorbed photons will
typically be re-emitted in the same transition. However, in some cases the upper levels have an alternate decay route—decay via
this transition can then lead to emission in this bound–bound transition. This is also known as the Swings mechanism [109].
15 C II emission is also predicted but this is masked by blending with other lines.
16 The 11 appended to WC denotes the ionization class of the star—in this case, a spectrum dominated by C II with little evidence
for C III.

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