Chemical Physics 515 (2018) 369–374

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Chemical Physics
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Inelastic processes in low-energy iron-hydrogen collisions T

a,b,⁎ a,b b
S.A. Yakovleva , A.K. Belyaev , W.P. Kraemer
a
Department of Theoretical Physics and Astronomy, Herzen University, St. Petersburg 191186, Russia
b
Max-Planck Institute for Astrophysics, Postfach 1371, D-85741 Garching, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: The simplified model approach is applied to low-energy collisions of iron atoms and cations with hydrogen
atomic processes atoms and anions.Inelastic collisional processes for all transitions involving 97 low-lying covalent Fe + H states
inelastic collisions and two ionic Fe+ + H− molecular states are treated, and rate coefficients for excitation, de-excitation, ion-pair
rate coefficients formation and neutralization processes are calculated within the 6 Σ+ 6Π, 6 Δ, 4 Σ−, 4 Π, 4 Δ and 4Φ molecular
symmetries.Rate coefficients with highest values correspond to the mutual neutralization processes Fe+ (3d6 4s 6D)
+ H−→ Fe(3d6 (3G)4s4p(3P°) w 5G°, v 5F°, y 5H°) + H(1s 2S) and Fe+ (3d7 4 F) + H−→ Fe(3d7 ( 2 G) 4p w 3F°, y 3H°,
v 3G°) + H(1s 2S). The highest rate coefficients for excitation and de-excitation correspond to the Fe(3d6 (3G)4s4p
(3P°) v 5F°) + H(1s 2S)→ Fe(3d6 (3G)4s4p(3P°) y 5H°) + H(1s 2S) process within the sextet molecular symmetries
and the Fe(3d7 (2D2 )4p v 3F°) + H(1s 2S) → Fe(3d7 (2G)4p v 3G°) + H(1s 2S) process within the quartet molecular
symmetries.

1. Introduction
Many inelastic physical processes and chemical reactions are based
on non-adiabatic transitions including those taken place in a vicinity of
conical intersections [1,2]. Many of them are of both fundamental and
practical interests, for example, in astrophysics.
One of the most important problems in modern astrophysics is to
determine absolute and relative abundances of chemical elements in the
Universe [3,4]. This information can be obtained from stellar spectra
modelling. For many stars, especially in case of cold stars, non-Local
Thermodynamic Equilibrium (non-LTE) effects should be considered in
stellar atmosphere modelling. Non-LTE modelling requires information
on radiative and collisional processes, mainly for collisions of different
species with electrons and hydrogen. Information on radiative pro-
cesses and inelastic collisions with electrons is known relatively well
while collisions with hydrogen still cause significant uncertainties for
spectra formation modelling in stellar atmospheres.
Iron is of significant interest for measurement of metallicity and a
stellar effective temperature. Many studies have been performed for
LTE and non-LTE modelling of iron line formation [5–7], see also re-
ferences therein. These studies used the Drawin formula [8–10] to es-
timate data on iron-hydrogen inelastic collisions. It has been shown
[11] that the Drawin formula is not reliable: It is based on a classical
assumption and provides data which deviate by several orders of
magnitude from quantum results. For this reason more reliable data
based on a quantum background are required. Very recently, such data
were estimated in [12] using the Linear Combination of Atomic Orbitals
(LCAO) method [13–15]. It is well known that the LCAO method is
approximate, so additional estimates are desirable. An alternative ap-
proach for atomic collision data estimates is the semi-empirical
asymptotic method proposed in [16]. Comparison of these methods
[17] showed that both approaches perform equally well on average.
That is why the present work provides an alternative set of atomic data
on low-energy iron-hydrogen inelastic collisions by means of the sim-
plified model [18] based on the semi-empirical asymptotic approach.
2. Simplified model
Atomic data calculations for collisions of iron atoms and positive
ions with hydrogen atoms and negative ions are performed within the
simplified model approach proposed in [18]. The approach is for-
mulated within the Born-Oppenheimer formalism and treats a scat-
tering problem into two steps: A fixed-nuclei electronic structure cal-
culation and a non-adiabatic nuclear dynamical treatment. Full
quantum studies of atomic collisions with hydrogen [19–26] showed
that an interaction of ionic and covalent molecular states provides the
dominant mechanism for non-adiabatic transitions. This conclusion
allowed us to develop a model approach for estimating rate coefficients
of inelastic processes in collisions of different species with hydrogen.
Within the simplified model, the fixed-nuclei electronic structure

⁎
Corresponding author at: Department of Theoretical Physics and Astronomy, Herzen University, St. Petersburg 191186, Russia.
E-mail address: cvetaja@gmail.com (S.A. Yakovleva).

https://doi.org/10.1016/j.chemphys.2018.08.012

Available online 09 August 2018

0301-0104/ © 2018 Elsevier B.V. All rights reserved.
S.A. Yakovleva et al. Chemical Physics 515 (2018) 369–374

Table 1
Scattering channels correlated to FeH molecular sextet states, molecular symmetries, the asymptotic energies (J-average experimental values taken from NIST [29])
with respect to the ground state and the electron bound energies with respect to the ionisation limit.
j Scattering channels Molecular symmetry Asymptotic Electron bound
energies (eV) energies (eV)

1 Fe(3d64s2 a 5D) + H(1s 2S) 6Σ+ 6Π 6Δ 0.04996085 −7.85251

2 Fe(3d7 ( 4F)4s a 5F) + H(1s 2S) 6Π 6Δ 0.92489133 −6.97758
3 Fe(3d7 ( 4P)4s a 5P) + H(1s 2S) 6Π 2.19260559 −5.70986
4 Fe(3d6 ( 5D)4s4p( 3P°)z 7D°) + H(1s 2S) 6Π 6Δ 2.43307424 −5.46939
5 Fe(3d6 ( 5D)4s4p( 3P°)z 7F°) + H(1s 2S) 6Σ+ 6Π 6Δ 2.84271475 −5.05975
6 Fe(3d6 ( 5D)4s4p( 3P°)z 7P°) + H(1s 2S) 6Σ+ 6Π 2.98272753 −4.91974
7 Fe(3d6 ( 5D)4s4p( 3P°)z 5D°) + H(1s 2S) 6Π 6Δ 3.24227730 −4.66019
8 Fe(3d6 ( 5D)4s4p( 3P°)z 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 3.37478335 −4.52768
9 Fe(3d6 ( 5D)4s4p( 3P°)z 5P°) + H(1s 2S) 6Σ+ 6Π 3.63635398 −4.26611
10 Fe(3d6 ( 5D)4s4p(1P°)y 5P°) + H(1s 2S) 6Σ+ 6Π 4.59059969 −3.31187
11 Fe(3d6 ( 5D)4s4p(1P°)x 5D°) + H(1s 2S) 6Π 6Δ 4.95581067 −2.90689
12 Fe(3d6 ( 5D)4s4p(1P°)x 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 5.03927561 −2.86320
13 Fe(3d6 ( 3P2)4s4p( 3P°)x 5P°) + H(1s 2S) 6Σ+ 6Π 5.30044964 −2.60202
14 Fe(3d6 ( 3H)4s4p( 3P°)y 5G°) + H(1s 2S) 6Π 6Δ 5.32704182 −2.57543
15 Fe(3d6 ( 5D)4s( 6D)5se 7D) + H(1s 2S) 6Σ+ 6Π 6Δ 5.35946962 −2.54300
16 Fe(3d6 ( 3H)4s4p( 3P°)z 5I°) + H(1s 2S) 6Π 6Δ 5.36061032 −2.54186
17 Fe(3d6 ( 3H)4s4p( 3P°)z 5H°) + H(1s 2S) 6Σ+ 6Π 6Δ 5.35408681 −2.54838
18 Fe(3d6 ( 3P2)4s4p( 3P°)w 5D°) + H(1s 2S) 6Π 6Δ 5.44322751 −2.45924
19 Fe(3d6 ( 3F2)4s4p( 3P°)v 5D°) + H(1s 2S) 6Π 6Δ 5.49396633 −2.30050
20 Fe(3d6 ( 3F2)4s4p( 3P°)w 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 5.50078154 −2.40169
21 Fe(3d6 ( 5D)4s( 6D)5se 5D) + H(1s 2S) 6Σ+ 6Π 6Δ 5.58580685 −2.31666
22 Fe(3d6 ( 3F2)4s4p( 3P°)x 5G°) + H(1s 2S) 6Π 6Δ 5.67465861 −2.58248
23 Fe(3d6 ( 3G)4s4p( 3P°)w 5G°) + H(1s 2S) 6Π 6Δ 5.89245994 −2.01001
24 Fe(3d6 ( 3G)4s4p( 3P°)v 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 5.94466598 −1.95780
25 Fe(3d6 ( 3G)4s4p( 3P°)y 5H°) + H(1s 2S) 6Σ+ 6Π 6Δ 5.97370641 −1.92876
26 Fe(3d6 ( 5D)4s( 6D)5pn 7D°) + H(1s 2S) 6Π 6Δ 6.15684845 −1.74562
27 Fe(3d6 ( 5D)4s( 6D)5pn 7F°) + H(1s 2S) 6Σ+ 6Π 6Δ 6.22074512 −1.68172
28 Fe(3d6 ( 5D)4s( 6D)5pn 7P°) + H(1s 2S) 6Σ+ 6Π 6.26165157 −1.64082
29 Fe(3d6 ( 5D)4s( 6D)4d e 7F) + H(1s 2S) 6Π 6Δ 6.30941927 −1.59305
30 Fe(3d6 ( 5D)4s( 6D)4d f 7D) + H(1s 2S) 6Σ+ 6Π 6Δ 6.28989269 −1.61258
31 Fe(3d6 ( 5D)4s( 6D)4d f 5D) + H(1s 2S) 6Σ+ 6Π 6Δ 6.27193121 −1.63054
32 Fe(3d6 ( 5D)4s( 6D)4d e 7P) + H(1s 2S) 6Π 6.27515346 −1.62731
33 Fe(3d6 ( 5D)4s( 6D)4d e 5G) + H(1s 2S) 6Σ+ 6Π 6Δ 6.30594892 −1.59410
34 Fe(3d6 ( 5D)4s( 6D)4d e 7G) + H(1s 2S) 6Σ+ 6Π 6Δ 6.33796825 −1.56450
35 Fe(3d6 ( 5D)4s( 6D)5pu 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 6.37606242 −1.52641
36 Fe(3d6 ( 5D)4s( 6D)4d e 5S) + H(1s 2S) 6Σ+ 6.34165655 −1.56081
37 Fe(3d6 ( 5D)4s( 6D)5pt 5D°) + H(1s 2S) 6Π 6Δ 6.37176858 −1.53070
38 Fe(3d6 ( 5D)4s( 6D)4d f 5F) + H(1s 2S) 6Π 6Δ 6.37741913 −1.52473
39 Fe(3d6 ( 5D)4s( 4D)5sg 5D) + H(1s 2S) 6Σ+ 6Π 6Δ 6.41592345 −1.48654
40 Fe(3d6 ( 5D)4s( 6D)4d e 7S) + H(1s 2S) 6Σ+ 6.39387709 −1.50859
41 Fe(3d6 ( 5D)4s( 6D)5pu 5P°) + H(1s 2S) 6Σ+ 6Π 6.42981876 −1.47265
42 Fe(3d6 ( 5D)4s( 6D)4d e 5P) + H(1s 2S) 6Π 6.44103706 −1.46143
43 Fe(3d6 ( 3D)4s4p( 3P°) 5F°) + H(1s 2S) 6Σ+ 6Π 6Δ 6.67718199 −1.22529
44 Fe(3d6 ( 5D)4s( 6D)6sg 7D) + H(1s 2S) 6Σ+ 6Π 6Δ 6.72018064 −1.18229
45 Fe(3d6 ( 3D)4s4p( 3P°) 5D°) + H(1s 2S) 6Π 6Δ 6.70261192 −1.19985
46 Fe(3d6 ( 3D)4s4p( 3P°)t 5P°) + H(1s 2S) 6Σ+ 6Π 6.70677938 −1.19569
ion Fe(3d64s6D) + H− (1s21S) 6Σ+ 6Π 6Δ 7.1484681 −0.754

calculations are performed via evaluating ionic and covalent diabatic Kif (T ) = ∑ pistat ,2S + 1,Λ Nif2S + 1,Λ (T ;Ef ),
potentials by their asymptotic forms and estimating the off-diagonal 2S + 1,Λ (1)
matrix elements by the semi-empirical asymptotic formula [27]. In
where pistat ,2S + 1,Λ
is a statistical probability for population of the initial
general, a non-adiabatic nuclear dynamical treatment is multichannel,
molecular state i with a given molecular symmetry 2S + 1Λ from a scat-
but in order to derive a general rule for a rate coefficient it is necessary
tering channel, S spin of a molecular state, T a temperature. Rate
to consider a two- or three-state problem. Papers [18,28] show how to
coefficients for excitation and de-excitation processes are expressed via
express a rate coefficient Kif (T ) for a transition i → f via reduced rate
reduced rate coefficients Dif2S + 1,Λ (T ;Ei, Ef ) depending on two electron
coefficients. A rate coefficient for a mutual neutralization process bound (binding) energies Ei and Ef of an atom in an initial i and a final f
(i = ionic ) is written via reduced rate coefficients Nif2S + 1,Λ (T ;Ef ) that
states
depend on a single electron bound (binding) energy Ef of an atom in a
final state f Kif (T ) = ∑ pistat ,2S + 1,Λ Dif2S + 1,Λ (T ;Ei, Ef ).
2S + 1,Λ (2)

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S.A. Yakovleva et al. Chemical Physics 515 (2018) 369–374

Table 2
Scattering channels correlated to FeH molecular states, molecular symmetries, the asymptotic energies (J-average experimental values taken from NIST [29]) with
respect to the ground state and the electron bound energies with respect to the ionisation limit.
j Scattering channels Molecular symmetry Asymptotic Electron bound
energies (eV) energies (eV)

1 Fe(3d7 ( 4F)4s a 5F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 0.92489133 −7.27720

2 Fe(3d7 ( 4F)4s a 3F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 1.53832188 −6.66377
3 Fe(3d7 ( 4P)4s a 5P) + H(1s 2S) 4Σ− 4Π 2.19260559 −6.00948
4 Fe(3d7 ( 2G)4s a 3G) + H(1s 2S) 4Π 4Δ 4Φ 2.72127508 −5.48081
5 Fe(3d7 ( 4P)4s b 3P) + H(1s 2S) 4Σ− 4Π 2.83901513 −5.36307
6 Fe(3d7 ( 2P)4s c 3P) + H(1s 2S) 4Σ− 4Π 3.04569224 −5.15640
7 Fe(3d7 ( 2H)4s b 3H) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 3.26449161 −4.93760
8 Fe(3d7 ( 2D2)4s a 3D) + H(1s 2S) 4Π 4Δ 3.27246249 −4.92963
9 Fe(3d8c 3F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 4.12441248 −4.07768
10 Fe(3d7 ( 4F)4p y 5D°) + H(1s 2S) 4Σ− 4Π 4Δ 4.15393730 −4.04815
11 Fe(3d7 ( 4F)4p y 5F°) + H(1s 2S) 4Π 4Δ 4Φ 4.23005308 −3.97204
12 Fe(3d7 ( 4F)4p z 5G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 4.35723829 −3.84485
13 Fe(3d7 ( 4F)4p z 3G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 4.42501882 −3.77707
14 Fe(3d7 ( 4F)4p y 3F°) + H(1s 2S) 4Π 4Δ 4Φ 4.59285060 −3.60924
15 Fe(3d7 ( 2F)4s d 3F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 4.58709337 −3.61500
16 Fe(3d7 ( 4F)4p y 3D°) + H(1s 2S) 4Σ− 4Π 4Δ 4.77425856 −3.42783
17 Fe(3d83P) + H(1s 2S) 4Σ− 4Π 5.08509890 −3.11699
18 Fe(3d7 ( 4P)4p y 5S°) + H(1s 2S) 4Σ− 5.51876129 −2.68333
19 Fe(3d7 ( 4P)4p w 5P°) + H(1s 2S) 4Π 5.73433944 −2.46775
20 Fe(3d7 ( 4P)4p u 5D°) + H(1s 2S) 4Σ− 4Π 4Δ 5.80666770 −2.39542
21 Fe(3d7 ( 4F)5se 5F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 5.88959744 −2.31249
22 Fe(3d7 ( 4P)4p w 3D°) + H(1s 2S) 4Σ− 4Π 4Δ 5.84062126 −2.36147
23 Fe(3d7 ( 4P)4p y 3S°) + H(1s 2S) 4Σ− 5.89614414 −2.30594
24 Fe(3d7 ( 4F)5se 3F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 5.99855299 −2.20354
25 Fe(3d7 ( 4P)4p x 3P°) + H(1s 2S) 4Π 5.99989483 −2.20219
26 Fe(3d7 ( 2G)4p w 3F°) + H(1s 2S) 4Π 4Δ 4Φ 6.10383604 −2.09825
27 Fe(3d7 ( 2G)4p y 3H°) + H(1s 2S) 4Π 4Δ 4Φ 6.14599331 −2.05610
28 Fe(3d7 ( 2G)4p v 3G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.15179743 −2.05029
29 Fe(3d7 ( 2P)4p w 3P°) + H(1s 2S) 4Π 6.21319464 −1.98889
30 Fe(3d7 ( 2D2)4p v 3F°) + H(1s 2S) 4Π 4Δ 4Φ 6.36041918 −1.84167
31 Fe(3d7 ( 2H)4p u 3G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.39623957 −1.80585
32 Fe(3d7 ( 2P)4p u 3D°) + H(1s 2S) 4Σ− 4Π 4Δ 6.47036892 −1.73172
33 Fe(3d7 ( 2D2)4p t 3D°) + H(1s 2S) 4Σ− 4Π 4Δ 6.50901018 −1.69308
34 Fe(3d7 ( 2H)4p w 3H°) + H(1s 2S) 4Π 4Δ 4Φ 6.51958310 −1.68251
35 Fe(3d7 ( 2H)4p y 3I°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.53176829 −1.67032
36 Fe(3d7 ( 4F)5p 3G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.64710081 −1.55499
37 Fe(3d7 ( 2D2)4p v 3P°) + H(1s 2S) 4Π 6.57536706 −1.62672
38 Fe(3d7 ( 4F)4d g 5F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.64371251 −1.55838
39 Fe(3d7 ( 4F)5p 5G°) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.65176115 −1.55033
40 Fe(3d7 ( 4F)5p 5F°) + H(1s 2S) 4Π 4Δ 4Φ 6.63472689 −1.56736
41 Fe(3d7 ( 4F)4d h 5D) + H(1s 2S) 4Π 4Δ 6.64063545 −1.56145
42 Fe(3d7 ( 4F)4d f 5P) + H(1s 2S) 4Σ− 4Π 6.62690168 −1.57519
43 Fe(3d7 ( 4F)4d f 5G) + H(1s 2S) 4Π 4Δ 4Φ 6.64617193 −1.55592
44 Fe(3d7 ( 4F)4d e 5H) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.67062383 −1.53146
45 Fe(3d7 ( 4F)5p 3F°) + H(1s 2S) 4Π 4Δ 4Φ 6.69228138 −1.50981
46 Fe(3d7 ( 4F)5p 5D°) + H(1s 2S) 4Σ− 4Π 4Δ 6.69230351 −1.50979
47 Fe(3d7 ( 4F)4d e 3G) + H(1s 2S) 4Π 4Δ 4Φ 6.69692913 −1.50516
48 Fe(3d7 ( 4F)4d f 3D) + H(1s 2S) 4Π 4Δ 6.69443917 −1.50765
49 Fe(3d7 ( 2P)4p x 3S°) + H(1s 2S) 4Σ− 6.67138580 −1.53070
50 Fe(3d7 ( 4F)5p 3D°) + H(1s 2S) 4Σ− 4Π 4Δ 6.71994846 −1.48214
51 Fe(3d7 ( 4F)4d e 3H) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.71716587 −1.48492
52 Fe(3d7 ( 4F)4d f 3F) + H(1s 2S) 4Σ− 4Π 4Δ 4Φ 6.81864978 −1.38344
53 Fe(3d7 ( 4F)4d e 3P) + H(1s 2S) 4Σ− 4Π 6.83639506 −1.36569
ion Fe+ (3d74F) + H− (1s21S) 4Σ− 4Π 4Δ 4Φ 7.44808881 −0.754

The dependences of the reduced rate coefficients Nif2S + 1,Λ (T ;Ef ) and
Dif2S + 1,Λ (T ;Ei, Ef ) on electron bound energies for the temperature range
from T = 1000 K till 10, 000 K are tabulated in Ref. [18] for a case of a
neutral collisional quasimolecule and in Ref. [28] for charged colli-
sional quasimolecules.
In the present work the neutral FeH quasimolecule is considered, so
the results of the paper [18] are employed. For this purpose, molecular
symmetries leading to non-adiabatic transitions should be determined
and collisional processes in each symmetry should be investigated.
Since the ionic-covalent interaction provides the dominant mechanism
for non-adiabatic transitions, these molecular symmetries are de-
termined by molecular symmetries of ionic molecular states.

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S.A. Yakovleva et al.
Fig. 1. Graphical representation of the rate coefficients (in units of cm3s−1) at T = 6′000 K in iron-hydrogen collisions due to transitions within the 6Σ+, 6Π and 6Δ
molecular symmetries.
3. Fe + H and Fe+ + H− collisions
Two ionic molecular states of a FeH quasimolecule are included into
consideration since the first-excited ionic molecular state has another
multiplicity than the ground state one and is energetically close to the
ground state providing significant rate coefficients. The ground ionic
state Fe+ (3d64s 6D) + H− has three molecular symmetries: 6Σ+, 6Π and
6Δ . The first-excited ionic state Fe+ (3d74F) + H− has the 4Σ−, 4Π, 4Δ and
4Φ molecular symmetries. For this reason two sets of dynamical cal-
culations are performed to treat non-adiabatic transitions between
molecular states of the same symmetry, that is, within the sextet and the
quartet molecular symmetries. The simplified model allows one to es-
timate rate coefficients only for inelastic collision processes due to one-
electron transitions, so only molecular states that lead to one-electron
processes are considered in the present paper. The molecular states are
listed in Tables 1 and 2. Table 1 contains 46 sextet molecular states
coupled with the ground ionic state, while 53 quartet molecular states
coupled with the first-excited ionic state are collected in Table 2. Note
that two states, Fe(3d 7 ( 4F )4s a 5F ) and Fe(3d 7 ( 4P )4s a 5P ) , appeal in
both tables since they provide molecular states of both spin multi-
plicities.
Rate coefficients for excitation, de-excitation, ion-pair formation
and mutual neutralization processes are calculated by using the sim-
plified model for temperatures from 1000 till 10, 000 K. Graphical re-
presentations of the calculated data at T = 6000 K for transitions within
different symmetries (different spin multiplicities) are shown in Fig. 1
and Fig. 2. These figures show that the largest rate coefficients belong
to the mutual neutralization processes. In particular, within the sextet
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Chemical Physics 515 (2018) 369–374
symmetries, the rate coefficients with the highest values, greater than
10−8 cm3/s , correspond to mutual neutralization processes into the fol-
lowing iron states Fe(y 5G°, z 5I°, z 5H°, e 7D, e 5D, w 5D°, v 5D°, w 5F°,
x 5G°, w 5G°, v 5F°, y 5H°, n 7D°, n 7F°, n 7P°, e 7F, f 7D, f 5D, e 5G) (scattering
channel labels j = 14–31, 33, see Table 1). Within the quartet sym-
metries, the highest rate coefficients with the values larger than
10−8 cm3/s correspond to the mutual neutralization processes into the
following iron states Fe(u 5D°, e 5F, w 3D°, e 3F, x 3P°, w 3F°, y 3H°, v 3G°,
w 3P°, v 3F°, u 3G°, u 3D°, t 3D°, w 3H°, y 3I°) (scattering channel labels
j = 20–22, 24–35, see Table 2). At T = 6000 K, the maximal value is
equal to 6.83 × 10−8 cm3 s−1 and corresponds to the mutual neutraliza-
tion process into the Fe(3d7 ( 2G)4p v 3G°) final state within the quartet
spin multiplicity. Within the sextet spin multiplicity the maximal value
of the rate coefficient at T = 6000 K is 6.78 × 10−8 cm3 s−1 and corre-
sponds to the mutual neutralization to the Fe(3d6 ( 3G)4s4p( 3P°)v 5F°)
final state. The reverse processes, ion-pair formation, also have sig-
nificant values, but typically an order of magnitude smaller. Among the
excitation and de-excitation processes, the largest rate coefficients with
the values greater than 10−9 cm3/s correspond to the partial processes
involving the same iron states in both spin multiplicities. The highest
rate coefficients for excitation and de-excitation correspond to the Fe
(3d6 (3G)4s4p(3P°) v 5F°) + H(1s 2S) →Fe(3d6 (3G)4s4p(3P°) y 5H°) + H(1s
2
S) process with the value of 5.65 × 10−9 cm3 s−1 at T = 6000 K within
the sextet molecular symmetries and the Fe(3d7 (2D2 )4p v 3F°) + H(1s
2
S) →Fe(3d7 (2G)4p v 3G°) + H(1s 2S) process with the value of
6.44 × 10−9 rmcm3 s−1 at T = 6000 K within the quartet molecular sym-
metries. It is worth to emphasize that the highest rates for excitation
and de-excitation processes are by an order of magnitude smaller than
S.A. Yakovleva et al.
Fig. 2. Graphical representation of the rate coefficients (in units of cm3s−1) at T = 6′000 K in iron-hydrogen collisions due to transitions within the 4Σ−, 4Π, 4Δ and 4Φ
molecular symmetries.
Fig. 3. The neutralization rate coefficients in iron – hydrogen collisions at
T = 6′000 K. Different triangle types stand for partial rates in each molecular
symmetry, crosses – for the sum over all molecular symmetries of the final state.
Solid line represents the reduced rate coefficient calculated by the simplified
model.
the highest rates for mutual neutralization processes. Note that some
off-diagonal squares in Fig. 1 and Fig. 2 are white, that is the corre-
sponding rate coefficients are equal to zero. The reason for these zero
values is that the corresponding processes refer to transitions between
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Chemical Physics 515 (2018) 369–374
molecular states of different symmetries.
The dependences of the rate coefficients for mutual neutralization
processes on the electron bound energies within the sextet and quartet
molecular symmetries are presented in Figs. 3 and 4, respectively.
Different triangle types stand for partial rates in each molecular sym-
metry, individual terms in Eq. (1), crosses for the sum over all mole-
cular symmetries of the final state, see Eq. (1). Molecular states with Σ
symmetry have smaller statistical probabilities than states with Π, Δ or
Φ symmetries and as a result have smaller partial rate coefficients. If a
covalent state has all molecular symmetries which the corresponding
ionic state has, then the rate coefficient coincides with the value of the
reduced rate coefficient depicted by the solid line. Otherwise, that is,
when not all molecular symmetries are present, the rate coefficient is
determined by the sum of the statistical probabilities of the contributing
molecular symmetries multiplied by the reduced rate coefficient, and
hence the calculated rate coefficient is smaller than the reduced rate
coefficient, see Figs. 3 and 4. It is also seen from these figures that the
most optimal windows are located in the vicinity of the electron bound
energy equal to −2 eV.
As mentioned above, the excitation and de-excitation rate coeffi-
cients depend on two bound energies Ei and Ef for the initial and the
final states. This dependence has a hill-shape with a maximum around
−2 eV for each bound energies. A general form for this dependence is
presented in Ref. [18].
The calculated estimates are in general agreement with the results
of Refs. [12]. A detailed comparison will be given elsewhere.
S.A. Yakovleva et al.
Fig. 4. The neutralization rate coefficients in iron-hydrogen collisions at
T = 6′000 K. Different triangle types stand for partial rates in each molecular
symmetry, crosses – for the sum over all molecular symmetries of the final state.
Solid line represents the reduced rate coefficient calculated by the simplified
model.
4. Conclusion
The inelastic processes in low-energy collisions of iron atoms and
positive ions with hydrogen atoms and negative ions are treated. The
partial processes for all transitions involving 97 low-lying covalent
Fe + H states and two ionic Fe+ + H− molecular states are studied, and
rate coefficients for excitation, de-excitation, ion-pair formation and
neutralization inelastic processes within the 6 Σ+ 6Π, 6Δ, 4 Σ−, 4 Π, 4 Δ
and 4Φ molecular symmetries are calculated by means of the simplified
model for the temperature range T = 1000−10, 000 K. The analysis of
the calculated rate coefficients for different temperatures shows that
the rate coefficients for exothermic processes weakly depend on tem-
perature, while for the endothermic processes the dependence is strong.
It is shown that rate coefficients with highest values correspond to the
mutual neutralization processes Fe+(3d6 4s 6D) + H−→Fe(3d6 (3G)4s4p
(3P°) w 5G°, v 5F°, y 5H°) + H(1s 2S) and Fe+ (3d74F) + H−→Fe(3d7 (2G) 4p
w 3F°, y 3H°, v 3G°) + H(1s 2S). At T = 6000 K the largest value
6.83 × 10−8 cm3 s−1 belongs to the mutual neutralization into the Fe
(3d7 (2G)4p v 3G°) final state within the quartet spin multiplicity and
6.78 × 10−8 cm3 s−1 to the mutual neutralization to the
Fe(3d6 ( 3G)4s4p( 3P°)v 5F°) final state within the sextet spin multiplicity.
Among the excitation and de-excitation processes, the highest rate
coefficient correspond to Fe(3d6 (3G)4s4p(3P°) v 5F°) + H(1s 2S) → Fe
(3d6 (3G)4s4p(3P°) y 5H°) + H(1s 2S) process with the value of
5.65 × 10−9 cm3 s−1 at T = 6000 K within the sextet molecular symme-
tries and Fe(3d7(2D2 )4p v 3F°) + H(1s 2S) → Fe(3d7(2G)4p v 3G°) +H
(1s 2S) process with the value of 6.44 × 10−9 cm3 s−1 at T = 6000 K within
374
Chemical Physics 515 (2018) 369–374
the quartet molecular symmetries. The present quantum estimates are
available online and can be used for non-LTE modellings of stellar at-
mospheres.
Acknowledgements
SAY and AKB gratefully acknowledge support from the Ministry for
Education and Science (Russian Federation), projects # 3.1738.2017/
4.6, 3.5042.2017/6.7.
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