molecules

Article
SF6 Negative Ion Formation in Charge Transfer Experiments
Sarvesh Kumar 1,2 , Masamitsu Hoshino 3 , Boutheïna Kerkeni 4,5 , Gustavo García 6 , Ghofrane Ouerfelli 7 ,
Muneerah Mogren Al-Mogren 8 and Paulo Limão-Vieira 1, *

1 Atomic and Molecular Collisions Laboratory, CEFITEC-Centre of Physics and Technological Research,
Department of Physics, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal;
[Link]@[Link] or skumar2@[Link]
2 Chemical Sciences Division, Lawrence Berkeley National Laboratory, One Cyclotron Road,
Berkeley, CA 94720, USA
3 Department of Materials and Life Sciences, Sophia University, Tokyo 102-8554, Japan; masami-h@[Link]
4 ISAMM, Université de la Manouba, La Manouba 2010, Tunisia; [Link]@[Link]
5 Département de Physique, LPMC, Faculté des Sciences de Tunis, Université de Tunis el Manar,
Tunis 2092, Tunisia
6 Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas (CSIC), Serrano 113-bis,
28006 Madrid, Spain; [Link]@[Link]
7 Department of Physics, College of Khurma University, Taif University, P.O. Box 11099,
Taif 21944, Saudi Arabia; [Link]@[Link]
8 Department of Chemistry, College of Sciences, King Saud University, P.O. Box 2455,
Ryiadh 11451, Saudi Arabia; mmogren@[Link]
* Correspondence: plimaovieira@[Link]; Tel.: +351-21-294-78-59

Abstract: In the present work, we report an update and extension of the previous ion-pair formation
study of Hubers, M.M.; Los, J. Chem. Phys. 1975, 10, 235–259, noting new fragment anions from time-
of-flight mass spectrometry. The branching ratios obtained from the negative ions formed in K + SF6
collisions, in a wide energy range from 10.7 up to 213.1 eV in the centre-of-mass frame, show that the
main anion is assigned to SF5 − and contributing to more than 70% of the total ion yield, followed
by the non-dissociated parent anion SF6 − and F− . Other less intense anions amounting to <20% are
assigned to SF3 − and F2 − , while a trace contribution at 32u is tentatively assigned to S− formation,
although the rather complex intramolecular energy redistribution within the temporary negative ion
Citation: Kumar, S.; Hoshino, M.; is formed during the collision. An energy loss spectrum of potassium cation post-collision is recorded
Kerkeni, B.; García, G.; Ouerfelli, G.; showing features that have been assigned with the help of theoretical calculations. Quantum chemical
Al-Mogren, M.M.; Limão-Vieira, P. calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom
SF6 Negative Ion Formation in Charge are performed to support the experimental findings. Apart from the role of the different resonances
Transfer Experiments. Molecules 2024, participating in the formation of different anions, the role of higher-lying electronic-excited states of
29, 4118. [Link] Rydberg character are noted.
molecules29174118

Academic Editor: Cecilia Coletti Keywords: sulphur hexafluoride; charge transfer; anion formation; mass spectrometry; energy loss

Received: 29 July 2024

Revised: 25 August 2024
Accepted: 27 August 2024
1. Introduction
Published: 30 August 2024
Sulphur hexafluoride (SF6 ) is an anthropogenic chemical compound that has raised
serious concerns across the globe given its role as a potent greenhouse gas and long-term
effects when released into the Earth’s atmosphere [1,2]. Such ability to contribute to global
Copyright: © 2024 by the authors. warming results from being an efficient infrared absorber within the atmospheric window
Licensee MDPI, Basel, Switzerland. (≈700–1300 cm−1 ) [3], despite modest contribution to radiative forcing [4]. Its considerably
This article is an open access article long atmospheric lifetime, up to 3200 years, is results from physical and chemical inertness
distributed under the terms and to atmospheric sink mechanisms such as photodissociation and reaction with radicals [1].
conditions of the Creative Commons SF6 has been widely used as a gaseous dielectric (e.g., in high-voltage lines and particle
Attribution (CC BY) license (https:// accelerators), in the semiconductor industry for plasma etching reactors, as well as in a
[Link]/licenses/by/ wide range of applied fields where its unique molecular and electronic structure play a
4.0/).

Molecules 2024, 29, 4118. [Link] [Link]

Molecules 2024, 29, x FOR PEER REVIEW 2 of 14

Molecules 2024, 29, 4118 2 of 14

play a relevant role in the underlying electron induced processes yielding a particular
reaction
relevantchannel
role in (see [5] and references
the underlying electron therein).
induced processes yielding a particular reaction
channel (see [5] and references therein).with SF6 has attracted the interest of the interna-
Interaction of low-energy electrons
tional Interaction
scientific community,
of low-energy withelectrons
several experimental
with SF6 has and theoretical
attracted studiesofbeing
the interest re-
the inter-
ported
national[5].scientific
SF6 is wellcommunity,
known to bewith an efficient
several electron scavenger
experimental and because
theoreticalof its large low-
studies being
energy
reportedelectron
[5]. SF attachment
6 is well known cross-section
to be anyielding
efficientlong-lived SF6− ions and
electron scavenger higher
because of energy
its large
formation
low-energy of SF 5 + F [5–21].
−
electron Dissociative
attachment electronyielding
cross-section attachment to sulphur
long-lived − ions and higher
SF6hexafluoride also
yields SF −, SF3−, SF2−, F2−, and − F − [5,14,19], while the lifetime of the metastable parent anion
energy formation of SF5 + F [5–21]. Dissociative electron attachment to sulphur hex-
4

has been investigated

afluoride also yields in SFa4 −few −
, SFoccasions, −
3 , SF2 , Fwith
− values
2 , and F− reported
[5,14,19], from
while10the μslifetime
up to 10ofms the
depending
metastableon the ro–vibrational
parent anion has beeninternal energyinstate,
investigated a fewyet with nowith
occasions, general agreement
values reported
within
from 10 theµsinternational scientific community
up to 10 ms depending [5,9,11,17,19–21].
on the ro–vibrational internal For a comprehensive
energy state, yet with de-no
scription
general on the lifetimes,
agreement within [Link]
[9]. scientific community [5,9,11,17,19–21]. For a
comprehensive
Electron-induced description
processes on the with lifetimes,
SF6 alsosee ref. [9].
include electron scattering absolute elastic
Electron-induced processes with SF
differential and total elastic cross-sections6(including momentum also include electron scattering absolute elastic
transfer cross-sections)
differential
from experiments and total elastic
[22–26] and cross-sections (including momentum
theoretical calculations [27–29] (and transfer cross-sections)
references therein),
from experiments
whereas cross-sections [22–26]
at low andenergies
theoretical calculations [27–29]
for vibrationally (andinelastic
elastic and references therein),
scattering
whereas
have beencross-sections
calculated using at low energies for effective
a multichannel vibrationally
rangeelastic
theoryand inelastic
(ERT) with scattering
complex
have been
boundary calculated
conditions using
[26]. a multichannel
Formation effective
of SF6 negative ionsrange
has theory (ERT) within
been investigated complex
state-
boundary conditions [26]. Formation
selected Rydberg electron transfer experiments of SF 6 negative ions has been investigated
[30–33], while Hubers and Los reported in state-
selected Rydberg electron transfer experiments [30–33], while
the dependence of ion-pair formation in collisions of fast alkali atoms (K, Na, and Li) from Hubers and Los reported the
dependence of ion-pair
a threshold up to 35 eV [34]. formation in collisions of fast alkali atoms (K, Na, and Li) from a
threshold up to 35 eV [34].
In this contribution, we report the experimental results on SF6 anion formation and
In this contribution,
its fragmentation pattern upon we report
electron the experimental
transfer in a wide results on SF6 energy
collision anion formation and its
range together
fragmentation pattern upon electron transfer in a wide collision
with quantum chemical calculations. Moreover, this is an update and extension of a pre- energy range together with
quantum chemical calculations. Moreover, this is an
vious ion-pair formation study [34], where new fragment anions have been assigned andupdate and extension of a previous
ion-pair
the collision formation
dynamics study [34], where
thoroughly new fragment
discussed from theanions have and
ionic yields beentheassigned and the
novel energy
collision dynamics thoroughly discussed from the ionic
loss spectrum. In Section 2, we present the results, whereas Section 3 deals with the dis- yields and the novel energy loss
spectrum. In Section 2, we present the results, whereas Section
cussion of the experimental data and the theoretical calculation results needed to support 3 deals with the discussion
of experimental
the the experimental data Section
findings. and the4theoretical
gives a brief calculation
description results needed
of the to support
experimental appa-the
experimental
ratus findings. Section
and the computational 4 gives
details. a briefsome
Finally, description of thethat
conclusions experimental
can be drawn apparatus
from
and the computational details. Finally, some conclusions that can be drawn from this study
this study are given in Section 5.
are given in Section 5.
[Link]
Results
Within
Withinthethescope
scopeofofnegative
negativeionionformation
formationininneutral
neutralpotassium
potassium(K)–neutral
(K)–neutralsulphur
sulphur
hexafluoride (SF 6) molecule collisions, we make use of theoretical calculations on the low-
hexafluoride (SF6 ) molecule collisions, we make use of theoretical calculations on the lowest
est unoccupied
unoccupied molecular
molecular orbitals
orbitals (LUMOs)
(LUMOs) to to obtain
obtain information
information about
about thethe most
most acces-
accessible
sible electronic states. Thus, SF 6 electronic structure in the presence of a K atom has been
electronic states. Thus, SF6 electronic structure in the presence of a K atom has been
obtained
obtainedwith withthe shape
the and
shape energy
and energy of the different
of the molecular
different molecular orbitals calculated
orbitals up to
calculated up21to
eV21 eV (Section 4). For detailed information on the calculated occupied and virtual Mos;see
(Section 4). For detailed information on the calculated occupied and virtual Mos; see
Table
TableS1.
[Link]
Theoptimised
optimisedgeometry
geometryofofthethebare
baremolecule
moleculeand andininthe
thepresence
presenceofofthe
theKKatom
atom
were
wereobtained
obtainedatatthetheM06-2X/6-311++g(3df,3pd)
M06-2X/6-311++g(3df,3pd)level levelofoftheory,
theory,with
witha aKKand
andF Fdistance
distanceofof
3.47
3.47ÅÅ,
, asasdepicted
depictedininFigure
Figure1.1.

Figure 1. Molecular optimised structure of sulphur hexafluoride, and orientation of the K + SF6
Figure 1. Molecular optimised structure of sulphur hexafluoride, and orientation of the K + SF6 col-
collisional system. Colours are purple for K, light blue for F, and yellow for S. Bond lengths are in Å.
lisional system. Colours are purple for K, light blue for F, and yellow for S. Bond lengths are in Å .
Negative ions formed in electron transfer experiments from K–SF6 collisions were
mass analysed by TOF mass spectrometry. The wide collision energy range probed in the
present study (15–300 eV in the lab frame, 10.7–213.1 eV in the centre-of-mass frame) shows
 Molecules2024,
Molecules 2024,29,
29,x xFOR
FORPEER
PEERREVIEW
REVIEW 3 3ofof1414

Negativeions
Negative ionsformed
formedininelectron
electrontransfer
transferexperiments
experimentsfrom fromK–SFK–SF collisionswere
6 6collisions were
Molecules 2024, 29, 4118 3 of 14
massanalysed
mass analysedby byTOF TOFmass
massspectrometry.
[Link] Thewide widecollision
collisionenergy
energyrange rangeprobedprobedininthethe
presentstudy
present study(15–300
(15–300eV eVininthe
thelab labframe,
frame,10.7–213.1
10.7–213.1eV eVininthe thecentre-of-mass
centre-of-massframe) frame)
showsthat
shows thatthethemain
mainanionanionisisassigned
assignedtotoSF SF andcontributing
5−5−and contributingtotomore morethan than70%
70%ofofthe the
totalthat
total ionthe
ion yield,main
yield, anion is
followed
followed byassigned
by the to SF5 − andparent
thenon-dissociated
non-dissociated contributinganionsto
parentanions SFSFmore
− and
6−6and than
FF 70% of2).
− (Figure
− (Figure the
2). total ion
Above
Above
yield, followed by the non-dissociated parent anions − and F− (Figure 2). Above 25 eV,
2525eV,
eV,strong
strong competition
competition isisnoted
notedbetween
between theSF
the SF andFSF
6−6−and F 6 yields,
− −yields, whichisisreminiscent
which reminiscentofof
strong competition isaffinity
notedofbetween the SF − −
therather
the ratherhighhighelectron
electronaffinity ofthe
thefluorine
fluorine 6 and
atom,
atom, F in
while
while yields,
inthe which
thecase
case ofofSF is6 reminiscent
SF 6 such
such of the
isisrelated
related
rather
totothe
theanion’shigh electron
anion’smolecular affinity
molecularstructure of the
structureability fluorine atom,
abilitytotoredistribute while
redistributeexcess in the
excessenergy case of
energythroughSF
through
6 such is related
avail- to
theavail-
the
able the anion’s
ableinternal molecular
internaldegrees structure
degreesofoffreedom.
[Link] ability
Otherminorto redistribute
minorfragments excess
fragmentsaccounting energy
accountingfor through
forless
lessthanthe
than1% available
1%areare
dueinternal
due totoSFSF degrees
and
3−3−and F F of freedom.
formation
2−2−formation
Other
across
across minor
the
the entire
entire fragments
collision
collision accounting
energy
energy range
range forinvestigated.
less than 1% are due to
investigated.
SF3 − and F2 − formation across the entire collision energy range investigated.

Figure
Figure [Link]
Figure SF
2. branching
6 6branching
SF6 branchingratios
ratios (anion
(anion
ratios yield/total
yield/total
(anion anion
anion
yield/total yield)
yield)
anion from
from
yield) theanions
the
from anions
the formed
formed
anions asasa aas
formed function
function
a function
ofofthe
the collision
ofcollision
the energy
energy
collision ininthe
energy the centre-of-mass
incentre-of-mass
the centre-of-mass frame
frame (CM).
(CM).
frame Error
Error
(CM). bars
bars
Error arerelated
are
bars related
are totothe
related the experimental
toexperimental
the experimental
uncertainty
uncertainty
uncertainty associated
associated with
with
associated each
each
with ionyield.
ion
each yield.
ion Thesolid
The
yield. solid
The lines
lines
solid arejust
are
lines justto
are toguide
just guide theeye.
the
to guide [Link].
the

InInorder
order
In totofurther
order further
to furtherourour
our knowledge
knowledge
knowledge ononthe
thethe
on nature
nature ofofthe
nature thethe
of different
different accessible
accessible
different anionic
anionic
accessible anionic
states,
states, after
after
states, electron
electron
after transfer
transfer
electron theK
the
transfer K + formed
ion
+ +ion
the K formed
ion waswas
was
formed energy
energy lossloss
loss
energy analysed
analysed ininthe
analysed the forward
in forward
the forward
scattering
scattering direction
direction
scattering (θ(θ≈(θ
direction ≈0°)
0°)
≈at ◦a) aat
0at collision
collision energy
energy
a collision ofof≈146
energy ≈146
of ≈eV eVineV
146 inthe
the centre-of-mass
in centre-of-mass
the centre-of-mass frame,
frame,
frame,
205 eV
205 205
eV in in the
eVthe laboratory
in laboratory
the laboratory frame
frame
frame (Figure
(Figure 3).
3). 3).
(Figure

Figure
Figure [Link]
Figure K+ energy
+ energy
energy
+3. lossspectrum
loss spectrum
loss fromKfrom
spectrum
from K+ +SF
SF
K 6+collisionsatat≈146
≈146at
SF6 collisions
6 collisions eV≈in146
eV inthe
the
eV centre-of-mass frame(205
in the centre-of-mass
centre-of-mass frame (205
frame
eVin(205
eV inthe
the lab
lab
eV frame)
frame)
in ininthe
the lab theforward
frame)forward scattering
in thescattering direction(θdirection
forward direction
scattering (θ≈ ≈0°).
0°).The
The 0◦ ). The
different
(θdifferent
≈ decomposed
decomposed features
features
different decomposed
result
result fromGaussian
from
features Gaussian
result from fittings
fittings withfittings
with
Gaussian theirrelated
their related uncertainties.
uncertainties.
with their related uncertainties.

Table 1 lists the vertical electron affinities (VEAs) and assignments of the different
features from the Gaussian fitting to the post-collision potassium cation (K+ ) energy loss
Molecules 2024, 29, 4118 4 of 14

spectrum. Briefly, in such an ion-pair formation collision process, there is an energy loss
(∆E) feature as follows:
∆E = IE(K) − EA(Imax ) (1)
with IE(K) being the potassium atom ionisation energy (4.34 eV [35]) and EA(Imax ) the
vertical electron affinity of a given state [36,37].

Table 1. Assignment of different features from Gaussian fittings to K+ energy loss spectrum from
K + SF6 collisions at ≈146 eV in the centre-of-mass frame *. VEA (vertical electron affinity), VE
(vertical energy), EA (electron attachment).

K+ Energy Loss Feature (eV) VEA (eV) Calculated VE (eV) Assignment EA resonances (eV) [5]
3.39 ± 0.11 0.95 ± 0.11 – – –
7.11 ± 0.14 −2.77 ± 0.14 3.81 LUMO+46 2.6 (2.8; ~2.9 [19])
10.67 ± 0.10 −6.33 ± 0.10 6.30 LUMO+57 ~5.4; (5.7 ± 0.1 [38])
12.33 ± 0.10 −7.99 ± 0.10 7.24 LUMO+65 8.8 (8.9)
15.39 ± 0.10 −11.05 ± 0.10 11.01 LUMO+73 11.3 (11.5; 11.6)
17.34 ± 0.10 −13.00 ± 0.10 12.89 LUMO+81 –
19.89 ± 0.10 −15.55 ± 0.10 15.68 LUMO+97 –
22.93 ± 0.10 −18.59 ± 0.10 17.60 LUMO+101 –
24.94 ± 0.10 −20.60 ± 0.10 21.56 LUMO+102 –
* The uncertainties result from the Gaussian fitting procedure.

A close inspection of Figure 3 shows a main feature peaking at 10.67 ± 0.10 eV (Imax )
that corresponds to a vertical electron affinity of (−6.33 ± 0.10) eV, which is related to the
broad dissociative electron attachment resonance at ~5.4 eV yielding F− [19]. An energy
difference of ~0.9 eV is acceptable within the energy resolution of the K+ energy loss data
and fitting uncertainties.

3. Discussion
Following a methodology previously established when dealing with negative ion
formation in charge transfer experiments [39–55], the information obtained from electron
attachment studies is relevant to assess the role of the main resonances involved, either
shape- and/or core-excited. In the electron transfer mechanism:

K + ABC → [K+ ABC−# ] (2)

K is the potassium atom, ABC a polyatomic molecule, and ABC−# a temporary negative ion
(TNI) formed with excess internal energy that may yield a stable parent anion or different
fragmentation channels. The role of the collision complex formed, [K+ ABC−# ], due to
the strong coulomb interaction while the potassium cation is in the vicinity of the TNI,
may dictate a different fragmentation pattern (and even anionic yields) from dissociative
electron attachment processes.
The collision dynamics are certainly different from the electron attachment (and
dissociative electron attachment, DEA) process and TNI autodetachment can be delayed
long enough to allow intramolecular energy redistribution within the TNI’s different
degrees of freedom. Such a stabilisation process can yield either a non-dissociated parent
anion (see, e.g., [50]) or fragment anions from effective bond excision within the TNI (via
direct or statistical dissociation). In atom–molecule collisions, electron transfer occurs in
the vicinity of the crossing between the ionic (K+ + ABC− ) and the covalent (K + ABC)
configurations of the colliding partners. The endoergicity of the process, ∆E, is given by
Equation (1), i.e., the ionisation energy of the electron donor and the electron affinity of
the target molecule. For a thorough description on ion-pair formation collisional processes,
see [36,37] and references therein.
The negative ions formed in K + SF6 collisions across the energy range 10.7–213.1 eV
in the centre-of-mass frame were assigned to SF6 − , SF5 − , SF3 − , F2 − , and F− (see Figure 2),
 Molecules 2024, 29, x FOR PEER REVIEW 5

molecule. For a thorough description on ion-pair formation collisional processes

Molecules 2024, 29, 4118 [36,37] and references therein. 5 of 14
The negative ions formed in K + SF6 collisions across the energy range 10.7–213
in the centre-of-mass frame were assigned to SF6−, SF5−, SF3−, F2−, and F− (see Figure 2),
− SF5−major
with SF5 as the as thecontribution.
major contribution.
It is worthIt is worth
noting noting
that that a contribution
a contribution barely discernib
barely discernible
32 u,bethat
at 32 u, that can can be to
assigned −
assigned to O2 formation
O2 formation − fromina the
from a leak leaksample
in the sample
system,system,
is also is also t
tentatively assigned to S− formation
tively assigned to S− formation
and was andnotwasincluded
not included
in thein branching
the branching ratios
ratios of of Figu
but will
Figure 2, but will be discussed
be discussed [Link].
We areWeaware
are aware of a previous
of a previous ion-pairion-pair formation
formation work work w
where only SFonly− SF6− − F 5− F− ions
6 , SF 5 , ,SF2 ,, Fand
2−, and F− ionsareare reported
reported [34],[34], however
however withwith no information abou
no information
−

about K+ post-collision energy

post-collision loss. loss.
energy FromFrom
the present experimental
the present data and
experimental datathe theoretical
and the theoretical c
calculations, the next the
lations, sections provide provide
next sections a discussion on the different
a discussion anions formed
on the different anionsand the and the
formed
role of the molecular orbitals participating
of the molecular in the K +inSF
orbitals participating 6 electron
the transfer process.
K + SF6 electron transfer process.

3.1. SF6 − Formation

3.1. SF6− Formation
The non-dissociated parent anion,parent
The non-dissociated together
anion, F− , contributes
withtogether with F−,as the secondasmost
contributes the second
abundant ionabundant
yield across
ionthe entire
yield collision
across energy
the entire range energy
collision investigated
range(see Figure 2).(see
investigated TheFigure 2)
reaction that involves parent
reaction that anion formation
involves is given
parent anion by Equation
formation is given(3):
by Equation (3):

K + SF6 → [K+ SFK6 −+#SF

]→ 6 →
K+[K
++ SF −#] → K+ + SF6−
SF66− (3)

with SF6 −# awith SF6−# a temporary

temporary negative ion negative
(TNI) ion
with(TNI) with
excess ofexcess
internalof internal
energy. energy.
Although Although S
an extremely
SF6 is an extremely efficient
efficient electronelectron scavenger,
scavenger, and and a highly
a highly symmetric
symmetric molecule,
molecule, itsits yield
yield does not surpass ~15% of the total anion yield. This is an interesting result when compa
not surpass ~15% of the total anion yield. This is an interesting result when
such
comparing such yield
yield with
with other
other polyatomic
polyatomic molecules,
molecules, e.g.,
e.g., hexachlorobenzene
hexachlorobenzene [51]
[51] andand nitroi
azoles
nitroimidazoles [52,56],
[52,56], wherewhere the non-dissociated
the non-dissociated parentparent
anionanion
is theismajor
the major ion signal.
ion signal. The The bra
ing in
branching ratios ratios in Figure
Figure 2 show2 thatshow inthat in the low-energy
the low-energy collisioncollision
region region
(<20 eV),(<20theeV),
ionthe ion si
is mostly
signal is mostly due todueSF5 −to (>80%), F− (<9%),
SF5− (>80%), F− (<9%),
andand a minor
a minor contribution
contribution of of
F2 F−2−(<0.4%).
(<0.4%). This be
iour
This behaviour is is reminiscent
reminiscent of of
SFSF− − stronglycompeting
competingwith witheither
eitherautodetachment
autodetachmentor or bond br
6 6 strongly
bond breakinging processes.
processes. Notwithstanding,
Notwithstanding, andandyetyet
notnot reported
reported here, SF6 −
here, SFformation
6− formation is ais a domi
anion
dominant anion for collision
for collision energies
energies belowbelow 10.7with
10.7 eV, eV, awith a threshold
threshold at±(3.86
at (3.86 0.10)± eV
0.10) eV [34].
[34].
The calculated Thelowest unoccupied
calculated lowest molecular
unoccupied orbitals (LUMOs)
molecular in the
orbitals presence
(LUMOs) of apresence
in the
potassium atom show a atom
potassium symmetric
show delocalized
a symmetricspin density over
delocalized spin the sulphur
density overatom, with atom,
the sulphur
LUMO+46 exhibiting
LUMO+46 a relevant
exhibiting S–Faσ* relevant S–F σ*character.
antibonding Given
antibonding the high Given
character. symmetry of symm
the high
SF6 molecules,
of strong competition
SF6 molecules, strongamong all six equivalent
competition among all six fluorine atomsfluorine
equivalent for the atoms
extra for the e
charge are noted
charge(seeare
Figure
noted 4 and
(see also Figure
Figure 4 andS1), thus
also yielding
Figure SF6 − oreither
eitheryielding
S1), thus F− . SF6− or F−.

(a) LUMO+46 (b) LUMO+57

Figure 4. Cont.
 Molecules
Molecules 2024, 2024, 29, x FOR PEER REVIEW
29, 4118 6 of 14 6 of 1

(c) LUMO+65 (d) LUMO+73

Figure 4. Calculated
Figure 4. Calculated lowest unoccupied
lowest unoccupied molecular molecular
orbitals fororbitals
K + SF6for
(K:Kpurple,
+ SF6 (K:
S: purple,
yellow, S:
F: yellow,
light F: ligh
grey): (a) LUMO+46; (b) LUMO+57; (c) LUMO+65; (d) LUMO+73. The K
grey): (a) LUMO+46; (b) LUMO+57; (c) LUMO+65; (d) LUMO+73. The K atom and one of the atom and one of Fthe F atom
are connected by a straight line, meaning the spatial mutual position
atoms are connected by a straight line, meaning the spatial mutual position only. only.

As theenergy
As the collision collision energy is more
is increased, increased,
energy more
mayenergy may be
be deposited indeposited in the SF6 mole
the SF6 molecule,
cule, leading to further fragmentation at the expense −
leading to further fragmentation at the expense of lower SF6 yield. However, the non- of lower SF 6− yield. However, the

non-dissociated
dissociated parent anion becomes parent anion becomes
somehow somehow
constantly constantlytoinsensitive
insensitive to the entire colli
the entire collision
sion albeit
energy range, energywith range, albeit
modest with modest
changes to within changes to within
±5% (Figure ±5%ability
2). This (Figure of2). This ability o
sulphur
sulphur
hexafluoride parenthexafluoride
anion yield parent aniontoyield
is related is related structure
its electronic to its electronic
with astructure
delocalized with a delo
calized
spin density overspin density over
all molecules, all molecules,
which is much more whichdiscernible
is much more fromdiscernible
the high-energyfrom the high
LUMO+97 energy LUMO+97
(see Figure (see Figure
S1). Another S1). Another
interesting aspectinteresting aspect of the
of the SF6 branching SFtogether
ratio, 6 branching ratio

with the other fragment

together with the anions
otherabove 25 eV,anions
fragment pertains to the25rather
above insensitive
eV, pertains tendency
to the rather ofinsensitive
the yieldstendency
with the of increasing
the yieldscollision
with theenergy.
increasingSuchcollision
behaviour can be
energy. Suchrelated to collision
behaviour can be related
dynamicstowith ratherdynamics
collision fast collision
with times (<30
rather fs)collision
fast above 75times eV, not allowing
(<30 fs) abovesufficient
75 eV,timenot allowing
for K+ post-collision
sufficient time to interact with the TNIto
for K+ post-collision viainteract
a relevant
withcoulomb
the TNI interaction
via a relevant andcoulomb
thus inter
allowing efficient
action and internal energy redistribution.
thus allowing efficient internalVibronic coupling
energy may not play
redistribution. a relevant
Vibronic coupling may
role regarding
not playtheafragmentation yields (seethe
relevant role regarding discussion below)yields
fragmentation and at(see
such high energies
discussion below) and a
the molecular target can be considered as “rigid”. The TNI is
such high energies the molecular target can be considered as “rigid”. mostly formed via theThe
fastTNI
andis mostly
direct vertical access above the neutral ground-state (within the Franck–Condon
formed via the fast and direct vertical access above the neutral ground-state (within the region)
yielding the relevant σSF ∗ antibonding character of the upper ∗ ionic states. This agrees with
Franck–Condon region) yielding the relevant 𝜎𝑆𝐹 antibonding character of the uppe
the electron spin
ionic densities
states. in Figures
This agrees with4theand S1. At spin
electron such densities
higher energies,
in Figurescollision
4 and [Link]
At such highe
fragmentation is dictated by the electron affinity of the different radicals, with
energies, collision induced fragmentation is dictated by the electron affinity of the differ particular
relevanceent
to SF 5 and Fwith
radicals, (see particular
Table 2). relevance to SF5 and F (see Table 2).

Table 2. Electron
Table [Link] andaffinity
Electron bond dissociation energy (at 0 K)
and bond dissociation relevant
energy (at 0inK)
electron attachment
relevant to attachment
in electron SF6 . to
See text forSFdetails.
6. See text for details.

Compound Electron
Compound Electron Affinity
Affinity (eV) [35]
(eV) [35] Bond Dissociation
Bond Dissociation Energy
Energy (eV) [57] (eV) [57]
SF6 SF6 0.910 0.910 ± 0.070
± 0.070 1 1
– –
SF5 SF5 ± 0.020
3.850 3.850 ± 0.020 – –
SF3 SF3 ± 0.020
3.070 3.070 ± 0.020 – –
F2 3.005 ± 0.071 –
F
F2 3.005 ± 0.071
3.401191 ± 0.000026 –
–
SF5 –F F 3.401191
– ± 0.000026 4.00 ± 0.16 [58]–
SF4 –F SF5–F – – 2.51 ±4.00
0.13± 0.16 [58]
SF3 –F SF4–F – – 3.47 ± 0.56
2.51 ± 0.13
SF2 –F – 2.64 ± 0.12
SF3–F – 3.47 ± 0.56
SF–F – 3.98 ± 0.24
S–F SF2–F – – 2.64 ± 0.12
3.51 ± 0.07
F–F SF–F – – 3.98
1.627 ± 0.100 ± 0.24
2 [59]

1 adiabatic value; 2 atS–F

298 K. – 3.51 ± 0.07
F–F – 1.627 ± 0.100 2 [59]
1 adiabatic value; 2 at 298 K.
Molecules 2024, 29, 4118 7 of 14

The K+ energy loss spectrum at ≈146 eV collision energy in the centre-of-mass frame
in the forward scattering direction (θ ≈ 0◦ ) is shown in Figure 3. The weak feature peaking
at (3.39 ± 0.11) eV yields a positive electron affinity of (0.95 ± 0.11) eV. The asymptotic
limit of SF5 − + F is 0.2 eV [19] above the ground state of the neutral (SF6 ), meaning that the
feature at 0.95 eV does not lead to bond excision, resulting in SF6 − formation. Such electron
affinity (0.95 eV) is in excellent agreement with the adiabatic values reported by Menk
et al. [60] and Fenzlaff et al. [19], (0.91 ± 0.07) and (1.05 ± 0.10) eV, respectively, whereas
Hubers and Los reported an SF6 adiabatic electron affinity of (0.32 ± 0.15) eV (at T = 0 K).

3.2. SF5 − and F− Formation

The TOF mass spectra are dominated by SF5 − formation across the collision energy
range of 10.7 up to 213.1 eV in the centre-of-mass frame (see Figure 2). At first glance, this
may not be unexpected given the relative high electron affinity of SF5 (see Table 2). The
complementary reactions with respect to the negative charge that involve SF5 − and/or F−
formation (Equations (4) and (5)) result from an S–F bond breaking within the TNI as:

K + SF6 → [K+ SF6 −# ] → K+ + SF5 − + F (4)

K + SF6 → [K+ SF6 −# ] → K+ + SF5 + F− (5)

where (SF5 –F) is a direct bond cleavage and the extra charge sitting either on the SF5 or •

F• radicals.
It is interesting to note that the electron affinities of such radicals are rather identical,
i.e., EA(F) = (3.401191 ± 0.000026) eV and EA(SF5 ) = (3.850 ± 0.020) eV [35], but the
SF5 − yield is over four times higher than the F− signal. This difference cannot be solely
explained in terms of electron affinities but rather based on the electronic structure of
the TNI formed upon electron transfer. A close inspection of the lowest unoccupied
molecular orbitals, where the extra electron can attach, shows LUMO+46 with a strong S–F
σ* antibonding character (Figure 4). Rosa et al. [61], with dissociative attachment studies,
have demonstrated that SF6 excited to the degenerate stretching ν3 (t1u ) = 948 cm−1 mode,
and its molecular structure “leaving out the apex fluorine atom” exhibits a resemblance with
that of SF5 − . The SF5 − branching ratio in Figure 2 shows a rather constant behaviour for
25 < ECM < 70 eV. Note that within the TNI, relevant vibronic coupling may occur in this
energy region because the collision time varies from ~33 to ~55 fs, with the upper limit being
the same period of the degenerate stretching S–F, ν3 (e) = 602.5/596 cm−1 mode in SF5 − [35].
Moreover, we cannot discard the possibility of stretching S–F, ν1 ( a1 ) = 795.8/795.5 cm−1
mode also contributing to such anion formation [6]. Therefore, mode selectivity of ν3 (t1u )
(and/or ν1 ( a1 )) may be responsible for the relevant SF5 − yield. Below 25 eV, and at the
expense of F− , we observe an enhancement in SF5 − formation (Figure 2).
At higher collision energies, i.e., above 75 eV, one notes a moderate decrease in the SF5 −
ion signal (Figure 2), reminiscent of vibronic coupling being no longer a relevant mechanism
in the dissociation dynamics. The molecular target at those energies can be considered
rigid, meaning that the excess energy within the TNI will no longer be channelled into the
internal degrees of freedom but rather into the main antibonding character MOs with the
extra electron sitting favourably on the radical with the higher electron affinity. It is worthy
of note that as the collision energy is further increased, so is the relevance of core-excited
resonances that may relax into a dissociative state by internal conversion.
The thresholds for reactions in Equations (4) and (5) can be obtained from the SF5 –F
bond dissociation energy [58] and the electron affinities of SF5 and F [35] after adding the
potassium ionisation energy (4.34 eV [35]), i.e., D(SF5 –F) = (4.00 ± 0.16) eV,
EA(SF5 ) = (3.850 ± 0.020) eV, and EA(F) = (3.401191 ± 0.000026) eV, yielding 4.490 and
4.939 eV. These values are obtained assuming no excess of internal energy (E*) in the process.
Hubers and Los [34] report SF5 − and F− thresholds at (4.85 ± 0.10) and (7.30 ± 0.10) eV.
However, the TOF translational excess energy release from the dissociative electron attach-
ment study of Fenzlaff et al. [19] shows F− being formed with thermal or quasi-thermal
Molecules 2024, 29, 4118 8 of 14

energies with a mean value < 0.15 eV. If we take this value, the expected thresholds’ upper
limits are now obtained at 4.640 (for SF5 − ) and 5.089 eV (for F− ). The energy loss feature
peaking at (10.67 ± 0.10) eV (Figure 3) yields a vertical electron affinity of (–6.33 ± 0.10) eV
(Table 1). Such an electronic state is calculated at 6.30 eV and can result from access to
LUMO+57 with a relevant σSF ∗ antibonding character. Note that DEA experiments report

a relevant F− signal with a main resonance peaking at ~5.4 eV (Table 1), whereas SF5 −
only exhibits a single resonance at ~0.5 eV [5]. The energy loss feature with an estimated
threshold of ~5.7 eV, i.e., a ~0.6 eV energy difference due to the K+ beam energy resolution
of the experimental setup (Section 4), can solely be due to an F− signal.

3.3. SF3 − , F2 − , and S− Formation

The branching ratios in Figure 2 show that SF3 − and F2 − account together for ≲1.2%
of the total anion yield. The possible reaction mechanisms related to such an anion’s
formation are given by the following:

K + SF6 → [K+ SF6 −# ] → K+ + SF3 − + 3F (6a)

K + SF6 → [K+ SF6 −# ] → K+ + SF3 − + F2 + F (6b)

K + SF6 → [K+ SF6 −# ] → K+ + F2 − + SF4 (7)
Note that in Equations (6a) and (6b), the loss of three fluorine atoms may proceed
through reactions yielding F + F + F and/or F2 + F, with calculated thresholds of 11.250
and 9.623 eV. In the energy loss data in Figure 3, the feature peaking at (15.39 ± 0.10) eV,
with an estimated appearance at (11.56 ± 0.10) eV, may be related to reaction (6a) within
the experimental uncertainties. However, we do not discard the possibility that the energy
loss feature peaking at (12.33 ± 0.10) eV can also be responsible for reaction (6b). The
information obtained from the DEA data of Fenzlaff et al. [19] shows SF3 − with a wide
resonance, a maximum at ~11 eV, and a threshold of ~9 eV, much more consistent with
SF3 − + F2 + F formation. Whether in electron transfer yielding a negative ion favours
reaction (6a) against DEA to SF6 , leading to SF3 − + F2 + F, still remains to be proven within
the framework of the collision dynamics in K + SF6 .
We look at reaction (7), where F2 − formation from SF6 −# requires the excision of two
S–F bonds and fluorine has to be formed. From F2 electron affinity (3.005 ± 0.071) eV [35]
and the bond dissociation energies from Table 2, D(SF5 –F) = (4.00 ± 0.16) eV, D(SF4 –F) =
(2.51 ± 0.13) eV, and D(F–F) = (1.627 ± 0.100) eV, and after adding the potassium ionisation
energy of 4.34 eV, the appearance energy of reaction (7) is given by ε th ( F2 ) = D(SF5 –F) +
D(SF4 –F) − D(F–F) − EA(F2 ) + IE (K) = (6.218 ± 0.150) eV. The energy loss data in Figure 3
at (10.67 ± 0.10) eV shows an estimated threshold at ~(7.34 ± 0.10) eV, in reasonable
agreement within the K+ beam energy resolution.
Finally, we detain ourselves on the contribution within the TOF mass spectra of the
fragment anion 32 u. Such an anion can either originate from electron transfer to O2 present
from a small leak in the sample system or can be assigned to S− formation. In order to assess
the origin of such an anion, we have comprehensively compared the background yields
of O2 − and O− with the total cross-section for negative ion formation in K + O2 collisions
from the benchmarking work of Kleyn et al. [62]. At 20 eV in the centre-of-mass frame,
the cross-section ratio O− /O2 − is ~0.67 [62]. Although our TOF mass spectrum at such
collision energy shows no traces of 32 u anion formation, while at 22 eV a barely detectable
signal is discernible from the background. The expected ratio of O− /O2 − at 22 eV is
~0.63 [62], which is not noted in the present experiments, thus suggesting S− formation.
The reaction yielding S− requires considerable intramolecular processes, with six S–F
bonds to be broken and the extra charge sitting on the sulphur atom. Such a process seems
unlikely to happen, at least from the DEA data available in the literature [5]. However,
we have observed on several occasions that within the framework of potassium–molecule
collisions either the fragmentation pattern or different anions being formed differ from
electron attachment/dissociative electron attachment experiments [44]. The differences
Molecules 2024, 29, 4118 9 of 14

have been put forward on the role of the collision complex (Equation (2)), with the K+ ion
being a relevant partner allowing stabilization of the TNI while in its vicinity before leaving
the collision region. Thus, under particular energy constraints, the role of the electronic,
and the structure of the molecular target, different fragmentation channels can be accessed.
The calculated threshold of formation with a lower limit at ~ 18.1 eV is obtained from the
bond dissociation energies and the sulphur electron affinity (Table 2), assuming no excess
of energy (E*). Within such dissociative electron attachment experiments, we observe in the
ion yields above 14 eV a continuous increase in the background signal, which is reminiscent
of ion-pair formation [19]. If such anions were to be formed, the expected low yield would
probably not become discernible from such a continuum. In the presence of a potassium
atom, the threshold of S− reaction is now expected at ~22.4 eV, which seems to be in good
agreement with the TOF mass spectrometry data at that collision energy. An energy loss
feature with a maximum at (22.93 ± 0.10) eV (Table 1) shows a threshold at ~21.1 eV
(Figure 3). The calculated vertical energy (17.60 eV) is in reasonable agreement with the
experimental value of (–18.59 ± 0.10) eV (Table 1) to within the energy loss resolution.
From the theoretical calculation, this was assigned to the contribution of LUMO+101 (see
Figure S1), where a strong antibonding character is visible along the S–F bonds, becoming
more relevant at higher energies, as is the case for LUMO+102. Electron promotion to these
MOs may yield S− .

3.4. Energy Loss Data

The energy loss spectrum in Figure 3 was smoothed and fitted with Gaussian functions
to decompose the energy loss spectrum, with vertical electron affinities and assignment of
the main MOs in Table 1. Different fittings up to (15.39 ± 0.10) eV were obtained from the
energy position of the resonances from DEA experiments [5] while accounting for the width
of the Gaussian fittings with the related energy resolution of the charge transfer experiment.
Assignments above 15 eV were performed based on information from quantum chemical
calculations, with the nature of the most relevant MOs depicted in Figures 4 and S1. Of rele-
vance are the electronic-excited states of SF6 with vertical electron affinities above 11 eV that
can be associated with features converging to different ionisation limits, 15.890 eV(2 T1g ),
16.938 eV(2 T1u ), 17.360 eV(2 T2u ), 18.434 eV(2 Eg ), and 22.7 eV(2 T1u ) [63,64], and so promo-
tion of an electron to higher orbitals of increasing Rydberg character are noted. These are
the cases of LUMO+73 in Figure 4, and all MOs in Figure S1. These higher-lying energy
MOs show delocalized electron spin densities evocative of such character, and from dif-
ferent ionisation energies, the MOs can be tentatively assigned to ns, np, and nd. At these
energies, the number of electronic states is considerably large, making an unambiguous
assignment difficult, so these can also be listed as (n + 1) or (n + 2).
A close inspection of the lowest unoccupied molecular orbitals, where the extra
electron can attach, shows LUMO+46 with a strong S–F σ* antibonding character (Figure 4).
The calculated vertical energy is 3.81 eV, a value quite higher than the related resonance
positions of F− and F2 − from DEA experiments (Table 1) [5]. Notwithstanding, the electron
spin densities are in agreement with the favourable bond excision yielding F− , while F2 −
formation certainly may require different dynamics within the TNI formed after electron
transfer. We have recently observed in the case of C6 Cl6 [65] a strong vibronic coupling in
the TNI involving the C–Cl bending motion, where the chlorine atoms are brought together
within the ring framework due to excess energy dissipation producing Cl2 − . Whether this
mechanism is also operative in SF6 stands to be proven but is certainly beyond the scope of
the present contribution.
Recently, we have investigated different polyatomic molecular targets, viz., CH3 OH [55],
H2 O/D2 O [53], and C2 H5 OH [41], where we stressed that the output of the calculations
performed providing information on electronically excited states are related to single occu-
pied MO being replaced by a non-occupied (virtual) MO only. Therefore, we are not able
to account for the role of doubly excited states, yet these can certainly be considered, in
particular given the energy loss features observed at higher energies. This will be crucial to
Molecules 2024, 29, 4118 10 of 14

evaluating the relevant competition between super-excited states and bond excision into
neutral fragments (and even dipolar dissociation), which has been noted for H2 O/D2 O
energy loss features above 17 eV [53].

4. Materials and Methods

Ion-pair formations in collisions between neutral potassium atoms and neutral SF6
molecules were been obtained in a crossed molecular beam apparatus described else-
where [50,53,54,66]. Briefly, the Lisbon apparatus (see Figure S2) comprises two intercon-
nected and differentially pump vacuum chambers with base pressures in the potassium
chamber of 4 × 10−5 Pa and in the collision chamber of 5 × 10−5 Pa. After SF6 admission
in the collision chamber, the working pressure was 1 × 10−3 Pa for both time-of-flight
(TOF) mass spectrometry and K+ energy loss measurements. A beam of hyperthermal
neutral potassium atoms is produced by resonant charge exchange between K+ ions and
thermal potassium atoms in a charge exchange oven (CEO). The ion beam is delivered from
a commercial ion source (HeatWave, USA) that is accelerated to a set kinetic energy towards
the entrance of the CEO, while thermal potassium atoms are obtained by heating solid
potassium at 393 K. From such an interaction, the resultant beam comprises hyperthermal
ions that did not charge exchange and are removed from the hyperthermal neutral beam by
a pair of deflecting plates placed outside the CEO, before traveling into the collision region.
From the resonant charge-exchange process and the CEO slit apertures, the hyperthermal
neutral beam is mainly composed of K atoms in the ground-state with its outermost electron
as 4s. This has been previously checked in other energy loss data from potassium collisions
with pyrimidine [46], halothane [67], tetrachloromethane [66], and more recently with
hexachlorobenzene [51,68], nimorazole [52], water [53], methanol [55], and ethanol [41].
Of relevance, the experimental thresholds of formation are in assertion of K in a 4s state
rather than in a 4p state, which otherwise would result in values at lower energies than
those reported here (see Section 3). The hyperthermal neutral potassium beam intensity is
monitored at the entrance of the collision chamber by a surface ionisation Langmuir–Taylor
detector. The beam is made to cross at right angles with an effusive SF6 beam, which is
admitted to vacuum through a 1 mm diameter capillary from an external sample holder.
The negative ions formed in the collision region were extracted by a pulsed electrostatic
field (380 Vcm−1 ), and mass analysed in a dual-stage linear TOF with a mass resolution
m/∆m ≈ 125. The potassium beam energy resolution for TOF mass spectra collection in the
collision energy range investigated was ∼0.6 eV. The TOF mass calibration was performed
from well-known fragmentation patterns from collisions of potassium atoms with CH3 NO2
and/or CCl4 molecules [50,66]. Note that comprehensive background spectra (without the
sample) were obtained and subtracted from the sample measurements. Branching ratios
(BRs) for the fragment anions were obtained and result from the fragment anion yield
divided by the total anion yield at a given collision energy.
Potassium cations formed in post-collision experiments were energy loss analysed in
the forward scattering direction (θ ≈ 0◦ ), while experiments were not performed in coinci-
dence with TOF mass spectrometry. The analyser was operated in constant transmission
mode, hence keeping the resolution constant throughout the entirety of the scans. The
estimated energy resolution during the experiments was ~1.2 ± 0.2 eV. The energy loss
scale was calibrated using the K+ beam profile from the potassium ion source serving as
the “elastic peak”. SF6 was supplied by Alphagaz with a stated purity ≥ 99.9% and was
used as delivered.
Vertical excitation energies of the lowest unoccupied molecular orbitals (LUMOs) of
SF6 in the presence of a K atom were calculated to assess the nature of the different electronic
states. The geometry of a sulphur hexafluoride + potassium system was optimised at the
M06-2X/6-311++g(3df,3pd) level of theory and the equilibrium mutual distance between
the potassium K and fluorine F atoms is 3.47 Å. The coordinates of the resulting optimised
system are depicted in Figure 1. Quantum chemical calculations were performed with
the Gaussian 16 program package [69] and carried out in Cartesian coordinates, with no
Molecules 2024, 29, 4118 11 of 14

symmetries. All electrons were considered for sulphur, fluorine, and potassium atoms with
the 6-311++g(3df,3pd) basis set. The natural molecular orbitals for K−SF6 were calculated
by the same model chemistry.

5. Conclusions
We have performed electron transfer experiments in potassium–sulphur hexafluoride
collisions in the centre-of-mass energy range from 10.7 to 213.1 eV (15–300 eV in the
laboratory frame). The different time-of-flight mass spectra recorded allowed extending
and updating the previous ion-pair formation study of Hubers and Los [34] with new
fragment anions assigned, namely, SF6 − , SF5 − , SF3 − , F2 − , and F− . Moreover, from the
mass spectrometry data, a tentative assignment of anion 32u is suggested to be S− , although
there would be a rather complex intramolecular mechanism within the TNI yielding such
an ion. The main anion across the entire collision energy range is assigned to SF5 − , with
>70% of the total anion yield, in strong contrast to electron attachment experiments yielding
the intact parent anion, SF6 − . In the low-energy collision region, the branching ratios show
a relevant dependence where the excess internal energy deposited in the TNI leads to
different fragmentation channels. The anions formed have been discussed with the help of
quantum chemical calculations from the shape of the electron spin densities in the different
MOs accessed during the collision process. We have made use of the K+ post-collision
energy loss data recorded in the forward scattering direction to infer on the electronic state
spectroscopy of SF6 . The information available in the literature from electron attachment
experiments and theoretical data have been critical to identifying the different resonances
involved in the charge transfer process. The role of higher-lying excited states with Rydberg
character was assessed from the energy loss features above 11 eV. However, due to the lack
of further information in the literature, no attempt was made to assign the role of possible
doubly excited states, which may be attained at such high collision energies.

Supplementary Materials: The following supporting information can be downloaded at: https:
//[Link]/article/10.3390/molecules29174118/s1. Results from theoretical calculations for
the shape of a selection of K + SF6 lowest unoccupied molecular orbitals and SF6 temporary negative
ion (TNI) lowest lying electronic states in the presence of K. Figure S1: Calculated lowest unoccupied
molecular orbitals for K + SF6 (K: purple, S: yellow, F: light grey): (a) LUMO+81; (b) LUMO+97;
(c) LUMO+101; (d) LUMO+102; Figure S2: Schematic overview of the crossed molecular beam setup
for electron transfer experiments; Table S1: Calculated occupied (O) and virtual (V) molecular orbitals
of K + SF6 at the M06-2X/6-311++g(3df,3pd) level of theory.
Author Contributions: Conceptualization, S.K., B.K., and P.L.-V.; methodology, S.K.; software, B.K.,
G.O., and M.M.A.-M.; validation, B.K.; formal analysis, S.K., M.H., B.K., and P.L.-V.; investigation,
S.K. and M.H.; resources, B.K., G.G., and P.L.-V.; data curation, S.K. and B.K.; writing—original draft
preparation, B.K., G.G., and P.L.-V.; writing—review and editing, M.H., G.O., M.M.A.-M., B.K., G.G.,
and P.L.-V.; visualization, S.K.; supervision, P.L.-V.; project administration, P.L.-V.; funding acquisition,
B.K. and P.L.-V. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Portuguese National Funding Agency (FCT), grant number
PD/BD/142831/2018 and COVID/BD/152673/2022 (S.K.), Radiation Biology and Biophysics Doc-
toral Training Programme RaBBiT, PD/00193/2012, and grant number CEFITEC UIDB/00068/2020,
DOI: 10.54499/UIDB/00068/2020 (P.L.-V.). Partial financial support from the Spanish Ministerio
de Ciencia e Innovación Project No. PID2019-104727RB-C21 (G.G.) is also acknowledged. The au-
thors would like to acknowledge the Deanship of Graduate Studies and Scientific Research, Taif
University for funding this work and extend their appreciation to the Researchers Supporting Project
(RSPD2024R808) of King Saud University, Riyadh, Saudi Arabia.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data that support the findings of this study are available from the
corresponding authors upon reasonable request.
Molecules 2024, 29, 4118 12 of 14

Acknowledgments: We acknowledge the allocation of computer time at Grappe de calcul Tycho de

l’Observatoire de Meudon, France and the supercomputers at Taif and King Saud Universities. The
work is part of COST Action CA18212—Molecular Dynamics in the GAS phase (MD-GAS).
Conflicts of Interest: The authors declare no conflicts of interest.

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