Astronomy & Astrophysics manuscript no.

aa52210-24corr ©ESO 2025

January 7, 2025

Production of linear alkanes via the solid-state hydrogenation of

interstellar polyynes
G. Fedoseev1, 2 , X. Li1, 2 , G. A. Baratta3 , M. E. Palumbo3 , and K.-J. Chuang4

1
Xinjiang Astronomical Observatory, Chinese Academy of Sciences, Urumqi 830011, China
e-mail: [email protected]
2
Xinjiang Key Laboratory of Radio Astrophysics, Urumqi 830011, China
3
INAF – Osservatorio Astrofisico di Catania, via Santa Sofia 78, 95123 Catania, Italy
4
Laboratory for Astrophysics, Leiden Observatory, Leiden University, P.O. Box 9513, NL-2300 RA Leiden, the Netherlands
Received XX XX, XX; accepted XX XX, XX
arXiv:2501.03031v1 [astro-ph.EP] 6 Jan 2025

ABSTRACT

Context. Highly unsaturated carbon chains, including polyynes, have been detected in many astronomical regions and planetary
systems. With the success of the QUIJOTE survey of the Taurus Molecular Cloud-1 (TMC-1), the community has seen a "boom" in
the number of detected carbon chains. On the other hand, the Rosetta mission revealed the release of fully saturated hydrocarbons,
C3 H8 , C4 H10 , C5 H12 , and (under specific conditions) C6 H14 with C7 H16 , from the comet 67P/Churyumov-Gerasimenko. The detection
of the latter two is attributed to dust-rich events. Similarly, the analysis of samples returned from asteroid Ryugu by Hayabusa2 mission
indicates the presence of long saturated aliphatic chains in Ryugu’s organic matter.
Aims. The surface chemistry of unsaturated carbon chains under conditions resembling those of molecular clouds can provide a possi-
ble link among these independent observations. However, laboratory-based investigations to validate such a chemistry is still lacking.
In the present study, we aim to experimentally verify the formation of fully saturated hydrocarbons by the surface hydrogenation of
C2n H2 (n > 1) polyynes under ultra-high vacuum conditions at 10 K.
Methods. We undertook a two-step experimental technique. First, a thin layer of C2 H2 ice was irradiated by UV-photons (≥ 121
nm) to achieve a partial conversion of C2 H2 into larger polyynes: C4 H2 and C6 H2 . Afterwards, the obtained photoprocessed ice was
exposed to H atoms to verify the formation of various saturated hydrocarbons.
Results. In addition to C2 H6 , which was investigated previously, the formation of larger alkanes, including C4 H10 and (tentatively)
C6 H14 , is confirmed by our study. A qualitative analysis of the obtained kinetic data indicates that hydrogenation of HCCH and
HCCCCH triple bonds proceeds at comparable rates, given a surface temperature of 10 K. This can occur on the timescales typical for
the dark cloud stage. A general pathway resulting in formation of other various aliphatic organic compounds by surface hydrogenation
of N- and O-bearing polyynes is also proposed. We also discuss the astrobiological implications and the possibility of identifying
alkanes with JWST.
Key words. Astrochemistry – solid state: volatile – comets: general – ISM: clouds – ISM: molecules – ISM:evolution

1. Introduction carbon chain constituents. These developments have raised ques-

tions about their associated formation and destruction routes
Interstellar polyynes are a large class of chemical compounds (Loomis et al. 2021; Cernicharo et al. 2021a,b, 2022; Fuente-
that can be described with the common formula R1 –(C)2n –R2 , taja et al. 2022a,b; Taniguchi et al. 2016, 2017, 2019). A steady
where n > 1. Due to the presence of the conjugated unsatu- growth in the number of carbon chain molecules identified to-
rated triple bonds, these chemical compounds are typically lin- wards protostars and protoplanetary disks can be outlined (Sakai
ear in shape and, along with the simplest alkynes HCCH (C2 H2 , & Yamamoto 2013; Bergner et al. 2018; Ilee et al. 2021; Guzmán
acetylene) and HCCCH3 (C3 H4 propyne), they are often referred et al. 2021; van Dishoeck et al. 2023).
as "carbon chains." Polyynes and other carbon chain molecules
comprise the large fraction of species identified to date in the It is generally assumed that carbon chain molecules in star-
inter- and circumstellar medium (ISM and CSM). Taniguchi forming regions are primarily produced in the gas phase through
et al. (2024) reported the detection of more than 100 carbon- various ion-molecule and neutral-neutral reaction sequences.
chain species. This accounts for about a third of species currently Astrochemical numerical simulations have a clear focus on the
identified in the ISM. introduction of new gas-phase formation routes explaining the
Polyynes and carbon-chain molecules are ubiquitous in the abundance of the newly observed species. Sometimes, the in-
ISM. They have been detected in extragalactic sources, pho- troduction of new gas-phase consumption routes is required to
todissociation regions (PDRs), planetary nebulae, and the en- avoid the overproduction of one of the observed intermediate
velopes around carbon-rich AGB stars (Pardo et al. 2005, 2022; species. Even though solid-state reactions on the surface of inter-
Cuadrado et al. 2015; Martín et al. 2021; Taniguchi et al. 2024). stellar dust grains are often required to produce the initial precur-
Observations of the Taurus Molecular Cloud-1 (TMC-1) using sors for these carbon chain species gas-phase formation routes,
the 40-meter Yebes telescope and the 100-meter Green Bank systematic studies of carbon chain reactivity on the grain surface
telescope resulted in the identification of many new gas phase are lacking.
Article number, page 1 of 12
 A&A proofs: manuscript no. aa52210-24corr

The dust temperature in the densest regions of molecular with respect to the H2 O (Schuhmann et al. 2019; Altwegg et al.
dark clouds drops to as low as ∼10 K, resulting in the contin- 2017). Moreover, the Hayabusa2 mission reported the presence
uous freeze-out of the species, including atoms and molecules of the saturated aliphatic chains identified in Ryugu’s organic
previously formed in the gas phase. The most prominent exam- matter (Yabuta et al. 2023).
ple is the freeze out of CO molecules produced in a sequence The surface chemistry of H-(C)2n H polyynes with n > 1
of gas-phase reactions starting from C+ ions. A CO freeze-out has not been investigated as systematically in the laboratory due
is the initial point for the formation of various complex organic to the difficulties associated with the acquisition and preserva-
molecules (COMs) as well as carbon chain oxides (Gerakines tion of polyyne samples. Experimental samples synthesized in
& Moore 2001; Öberg et al. 2009; Modica & Palumbo 2010; the laboratory are kept at liquid-N2 temperature to avoid spon-
Maity et al. 2015; Fedoseev et al. 2015, 2022; Chuang et al. taneous explosive decomposition (see Khlifi et al. (1995) and
2017; Qasim et al. 2019a; Urso et al. 2019). Surface interac- Kim & Kaiser (2009), for example). In the present study, a two-
tions of accreting CO molecules and H-atoms result in the for- step approach has been utilized. For the first time, a mixture of
mation of CH3 OH ice and organic molecules as complex as glyc- polyynes was obtained in situ on the substrate and the reactivity
erol, a key component of lipids and the membranes of living of this mixed polyyne ice with H-atoms was investigated in the
cells (Fedoseev et al. 2017). Unsaturated triple bonds compris- same experimental setup.
ing polyynes have high reactivities with accreting H atoms and Section 2 describes the applied experimental methodology
other open-shell species, such as free radicals, even at 10 K tem- and utilised ultra-high vacuum (UHV) cryogenic setup. In Sect.
perature (Molpeceres & Rivilla 2022). Indeed, dedicated labora- 3, the experimental results are presented and discussed. Section
tory studies performed by Hiraoka et al. (2000) and Kobayashi 4 focuses on the astrochemical implications and offers our con-
et al. (2017) revealed high reactivity of the simplest alkyne C2 H2 clusions.
(HCCH, acetylene) with H atoms, resulting in the formation of
C2 H4 (CH2 CH2 , ethylene) and C2 H6 (CH3 CH3 , ethane). Sub-
2. Experimental
sequently, Qasim et al. (2019b) reported similar results for the
surface hydrogenation of C3 H4 (HCCCH3 , propyne). The for- All experiments are performed using an ultra-high vacuum
mation of C3 H6 (CH2 CHCH3 , propene) followed by the ultimate (UHV) setup, SURFRESIDEUV , with a UV-photon source mod-
formation of the fully saturated C3 H8 (CH3 CH2 CH3 , propane) at ule. The original SURFRESIDE design is optimized to study
10 K. Saturation of triple bonds is also observed in the presence various astrochemically relevant solid-state atom- and radical-
of other radicals upon (non)energetic processing. Chuang et al. addition reactions at temperatures as low as 10 K, as described
(2020, 2021) and Qasim et al. (2019b) investigated the solid- in Ioppolo et al. (2013). The implementation of a UV-photon
state reactivity of C2 H2 and C3 H4 with OH (hydroxyl) radicals, source allows us to make a quantitative comparison between the
a well-known intermediate in forming H2 O ice. It was found that outcome of these "non-energetic" reaction routes, i.e., the reac-
the addition of OH radicals to the triple CC bonds can proceed tion routes between the species in the thermal equilibrium with
at 10 K. The activation barrier for this reaction is expected to be the surface, and the outcome of UV photon-induced "energetic"
lower than that for the similar addition of H atoms. Moreover, reaction routes (Chuang et al. 2017). The description of the up-
the addition of OH radicals to the double CC bonds proceeds grade of the setup is presented in Fedoseev et al. (2016) and
with even lower activation barriers, see Qasim et al. (2019b) and Chuang et al. (2018a). In this work, a UV-photon source is used
Molpeceres & Rivilla (2022) for more details. The final products to produce the thermodynamically unstable species directly in
obtained after the simultaneous exposure of C2 H2 and C3 H4 to the ice samples. This allows for the study of the chemical reac-
OH radicals and H atoms are various alcohols and aldehydes (ke- tivity between species that cannot be introduced into UHV setup
tones). These new reaction routes have been used to explain re- by other means (see, e.g., Butscher et al. 2015, 2016, 2017). Fol-
cent detections of i-C3 H7 OH (2-propanol) in Sgr B2(N2) in Bel- lowing this latter approach, a mixture of unsaturated hydrocar-
loche et al. (2022). They used a modified rate equation code ac- bons, including unstable C4 H2 and C6 H2 , can be synthesized in
counting for the non-diffusive reactions, such as the interactions situ by UV irradiation of C2 H2 ice. Then the reactivity of the
of species with immobile OH radicals. Similarly the routes pro- newly produced hydrocarbons with H atoms is investigated fol-
vided by Qasim et al. (2019a) have been suggested to explain the lowing the exposure of the ice samples to an H-atom beam. It
first detection of n-C3 H7 OH (n-propanol; Jiménez-Serra et al. should be noted that this experimental approach does not aim to
2022). So far, the simplest alkynes HCCH and HCCCH3 are mimic the exact composition of ice mantles in the ISM or their
the only representatives of H-(C)2n H and H-(C)2n -CH3 rows of complex interactions with impinging UV-photons and H-atoms.
alkynes and polyynes, whose surface reactivity with H atoms and Instead, it is aimed at an experimental verification that the hy-
OH radicals are systematically investigated. drogenation of polyynes occurs on a 10 K surface by accreting
This work aims to provide the first experimental confirma- H atoms using astronomically relevant H-atom fluences.
tions for surface hydrogenation of H-(C)2n H (n > 1) polyynes
under the conditions relevant to the early stages of star forma- 2.1. Experimental setup
tion. Based on the outcome of the aforementioned experimen-
tal and theoretical studies, we expect that hydrogenation of H- The SURFRESIDEUV setup is composed of a UHV main cham-
(C)2n H (n > 1) polyynes results in the intermediate formation ber with a typical base pressure of ∼10−10 mbar. The background
of various semi-saturated and fully saturated linear alkanes de- residual gas mainly comprises H2 , while the accretion rate of
scribed by the formula C2n H4n+2 . This will result in the presence background H2 O is negligible (<6.3 × 1010 molecules cm−2 s−1 ,
of linear alkanes on the surface of icy grains already at prestellar Chuang et al. (2018b) for the period of the experiment. A ro-
stages. The partial survival of the pristine ice through the later tatable gold-plated copper substrate is mounted on the cold tip
stages of star formation would enrich celestial bodies with alka- of a helium closed-cycle cryostat that is positioned in the center
nes. Linear alkanes, including C2 H6 , C4 H10 , and C6 H14 , have of the UHV main chamber. The temperature of the substrate is
been identified in comet 67P/Churyumov–Gerasimenko with regulated in the range between 8 and 450 K by means of resis-
high abundances of ∼5 × 10−1 (C2 H6 ) and ∼5 × 10−3 (C4 H10 ) tive heating and monitored using two silicone diodes with the
Article number, page 2 of 12
 G. Fedoseev et al.: Production of linear alkanes by solid-state hydrogenation of interstellar polyynes

absolute accuracy of ± 0.5 K. The C2 H2 :He gas mixture or Ar The ice composition is monitored in situ by means of
gas is admitted to the main chamber through high-precision all- Fourier-transform reflection absorption infrared spectroscopy
metal leak valves with the 22◦ angle to the substrate surface (RAIRS). Upon completion of the UV-exposure stage, a
normal. Two independent dosing lines are used to keep these quadrupole mass spectrometer-temperature programmed des-
gases for the whole extent of the experiment. A mixture of C2 H2 orption (QMS-TPD) measurement is performed. The substrate is
in He "bathing" gas is used to avoid the risk of spontaneous rotated by 135◦ to face directly the ion source of the QMS. Then,
C2 H2 decomposition. The substrate temperature is maintained during the TPD measurements, the ice is gently warmed up with
far above the He condensation point. This prevents the forma- a 2 K/min rate from 10 to 50 K to remove the "pillow" of Ar ice.
tion of He ice in all experiments. The mixed beam of H atoms Subsequently, the 5 K/min heating rate is used in the range of
and undissociated H2 molecules is obtained by thermal cracking 50 to 250 K to increase the sensitivity of the applied TPD tech-
of H2 molecules, using a Hydrogen Atom Beam Source (HABS; niques. The sublimating species are continuously monitored by
Tschersich 2000). HABS is mounted in an independent UHV means of QMS. The formed species are then identified through
chamber separated from the main chamber by a UHV shutter. the presence of their characteristic m/z (mass-to-charge) values
A U-bent quartz pipe is placed along the path of H-atom beam at characteristic desorption temperatures. Thus, two independent
to efficiently quench the high translational or ro-vibrational ex- parameters are used to identify the obtained products.
cited states of H-atoms and H2 -molecules prior to their impact The described experiment is then repeated using the very
on the substrate under the incident angle of 45◦ . The application same experimental conditions followed by irradiation of the ob-
of two independent commercial H-atom beam sources allows for tained ice with an overabundance of H atoms. Upon comple-
the crosscheck of the obtained results. UV-photons are generated tion of the H-atom exposure stage, QMS-TPD measurement is
by a microwave-discharged hydrogen flowing lamp (MDHL) at- performed by applying the same heating routine. The difference
tached to a MgF2 viewport (with a cutoff at 115 nm) on the main in the outcome of the performed experiments is used to iden-
chamber. The MgF2 viewport is positioned in front of the sub- tify the presence of four- and six-carbon bearing products of
strate parallel to the substrate plane. This configuration allows C2n H2 (n>1) polyynes hydrogenation, formed along with the ex-
incident photons to cover uniformly the whole area of the 2.5 pected products of well-investigated C2 H2 hydrogenation (Hi-
× 2.5 cm2 substrate. The H-atom and UV-photon fluxes are cali- raoka et al. 2000; Kobayashi et al. 2017; Chuang et al. 2020).
brated in situ, and the details of this procedure are available from Only the top monolayer of C2 H2 ice is assumed to be avail-
Ioppolo et al. (2013) as well as Fedoseev et al. (2016) and Lig- able for hydrogenation by incident H-atoms (Ioppolo et al. 2013;
terink et al. (2015), respectively. The H-atom flux utilised in the Chuang et al. 2018b). This assumption is in agreement with the
present study amounts to 2.4 × 1013 atoms cm−2 s−1 . The lower results of the pure HCCH ice hydrogenation experiment reported
limit on UV-photon flux at the substrate plane is estimated to by Kobayashi et al. (2017). The hydrogenation of 12 ML of
be ∼1.3 × 1013 cm−2 s−1 . The example of UV emission spectra pure HCCH ice at 10 K resulted in a relative HCCH consump-
obtained for the used F-type MDHL is available in Chen et al. tion of 0.06 at an equilibrium state (see Fig. 7 of Kobayashi
(2014) and Ligterink et al. (2015). The following commercially et al. 2017). This observation allows for the derivation of RAIRS
available reagents are used in the experiments: a 5% mixture of setup-specific C2 H2 band strength value. With this goal, pure
HCCH in He (Praxair), H2 (Linde, 5.0), and Ar (Linde, 5.0). C2 H2 ice is hydrogenated upon reaching the maximum C2 H2
consumption. Then, the difference in the total area for the se-
lected C2 H2 absorption features is obtained at the end of the
2.2. Experimental methods experiment. This area corresponds to the absorption by ∼1 ML
The experiments are performed in the following procedure. First, of C2 H2 ice (where 1 ML surface coverage is assumed to be
a "pillow" of Ar ice (10 Langmuir1 ) is deposited on top of a bare 1 × 1015 cm−2 ). With the geometry utilized in our setup, the
gold substrate. Then a ∼10 monolayer (ML) thick C2 H2 ice layer absorbance area equal to 0.028 cm−1 was obtained for the C-
is deposited on top of the predeposited Ar ice layer. The lay- H stretching mode of C2 H2 (ν3 , 3244 cm−1 ). This corresponds
ered ice sample is exposed to the UV-photon beam generated by to 0.064 cm−1 in optical depth, resulting in the setup-specific
MDHL to achieve partial polymerization of C2 H2 into its C2n H2 RAIRS band strength values equal to 6.5 × 10−17 cm molecule−1 .
(n > 1) polyynes derivatives. This polymerization has been ex-
tensively studied by Cuylle et al. (2014) using a combination of
mid-infrared and ultraviolet-visible (UV-VIS) spectroscopy (see 3. Results and discussion
also Compagnini et al. 2009; Wu et al. 2010; Puglisi et al. 2014; 3.1. Application of QMS-TPD technique
Abplanalp & Kaiser 2020). The thickness of the grown C2 H2 ice
is well below the penetration depth of UV-photons. This aims The QMS-TPD spectra obtained after the UV-exposure of the de-
to secure the uniform distribution of the formed products in the posited C2 H2 ice are presented in the left panel of Fig. 1. It is im-
photo-processed ice. On the other hand, the interaction of UV- portant to note that the ordinate axis is presented as a logarithm
photons passing through the ice with the gold substrate may of 10 to highlight the appearance of the small desorption signals
result in the production of photoelectrons. Hopkins & Riviere following the deviations from the exponential decays. Only the
(1964) reported the work function of >4.7 eV for gold. The de- most relevant m/z values are selected and shown for better clar-
posited ten Langmuir layer of Ar ice aims to prevent the interac- ity. Three distinct TPD peaks corresponding to the desorption
tion of the HCCH ice with the photoelectrons due to the limited of three individual H-(C)2n -H alkynes or polyynes can be clearly
penetration depth of photoelectrons in condensed phases (Jo & observed in the spectrum. These are C2 H2 (m/z = 26), C4 H2 (m/z
White 1991). = 50), and C6 H2 (m/z = 74). Under our experimental conditions,
the desorption of C2 H2 starts at about 55 K and peaks at 75 K,
1
1 Langmuir (L) corresponds to exposure of substrate at 1 × 10−6 torr while the desorption of C4 H2 occurs at 95 K and peaks at 120
pressure during one second at room temperature. This results in a sur- K. These temperature ranges are in agreement with the previ-
face coverage of about 1 monolayer. The usage of Langmuir estimation ous experimental results (see Zhou et al. 2009, 2010; Abplanalp
for the Ar ice is caused by the lack of absorption in the IR range. & Kaiser 2017). To our knowledge, no literature value has been
Article number, page 3 of 12
 A&A proofs: manuscript no. aa52210-24corr

Temperature, K Temperature, K
50 75 100 125 150 175 200 225 50 75 100 125 150 175 200 225
1E-07 1E-07
C2Hn desorption C2H2 (m/z=26) C2H6 desorption C2H2 (m/z=26)
C4H2 (m/z=50) C4H2 (m/z=50)
1E-08 C6H2 (m/z=74) 1E-08 C6H2 (m/z=74)
C4Hn desorption CH3CH2-X (m/z=29)
C4Hn desorption CH3CH2-X (m/z=29)
CH3CH2CH2-X (m/z=43) CH3CH2CH2-X (m/z=43)
C2H6 (m/z=30) C2H6 (m/z=30)
Intensity, counts

Intensity, counts
1E-09 C6Hn desorption C4H10 (m/z=58)
1E-09 C6Hn desorption C4H10 (m/z=58)

1E-10 1E-10

1E-11 1E-11

1E-12 1E-12

1E-13 1E-13

1E-14 1E-14
50 75 100 125 150 175 200 225 50 75 100 125 150 175 200 225
Temperature, K Temperature, K

Fig. 1. Left: QMS-TPD spectra in the range from 50 to 225 K for the selected m/z values obtained after the UV-exposure of 10 ML of pure HCCH
ice with 4.6 × 1016 photons cm−2 at 10 K. Right: QMS-TPD spectrum obtained after the hydrogenation of UV-exposed ice with 1.3 × 1017 cm−2
atoms at 10 K. The ordinate axis is presented as a logarithm of 10. An exponential decay of ion intensity appears as a straight line.

reported for pure C6 H2 ice. Under our experimental conditions, CCCCH, m/z=74) molecules, the observation of such a drop can
the corresponding m/z = 74 peak appears at 125 K and reaches only be considered tentative because of the low signal-to-noise
the maximum at about 150 K. Several additional m/z values are ratio. These drops in the areas of TPD curves in the right panel
presented in the spectra for reference. The m/z = 30 and m/z = of Fig. 2 are due to the consumption of C2 H2 , C4 H2 and C6 H2
58 correspond to the "parent masses" of C2 H6 and C4 H10 , i.e., molecules in the upper layer of the UV-exposed ice through the
the masses of ions obtained by the direct non-dissociative ioni- reactions with H atoms. These experimental results show that
sation of C2 H6 and C4 H10 , respectively. While the m/z = 29 and the reactivity of unsaturated triple bonds of C4 H2 (and, likely,
m/z=43 spectra correspond to the signals of C2 H5 + and C3 H7 + , C6 H2 ) with H-atoms is similar to the reactivity of the C2 H2 triple
the two most likely ions obtained by dissociative ionization of bond (see also Hiraoka et al. 2000; Kobayashi et al. 2017). The
various short linear aliphatic hydrocarbons in the ion head of shape and profile changes in the TPD curves obtained after the
the QMS. Appendix B in Schuhmann et al. (2019) offers typical hydrogenation of the ice can be attributed to the more complex
examples of mass-spectra obtained for the short linear hydrocar- (non-uniform) composition of the ice. Indeed, the binding ener-
bons. The QMS-TPD spectra presented in the left panel of Fig. gies for polyynes are higher than those for their corresponding
1 reveal the traces of C2 H6 ice through the rise of m/z =30 and saturated counterparts (see, e.g., Abplanalp & Kaiser 2017). This
m/z = 29 signals in the range from 55 to 80 K. No signs of other can be explained by the interactions between π-electrons of their
saturated hydrocarbons can be found. triple bonds. This difference in the binding energies can affect
The right panel of Fig. 1 presents a general view of the QMS- the shape and profile of polyyne desorption features obtained for
TPD spectra obtained after the hydrogenation of the UV-exposed the mixed ice.
C2 H2 ice under the same experimental conditions. Here, a mi- In addition to the data presented in Fig. 2, we present the
nor drop in the intensity of C2 H2 , C4 H2 , and C6 H2 desorption comparison between the QMS-TPD curves corresponding to the
features can be distinguished (see Fig. 2 for more details). On fully saturated aliphatic hydrocarbons obtained with and with-
the other hand, the appearance of new desorption features cor- out H-atom exposure to the ice in Fig. 3. The dissociative ion-
responding to the saturated aliphatic hydrocarbons can be ob- isation of various linear saturated aliphatic hydrocarbons in the
served. The rise of m/z = 30 (C2 H6 + ) and m/z = 29 (C2 H5 + ) ion source of the QMS results in the efficient cleavage of both C-
signals in the temperature range between 55 and 85 K can be C and C-H bonds. The upper panels in Fig. 3 show QMS-TPD
attributed to the desorption of C2 H6 . The rise of m/z = 58 curves obtained for the "parent masses" of C2 H6 (CH3 CH3 + , m/z
(C4 H10 + ), m/z = 43 (C3 H7 + ) and m/z = 29 (C2 H5 + ) in the range = 30) and C4 H10 (CH3 CH2 CH2 CH3 + , m/z = 58). At the same
from 95 to 115 K can be attributed to the desorption of C4 H10 . time, the m/z = 29 (CH3 CH2 + ) and m/z = 43 (CH3 CH2 CH2 + )
The third desorption feature in the range from 130 to 150 K can correspond to the common fragments obtained after dissociative
be tentatively assigned to semi-saturated or fully saturated hy- ionization of various linear aliphatic hydrocarbons. The peak in
drocarbons with six carbon atoms through the rise of m/z = 29 the range from 55 to 85 K can be confidently assigned to C2 H6 .
(C2 H5 + ). More details are given in Fig. 3. The m/z = 29 to m/z = 30 signal ratio of 0.8 is consistent with the
ratio reported for C2 H6 in the NIST database2 . The clear peaks
The detailed comparison between the QMS-TPD curves ob- for the characteristic m/z signals of linear C4 H10 equal to 58, 43
tained for the H-(C)2n -H polyynes with and without the hydro- and 29 are observed in the range from 90 to 105 K. These desorp-
genation of the ice is presented in Fig. 2. The linear scale is used
for all of the plots for the direct comparison of the corresponding 2
NIST Mass Spec Data Center, S. E. Stein, director, "Mass Spectra" in
areas. The m/z signals assigned to C2 H2 (HCCH, m/z = 26) and NIST Chemistry WebBook, NIST Standard Reference Database Num-
C4 H2 (HCCCCH, m/z =50) demonstrate about 0.1 drop in the in- ber 69, eds. P. J. Linstrom and W. G. Mallard, National Institute of Stan-
tensity upon hydrogenation of the ice. In the case of C6 H2 (HCC- dards and Technology, Gaithersburg, MD 20899, USA.

Article number, page 4 of 12

 G. Fedoseev et al.: Production of linear alkanes by solid-state hydrogenation of interstellar polyynes

Temperature, K Temperature, K
50 75 100 125 150 175 200 225 50 75 100 125 150 175 200 225
1E-10
+
C2H2 (m/z = 26, HCCH ) C2H6 (m/z = 30, CH3CH3+)
4E-9
5E-11
2E-9

0E+0 1E-12 C4H10 (m/z = 58, CH3CH2CH2CH3+)

Intensity, counts

3E-11 C4H2 (m/z = 50, HCCCCH+)

5E-13

Intensity, counts
2E-11

1E-11
7E-11
0E+0 C2H5-X (m/z = 29, CH3CH2-+)
5E-11
C6H2 (m/z = 74, HCCCCCCH+)
1E-12 3E-11

5E-13
1E-11

0E+0
C3H7-X (m/z = 43, CH3CH2CH2-+)
50 75 100 125 150 175 200 225 1E-11

Temperature, K
5E-12
Fig. 2. Direct comparison between the fragments of QMS-TPD spectra
in the range from 50 to 225 K obtained after the UV-exposure of 10 ML
thick pure HCCH ice at 10 K with >4.6 × 1016 cm−2 photons (black 50 75 100 125 150 175 200 225
empty circles) and the subsequent exposure of this photoprocessed ice Temperature, K
with 1.3 × 1017 cm−2 H atoms at 10 K (red filled circles). The results
Fig. 3. Similar to Fig. 2. M/z signals corresponding to linear saturated
obtained upon subtraction of the initial mass spectrum from the mass
aliphatic hydrocarbons are shown.
spectrum obtained upon hydrogenation of the ice for each of the pre-
sented m/z values are presented in Appendix A
C4 H10 and is consistent with the literature value reported for the
pure CH2 CHCCH ice by Kim & Kaiser (2009) (see Fig. 4 of Kim
tion temperatures are in close agreement with the values reported & Kaiser 2009). Generally, a gradual shift towards lower des-
previously for C4 H10 (Abplanalp & Kaiser 2017, the structural orption temperature is expected with the increase of hydrogena-
isomer is not specified). In addition to the two resolved desorp- tion degree, namely, Tdep (C4 H2 ) > Tdep (C4 H4−8 ) > Tdep (C4 H10 ),
tion peaks, a weaker desorption feature can be observed in the as, for example, described in Abplanalp & Kaiser (2017). The
range from 125 to 150 K for m/z = 29 (CH3 CH2 + ) and m/z = formation of CH2 CHCCH upon UV exposure of C2 H2 ice is in
43 (CH3 CH2 CH2 + ). Observation of these dissociative ionization agreement with the experimental results of Cuylle et al. (2014).
products is in agreement with the possible presence of C6 H14 The exact identification of produced semi-saturated hydrocar-
(CH3 CH2 CH2 CH2 CH2 CH3 ); namely, a fully saturated deriva- bons requires other experimental techniques and is beyond the
tive of C6 H2 (HCCCCCCH). The observed desorption temper- scope of this work.
ature range overlaps with that reported by Abplanalp & Kaiser A weak desorption feature observed for the m/z = 54
(2017) for various hydrocarbons consisting of six carbon atoms. (C4 H6 + ) signal can be attributed to the traces of one of the C4 H6
However, without the identification of m/z = 86 “parent mass,” isomers in the irradiated ice. The most probable candidates are
this attribution is considered tentative. The comparison between ethylacetylene (CH3 CH2 CCH) and divinyl (CH2 CHCHCH2 ).
the observed intensities of m/z signals and the standard mass Here, the preference can be given to CH3 CH2 CCH. The ob-
spectra available from the NIST database is presented in Ap- served m/z = 54 signal is the most intense peak in the mass spec-
pendix B. tra of CH3 CH2 CCH and corresponds to its non-dissociative ion-
It should be noted that the m/z signals associated with the ization in the ion source of the QMS. Previous laboratory stud-
presence of semi-saturated hydrocarbons can also be identified ies showed that surface hydrogenation of HCCH and HCCCH3
in the mass spectra. However, the unambiguous identification of triple bonds proceeds with a higher activation barrier than the
semi-saturated hydrocarbons becomes increasingly difficult due hydrogenation of CH2 CH2 and CH2 CHCH3 double bonds, see
to the high number of possible structure isomers and the exist- Kobayashi et al. (2017) and Qasim et al. (2019b). Similar be-
ing overlap between the m/z signals of fully saturated and semi- havior can be expected for the hydrogenation of CH2 CHCCH
saturated hydrocarbons. The combination of C4 H4 , C4 H6 , and triple and double bonds. Preferable formation of CH3 CH2 CCH
C4 H8 alone has more than 20 stable structural isomers, excluding can be suggested in this case. Although CH2 CHCHCH2 is ther-
isotopes. Meanwhile, C6 Hn semi-saturated hydrocarbons have modynamically more stable than CH3 CH2 CCH due to the pres-
more than 100 isomers. Some observations can be made based ence of the conjugated double bonds, the preference should be
on the obtained laboratory data, see Fig. 4. It is seen that prior given to the kinetic argument. Only traces of the C4 H8 + m/z des-
to the hydrogenation of the UV-exposed ice, the peaks of m/z orption feature can be observed in the QMS-TPD spectrum of
=52 (C4 H4 + ) and m/z = 54 (C4 H6 + ) signals are already present UV-exposed ice prior to hydrogenation.
in the spectra. The desorption starts from 100 K and peaks in The m/z curves obtained after the hydrogenation of the ice
the range from 115 to 120 K. The m/z = 52 value corresponds reveal the overall consumption of C4 H4 and the formation of
to the “parent” and most intense signal of vinylacetylene (C4 H4 , C4 H6 and C4 H8 . This observation is consistent with the increase
CH2 CHCCH). The desorption temperature registered for the m/z of hydrocarbon hydrogenation degree following various H-atom
= 52 signal is higher than that observed for the m/z = 58 signal of addition reactions in the mixed ice. The simultaneous rise of
Article number, page 5 of 12
 A&A proofs: manuscript no. aa52210-24corr

Temperature, K phase should impact only a few adjunct MLs of the ice. Thus,
50 75 100 125 150 175 200 225 the contribution of the interphase is consistent with the low 10
3E-11 C4H4 (m/z = 52, CH2CHCCH+) ML thickness of the ices used in present study, in comparison to
2E-11 the thick µm ice used by Hudson et al. (2014). A clear growth
1E-11
0E+0
of the absorption feature in the range from 3308 to 3265 cm−1
4.0E-12 centered around 3285 cm−1 is observed. This feature can be suc-
3.0E-12 C4H6 (m/z = 54, CH2CHCHCH2+
Intensity, counts

cessfully assigned to the C-H stretching modes of both HCC-

2.0E-12
or CH3CH2CCH+) CCH and CH2 CHCCH (Tørneng et al. 1980; Zhou et al. 2009;
1.0E-12
0.0E+0 Kim & Kaiser 2009), one of the most intensive modes for both
2.0E-12
C4H8 (m/z = 56, CH2CHCH2CH3+) of the species. The assignment of CH2 CHCCH can be further
1.5E-12 supported by the observation of a broad merged absorption fea-
1.0E-12
ture in the range from 1020 to 900 cm−1 with two peaks centered
5.0E-13
2.5E-11
around 975 and 935 cm−1 . These features can be tentatively as-
2.0E-11 C2H3 (m/z = 27, CH2CH-+ signed to the ν14 and ν15 modes of CH2 CHCCH (Tørneng et al.
1.5E-11 or H13CCH+) 1980; Kim & Kaiser 2009), along with the ν7 mode of C2 H4 .
1.0E-11
5.0E-12
These observations further support the assignments done by the
50 75 100 125 150 175 200 225
QMS-TPD technique, confirming the formation of both species
Temperature, K already at 10 K.
In the right panel of Fig. 5, the RAIRS spectra (a) and (b) ob-
Fig. 4. Similar to Figs. 2 and 3. M/z signals associated with the semi- tained prior to and after the H-atom exposure of the ice are pre-
saturated aliphatic hydrocarbons are presented. sented. In a similar way, the RAIR difference spectrum (b)-(a)
is shown for comparison. The expected decrease in the intensity
of absorption features associated with unsaturated hydrocarbons
m/z = 56 (C4 H8 + ) and m/z = 27 (CH2 CH+ ) signals in the range (i.e., HCCH, HCCCCH and CH2 CHCCH) is observed. Simul-
from 100 to 115 K is consistent with the desorption of 1-butene taneously, multiple absorption features appear in the range from
(CH2 CHCH2 CH3 ). The lower desorption temperature registered 2990 to 2870 cm−1 and can be assigned to the C-H stretching
for m/z = 56 (C4 H8 + ) in comparison to m/z=52 (C4 H4 + ) and modes of newly formed saturated hydrocarbons. The zoom-in
m/z=54 (C4 H6 + ) is in line with the higher hydrogenation degree spectral region of interest is presented in Fig. 6. Three character-
of CH2 CHCH2 CH3 . It should be noted that the rise of m/z = 56 istic absorption features of CH3 CH3 are observed at 2975, 2943,
and m/z = 27 signals is also observed in the range from 125 to and 2882 cm−1 corresponding to the ν10 , ν8 +ν11 and ν5 modes,
150 K. In this range, the desorption of 6-carbon bearing hydro- respectively (Comeford & Gould 1961; Kim et al. 2010; Turner
carbons should occur, see Abplanalp & Kaiser (2017). Both of et al. 2018). However, in addition to the indicated absorption
these m/z values are present in the mass spectra of fully saturated features of CH3 CH3 , the traces of two distinct absorption fea-
linear C6 H14 . tures of CH3 CH2 CH2 CH3 can be tentatively identified at 2959
(ν12 , ν27 ) and 2925 cm−1 (ν13 ) corresponding to the asymmet-
ric CH stretching modes of CH3 - and -CH2 - respectively (Tør-
3.2. RAIRS and kinetic analysis
neng et al. 1980; Kim et al. 2010; Turner et al. 2018). To fur-
Complementarily to the QMS-TPD data, RAIRS results provide ther outline the plausible presence of -CH2 - asymmetric stretch-
information about the ice composition at 10 K prior to the sample ing mode of CH3 CH2 CH2 CH3 the reference RAIRS spectrum
thermal processing and consequent destruction during the TPD of C2 H6 obtained from Öberg et al. (2009) is plotted versus the
experiment. Moreover, information about the phase changes and data obtained in the hydrogenation experiment. The asymmet-
kinetic data can be acquired during the UV-processing and H- ric stretching mode of -CH2 - at 2925 cm−1 can be considered a
atom exposure of the ice. In the left panel of Fig. 5, the RAIR characteristic absorption feature for all saturated linear aliphatic
spectra obtained after the deposition of pure C2 H2 ice at 10 K on hydrocarbons (see, e.g., Yabuta et al. 2023). The RAIR differ-
top of the 10 Langmuir Ar "pillow" (spectrum a), and the conse- ence spectrum obtained after hydrogenation of the ice does not
quent UV-exposure of C2 H2 ice (spectrum b) are presented. The reveal the growth of any absorption features that can be assigned
obtained RAIR difference spectrum; namely, (b)-(a), is added to the semi-saturated hydrocarbons with C=C double bonds.
for comparison. A clear decrease in the total area of the absorp- In first approximation the column density of the species is
tion features associated with the CH stretching mode (ν3 , 3265- directly proportional to the total absorbance areas of their corre-
3210 cm−1 ), CCH bending mode (ν5 , 825-725 cm−1 ), and the sponding RAIRS absorption features. The "in situ" RAIRS tech-
combinational mode (ν4 +ν5 , 1430-1350 cm−1 ) is observed, in- nique allows for tracking the evolution of the total areas of the
dicating the consumption of HCCH. Moreover, the morpholog- assigned absorbance features over the time of the H-exposure
ical changes in HCCH ice can be observed following the dis- experiment. Figure 7 presents the obtained kinetic curves for
appearance of C-H stretching and ν4 +ν5 combinational mode the species identified in RAIR data. The total areas of absorp-
absorption features associated with the contribution of "poly- tion features assigned to the − −CH stretching modes of HC− −CH
crystalline" HCCH ice (i.e., 3226 and 1390 cm−1 ) and the cor- (3265-3210 cm−1 ) or HC− CC
− − − CH and CH 2 − CHC −
−CH (3308-
responding growth of the C-H stretching mode absorption fea- 3265 cm−1 ) were used to track the consumption of these species
ture (i.e., 3240 cm−1 ) associated with "amorphous" HCCH ice following hydrogenation of their C− −C triple bonds. The forma-
(see Fig. 8 of Hudson et al. 2014). The "amorphous" and "poly- tion of C2 H6 is tracked through the absorption of its CH asym-
crystalline" terms are used in quotes, as this band profile mod- metric stretching mode (ν10 , 2995-2964 cm−1 ). The integration
ification can also be attributed to the different orientation of of the peak (2929-2909 cm−1 ) is used to track C4 H10 follow-
HCCH molecules located in the interphase with vacuum or with ing the tentative assignment of this absorption feature to the
the Ar ice "pillow", in comparison to the orientation of HCCH CH asymmetric stretch of -CH2 -. The modulus of absorbance
molecules in the bulk of HCCH ice. The effects in the inter- is taken for C2 H2 and C4 H2 consumed in the experiments. This
Article number, page 6 of 12
 G. Fedoseev et al.: Production of linear alkanes by solid-state hydrogenation of interstellar polyynes

Wavelength, mm Wavelength, mm
2.9 3 3.1 3.2 3.3 8 10 12 14 3 3.2 3.4 3.6 8 10 12 14
0.025 0.025
C2H2 UV exposed HCCH
HCCH
HCCH UV exposed C2H2 Hydrogenated UV-exposed ice
Difference spectrum Difference spectrum
0.020 C4H2 (Zhou et al. 2009) 0.020
C4H2 (Zhou et al. 2009)
C4H4 (Kim et al. 2009) C4H4 (Kim et al. 2009)
HCCCCH HCCH

Absorbance
Absorbance

CH2CHCCH
0.015 CH3CH3 CH2CH2 0.015
CH2CH2 HCCCCH
HCCH CH3CH3 CH2CHCCH
CH2CHCCH CH2CHCCH
CH3CH2CH2CH3 HCCH
0.010 (a) 0.010
(a)
(b)
(b)
0.005 (b)-(a) (b)-(a) 0.005

0.000 0.000
3450 3250 3050 1400 1200 1000 800 3450 3250 3050 2850 1400 1200 1000 800

Wavenumber, cm-1 Wavenumber, cm-1

Fig. 5. Left: RAIR spectra obtained after the deposition of 10 ML of HCCH ice at 10 K (a, black line), after the exposure of this obtained ice with
4.6 × 1016 cm−2 photons (b, red line) and by subtracting the initial spectrum (a) from spectrum (b) (green line). Right: RAIR spectra obtained after
the UV-exposure of 10 ML thick pure HCCH ice at 10 K with 4.6 × 1016 cm−2 photons (a, red line), the consequent exposure of this photoprocessed
ice with 1.3 × 1017 cm−2 H atoms at 10 K (b, blue line), and by subtracting the initial spectrum (a) from spectrum (b) (green line). The grey dashed
and dotted lines are the reference RAIRS spectra obtained for the pure C4 H2 and C4 H4 ices by Zhou et al. (2009) and Kim & Kaiser (2009). All
spectra are offset for clarity.

W a v e le n g th , m m of the fully saturated hydrocarbons with respect to the consump-

0 .0 0 3 0
3 3 .0 5 3 .1 3 .3 5 3 .4 3 .4 5 3 .5
0 .0 0 3 0
tion of the initial reagent. Similarly, there is no shift between the
D iffe r e n c e s p e c tr u m C4 H2 and C4 H10 kinetic curves. Thus, a faster rate for hydro-
C 2 H 6 r e fe r e n c e s p e c tr u m ( O b e r g e t a l. 2 0 0 9 ) genation of the intermediate C4 H4−8 double bonds in compari-
0 .0 0 2 5 0 .0 0 2 5
C 4 H 1 0 ( S tr a z z u lla & B a r a tta 1 9 9 2 )
son to the hydrogenation of C4 H2 triple bonds can be inferred.
0 .0 0 2 0
C H 3 C H 2 C H 2 C H 3 (n 1 2 ,n 2 7 )
0 .0 0 2 0
This observation is also consistent with the lack of absorption
C H 3 C H 3 (n 1 0 )
features that can be assigned to the semi-saturated hydrocarbons
A b s o r b a n c e

H C C C C H (n 4)
A b s o r b a n c e

C H C H C H C H (n )
C H C C H (n 1) C H C H (n 8+ n ) 3 2 2 3 1 3

0 .0 0 1 5
C H 2 3 3 1 1
0 .0 0 1 5
with double bonds. The plateau appears in the range of H-atom
(n 5)
H C C H (n 3)
C H 3 C H 3
fluence from 3 × 1016 to 6 × 1016 cm−2 . Assuming the H-atom
0 .0 0 1 0 0 .0 0 1 0
flux in dark clouds is ∼104 atoms cm−2 s−1 , these values of H-
atom fluences are obtained at ∼1 × 105 and ∼2 × 105 years,
0 .0 0 0 5 0 .0 0 0 5
respectively. It should be noted that these periods fall within the
characteristic timescales of the dark clouds stage (Boogert et al.
0 .0 0 0 0 0 .0 0 0 0
2015; Chevance et al. 2020).
3 3 5 0 3 3 0 0 3 2 5 0 3 2 0 0 2 9 7 5 2 9 2 5 2 8 7 5
-1
W a v e n u m b e r, c m

Fig. 6. Zoom-in into the CH stretching vibration modes region for the 4. Astrochemical implications and conclusions
RAIR difference spectrum obtained after hydrogenation of UV-exposed
C2 H2 ice (green line). See the right panel of Fig. 5 for more details. Our laboratory results show that fully saturated linear hydrocar-
The spectrum of pure C2 H6 ice at 20 K is adapted from Öberg et al. bons (n-alkanes) such as n-C4 H10 and plausibly n-C6 H14 can
(2009) (black dots). The spectrum of pure C4 H10 at 10 K is obtained by be produced by the surface hydrogenation of the correspond-
Strazzulla & Baratta (1992) (blue line). All spectra are offset for clarity. ing C2n H2 (H-(C)2n -H) polyynes at 10 K. This work further ex-
tends the experimental finding obtained by Hiraoka et al. (2000),
Kobayashi et al. (2017) and Qasim et al. (2019b), which demon-
allows for the direct comparison with produced species. The pre- strates the formation of C2 H4 , C2 H6 , C3 H6 , and C3 H8 by surface
sented kinetic curves show that the total areas of all selected fea- hydrogenation of simplest alkynes C2 H2 and C3 H8 , under the
tures follow a very similar profile and reach the plateau around physical conditions resembling those founds in dark molecular
the same hydrogenation time. This indicates that the rates (or ac- clouds. Kobayashi et al. (2017) reported a four times higher rate
tivation barriers) of H-atom addition reactions to the triple bonds for the hydrogenation of the HCCH triple bond than for the hy-
of C2 H2 , C4 H2 , and C4 H4 have similar values. Otherwise, a de- drogenation of CO molecules. This makes HCCH hydrogenation
lay in the appearance of a plateau could be observed for the ki- efficient at dark molecular cloud conditions. Comparable rates
netic curve of a molecule with a slower H-atom addition rate. for the hydrogenation of HCCH, HCCCCH, and H2 CCHCCH
The lack of shift between the C2 H2 and C2 H6 kinetic curves is triple bonds can be proposed based on the analysis of the pre-
observed. This is in agreement with the faster rate for hydrogena- sented kinetic data. Even higher rates are expected for hydro-
tion of C=C double bonds of the intermediate C2 H4 previously genation of C−C double bonds of intermediate semi-saturated
reported by (Kobayashi et al. 2017). The slower hydrogenation hydrocarbons produced by hydrogenation of triple bonds (see
rate of the intermediate would result in a delay in the appearance also Kobayashi et al. 2017; Qasim et al. 2019b).
Article number, page 7 of 12
 A&A proofs: manuscript no. aa52210-24corr

tion of the icy grains can provide limited protection from UV-
photons originating both from the cosmic ray induced UV-field
Modulus of Absorbance area, cm-1

1E-2
and the protostar. Preservation of produced linear alkanes and
the intermediate semi-saturated hydrocarbons followed by their
integration into the pristine material of comets is consistent with
the detection of alkanes released by comet 67P/Churyumov-
Gerasimenko (see Schuhmann et al. 2019; Altwegg et al. 2017).
In addition, Schuhmann et al. (2019) reported that saturated alka-
1E-3 nes account for 42% of the total amount of detected hydrocar-
bons in Comet 67P/Churyumov-Gerasimenko, while the contri-
bution of unsaturated hydrocarbons is 56%. The cycloalkanes
contribution is calculated to be at most 2 %. A minimum con-
tribution of cycloalkanes is consistent with the production of
C2H2 (n3) C2H6 (n10)
aliphatic hydrocarbons by the hydrogenation of linear polyynes.
C4H2 (n4) (+C4H4 (n1)) C4H10 (n13)
It should be noted that even though the reference spectra of lin-
1E-4 ear alkanes were used in the study by Schuhmann et al. (2019),
0.0 4.0×1016 8.0×1016 1.2×1017 the contribution of branched alkanes could not be deconvoluted
H-atom fluence, cm-2 in that work.
Besides observations in comet 67P, hydrocarbons have been
Fig. 7. Kinetic curves obtained for C2 H2 , C6 H2 , C4 H2 , and C4 H10 . Note: recently identified on the surface of Ceres (De Sanctis et al.
the area of the (ν4 ) absorption feature of C4 H2 cannot be deconvoluted 2017) and in the samples from the asteroid Ruygu delivered by
from the contribution of the (ν1 ) absorption feature of C4 H4 . Thus, the
combined area is used for the integration. The modulus of absorbance
the Hayabusa2 mission. Observation of asymmetric stretching
is taken for C2 H2 and C4 H2 consumed in the experiments. This allows modes of CH3 - (2960 cm−1 , 3.38 µm) and -CH2 - (2930 cm−1 ,
for the direct comparison with produced species. The ordinate axis is 3.41 µm) along with the other bands in the infrared range is used
presented as a logarithm of 10. to constrain the presence of aliphatic hydrocarbons in Ryugu
samples by Yabuta et al. (2023). Identification of characteris-
tic -CH2 - modes is consistent with the presence of linear alka-
These experimental findings have a direct application to the nes comprising three or more carbon atoms or with the pres-
surface chemistry at the early stages of star formation and, in par- ence of linearly saturated hydrocarbon segments incorporated
ticular, dark molecular clouds. This evolutionary stage is charac- into the organic residue. Moreover, Yabuta et al. (2023) report
terized by low pressures (104 -106 cm−3 ) and temperatures (∼10 a relatively high -CH2 - to -CH3 peak intensity ratio equal to 1.9.
K). It sets up the initial chemical composition for the future Based on these observations and on the comparison with the ra-
evolutionary stages of star formation, providing material for the tios observed in Murchison and Ivuna meteorites, Yabuta et al.
formation of protostars and protoplanetary disks. The data ob- (2023) inferred that Ryugu’s organic matter may contain longer
tained by various space exploration missions such as Rosetta and aliphatic chains than in the meteoritic insoluble organic matters
Hayabusa2 suggests that part of the chemical inventory produced (IOMs).
during the dark clouds stage may survive the harsh later stages Gas-phase observations of saturated linear hydrocarbons
of star formation and provide pristine material for comets and are challenging because of the low dipole moment of these
asteroids (Rubin et al. 2015; Yabuta et al. 2023). The chemistry molecules. Alternative method for alkanes identification in the
of dark clouds is driven by the interplay between gas and dust. ISM can be suggested. If alkanes are present on the grain sur-
Ubiquitous sub-µm dust grains provide the surface on which the face early during the dark cloud stage, these species can become
simplest gas-phase chemical species (e.g., H, O, N, CO, etc.) ac- a target for JWST observations in the mid-infrared range. Albeit
crete and react. Atom addition reactions among accreting species the abundance of each individual alkane is expected to be low,
result in the formation of "H2 O-rich" and "CO-rich" ice mantles their absorption features overlap (Tørneng et al. 1980; Turner
on the surface of the dust grains (Öberg et al. 2011; Boogert et al. et al. 2018). This will result in the cumulative add-up of individ-
2015). ual absorption of each species into the combined optical depth.
Interstellar carbon chains and polyynes are efficiently pro- In this way the whole class of chemical compounds can be ob-
duced early in dark molecular clouds through cold gas-phase re- served simultaneously. Besides the CH3 - (2960 cm−1 , 3.38 µm)
action routes, see Taniguchi et al. (2024) and references therein. and -CH2 - (2930 cm−1 , 3.41 µm) bands mentioned earlier, the
The produced polyynes and carbon chains should accrete on the CH3 -/-CH2 - deformation/scissoring modes at 1460 cm−1 (6.85
surface of dust grains and become available for reactions with µm) and CH3 - symmetric deformation mode at 1380 cm−1 (7.25
other accreting species, such as H atoms. The efficient hydro- µm) are good potential candidates for such "family" spectral in-
genation of polyynes demonstrated in the present study indi- dicators.
cates that the formation of various linear aliphatic hydrocarbons Semi-saturated hydrocarbons can be observed in the gas
can be expected at the beginning of the dark cloud stage. More- phase. Such observations would require a mechanism respon-
over, the incorporation of other species (e.g., OH, O, N, etc.) sible for the partial grain-to-gas transfer of produced interme-
into the polyyne hydrogenation chain will result in the formation diate species at low temperatures, such as reactive desorption
of even more complex organic species (see Qasim et al. 2019a; (see, e.g., Minissale et al. 2016; Oba et al. 2018; Chuang et al.
Molpeceres & Rivilla 2022; Santos et al. 2024; Chuang et al. 2018b). Cernicharo et al. (2021b) reported the first detection of
2020, 2021, 2024). C4 H4 (vinylacetylene) in TMC-1 through observation of its 6
The formation of n-alkanes and semi-saturated aliphatic hy- transitions. C4 H6 (ethylacetylene) was also tentatively identified
drocarbons early in dark clouds is important for the preserva- in their study. So far, there have been no reports about successful
tion of these species during the later stages of star formation. detections of 1-butene, despite the fact that its structural isomer
The "H2 O-rich" and "CO-rich" ice mantles along with coagula- isobutene was observed in TMC-1; see Fatima et al. (2023). If
Article number, page 8 of 12
 G. Fedoseev et al.: Production of linear alkanes by solid-state hydrogenation of interstellar polyynes

Fig. 8. Schematic representation of the overall suggested mechanism. Various polyynes observed in dark clouds (e.g., TMC-1) are presented in
the left part of the reaction scheme. The accretion of polyynes on the surface of the grains is followed by hydrogenation of their unsaturated
CC triple bonds, resulting in the formation of their semi-saturated and fully saturated counterparts. Besides CH2 CHCCCHO, all of the first-
generation products obtained by such hydrogenation have also been observed in the gas phase in TMC-1 or other dark clouds (Brown 1981; Irvine
& Hjalmarson 1984; Agúndez et al. 2021; Cernicharo et al. 2001, 2020, 2021a,b, 2024; Lee et al. 2021; McGuire et al. 2017). In the right part
of the reaction scheme, we present the fully saturated aliphatic organic compounds. Most of these molecules have been observed in the comet
67P/Churyumov-Gerasimenko. The heavy molecules whose identifications are still lacking are marked with asterisks. It should be noted that UV-
photolysis and cosmic ray processing of fully saturated aliphatic compounds result in their efficient dehydrogenation. The high saturation degree
of the detected aliphatic compounds hints at their partial formation through surface hydrogenation mechanisms (Altwegg et al. 2017; Schuhmann
et al. 2019; Hänni et al. 2021, 2022, 2023). The image of comet 67P/Churyumov-Gerasimenko is taken by ESA Rosetta on September 2, 2014.3

solid-state formation routes contribute to the gas-phase enrich- we can expect that C− −C triple bonds of cyanopolyynes can par-
ment of these species, then other semi-saturated hydrocarbons ticipate in hydrogenation reactions that result in the formation
can be set as targets for future gas-phase observations. The pre- of aliphatic nitriles or even amines (see also Theule et al. 2011;
cise identification of intermediate four- and six-carbon bearing Nguyen et al. 2019). Similarly, the hydrogenation of (H)Cn O and
semi-saturated hydrocarbons in the present work was challeng- Cn S carbon chains can result in the formation of various aliphatic
ing. This is mainly because of the high number of possible iso- aldehydes, alcohols, and thiols. We give more details in Fig. 8.
mers and an overlap between their characteristic m/z values in These substituted hydrocarbons have direct astrobiological im-
the mass spectra. The determination of the exact C4 H2 and C6 H2 plications as they are amphiphilic and may play a part in the
hydrogenation sequences could serve as the subject of future formation of micelles in aqueous solutions, the most primitive
experimental and theoretical studies. Nevertheless, we suggest prototypes of cells and organelles (Segré et al. 2001; Trevors &
that the preference should be given to the observations of semi- Psenner 2001; Stevenson et al. 2015).
saturated hydrocarbons with triple bonds due to their higher sta- Acknowledgements. This work is dedicated to the memory of Prof. dr. Harold V.
bility. J. Linnartz. This research was funded through financial support from the Euro-
Finally, the present work uses the two-step experimental pean Union’s Horizon 2020 research and innovation programme under the Marie
technique to investigate the polyynes reactions with H atoms. Skłodowska-Curie actions grant agreement no. 664931, and the Netherlands Re-
search School for Astronomy (NOVA). GF thanks the Xinjiang Tianchi Talent
The mixture of unstable polyynes was synthesized in situ on Program (2024). GAB and MEP acknowledge Progetto Premiale 2012 ‘iALMA’
the substrate in the main UHV chamber of the setup by UV- grant (CUP C52I13000140001) and INAF Grant “Ricerca Fondamentale 2022”
irradiation of C2 H2 ice. Then, the hydrogenation process of the (CUP C63C22000900005). KJC is grateful for support from NWO via a VENI
obtained mixed ice using an H-atom beam was performed. Si- fellowship (VI.Veni.212.296). We would like to thanks Juan Tuo for her help in
preparation of this manuscript.
multaneous hydrogenation of the mixed ice allowed us to com-
pare the relative reactivity of involved species. This approach can
be used to study the hydrogenation of other species, which might
not otherwise be so easily obtained in the lab. This may include References
cyanopolyynes or oxygen- and sulphur-bearing carbon chains.
Abplanalp, M. J. & Kaiser, R. I. 2017, ApJ, 836, 195
The former, for example, can be synthesized by UV-exposure Abplanalp, M. J. & Kaiser, R. I. 2020, ApJ, 889, 3
to HCN/C2 H2 mixed ice. Then, their overall reactivity with H- Agúndez, M., Marcelino, N., Tercero, B., et al. 2021, A&A, 649, L4
atoms can be investigated. Analogously to the present study and Altwegg, K., Balsiger, H., Berthelier, J. J., et al. 2017, MNRAS, 469, S130
the works of Kobayashi et al. (2017) and Qasim et al. (2019b), Belloche, A., Garrod, R. T., Zingsheim, O., Müller, H. S. P., & Menten, K. M.
2022, A&A, 662, A110
3
Bergner, J. B., Guzmán, V. G., Öberg, K. I., Loomis, R. A., & Pegues, J. 2018,
Emily Lakdawalla, Comet jets! NavCam view of comet ApJ, 857, 69
Churyumov-Gerasimenko on September 2, 2014, ESA, Rosetta, Boogert, A. C. A., Gerakines, P. A., & Whittet, D. C. B. 2015, ARA&A, 53, 541
https://www.planetary.org/space-images/comet-cg-20140902-jets Brown, R. L. 1981, ApJ, 248, L119

Article number, page 9 of 12

 A&A proofs: manuscript no. aa52210-24corr

Butscher, T., Duvernay, F., Danger, G., & Chiavassa, T. 2016, A&A, 593, A60 Pardo, J. R., Cernicharo, J., Tercero, B., et al. 2022, A&A, 658, A39
Butscher, T., Duvernay, F., Rimola, A., Segado-Centellas, M., & Chiavassa, T. Puglisi, O., Compagnini, G., D’Urso, L., et al. 2014, Nuclear Instruments and
2017, Physical Chemistry Chemical Physics (Incorporating Faraday Transac- Methods in Physics Research B, 326, 2
tions), 19, 2857 Qasim, D., Fedoseev, G., Chuang, K. J., et al. 2019a, A&A, 627, A1
Butscher, T., Duvernay, F., Theule, P., et al. 2015, MNRAS, 453, 1587 Qasim, D., Fedoseev, G., Lamberts, T., et al. 2019b, ACS Earth and Space Chem-
Cernicharo, J., Agúndez, M., Cabezas, C., et al. 2021a, A&A, 656, L21 istry, 3, 986
Cernicharo, J., Cabezas, C., Agúndez, M., et al. 2021b, A&A, 648, L3 Rubin, M., Altwegg, K., Balsiger, H., et al. 2015, Science, 348, 232
Cernicharo, J., Fuentetaja, R., Cabezas, C., et al. 2022, A&A, 663, L5 Sakai, N. & Yamamoto, S. 2013, Chemical Reviews, 113, 8981
Cernicharo, J., Heras, A. M., Tielens, A. G. G. M., et al. 2001, ApJ, 546, L123 Santos, J. C., Enrique-Romero, J., Lamberts, T., Linnartz, H., & Chuang, K.-J.
Cernicharo, J., Marcelino, N., Agúndez, M., et al. 2020, A&A, 642, L8 2024, ACS Earth and Space Chemistry, 8, 1646
Cernicharo, J., Tercero, B., Agúndez, M., et al. 2024, A&A, 686, A139 Schuhmann, M., Altwegg, K., Balsiger, H., et al. 2019, A&A, 630, A31
Chen, Y. J., Chuang, K. J., Muñoz Caro, G. M., et al. 2014, ApJ, 781, 15 Segré, D., Ben-Eli, D., Deamer, D. W., & Lancet, D. 2001, Origins of Life and
Chevance, M., Kruijssen, J. M. D., Vazquez-Semadeni, E., et al. 2020, Evolution of the Biosphere, 31, 119
Space Sci. Rev., 216, 50 Stevenson, J., Lunine, J., & Clancy, P. 2015, Science Advances, 1, 1400067
Chuang, K. J., Fedoseev, G., Qasim, D., et al. 2020, A&A, 635, A199 Strazzulla, G. & Baratta, G. A. 1992, A&A, 266, 434
Chuang, K. J., Fedoseev, G., Qasim, D., et al. 2017, MNRAS, 467, 2552 Taniguchi, K., Gorai, P., & Tan, J. C. 2024, Ap&SS, 369, 34
Chuang, K. J., Fedoseev, G., Qasim, D., et al. 2018a, A&A, 617, A87 Taniguchi, K., Herbst, E., Ozeki, H., & Saito, M. 2019, ApJ, 884, 167
Chuang, K. J., Fedoseev, G., Qasim, D., et al. 2018b, ApJ, 853, 102 Taniguchi, K., Ozeki, H., & Saito, M. 2017, ApJ, 846, 46
Chuang, K. J., Fedoseev, G., Scirè, C., et al. 2021, A&A, 650, A85
Taniguchi, K., Saito, M., & Ozeki, H. 2016, ApJ, 830, 106
Chuang, K. J., Jäger, C., Santos, J. C., & Henning, T. 2024, A&A, 687, A7
Theule, P., Borget, F., Mispelaer, F., et al. 2011, A&A, 534, A64
Comeford, J. & Gould, J. H. 1961, Journal of Molecular Spectroscopy, 5, 474
Tørneng, E., Nielsen, C. J., Klaeboe, P., Hopf, H., & Priebe, H. 1980, Spec-
Compagnini, G., D’Urso, L., Puglisi, O., Baratta, G., & Strazzulla, G. 2009,
trochimica Acta Part A: Molecular Spectroscopy, 36, 975
Carbon, 47, 1605
Cuadrado, S., Goicoechea, J. R., Pilleri, P., et al. 2015, A&A, 575, A82 Trevors, J. T. & Psenner, R. 2001, FEMS Microbiology Reviews, 25, 573
Cuylle, S. H., Zhao, D., Strazzulla, G., & Linnartz, H. 2014, A&A, 570, A83 Tschersich, K. G. 2000, Journal of Applied Physics, 87, 2565
De Sanctis, M. C., Ammannito, E., McSween, H. Y., et al. 2017, Science, 355, Turner, A. M., Abplanalp, M. J., Blair, T. J., Dayuha, R., & Kaiser, R. I. 2018,
719 ApJS, 234, 6
Fatima, M., Müller, H. S. P., Zingsheim, O., et al. 2023, A&A, 680, A25 Urso, R. G., Palumbo, M. E., Ceccarelli, C., et al. 2019, A&A, 628, A72
Fedoseev, G., Chuang, K. J., Ioppolo, S., et al. 2017, ApJ, 842, 52 van Dishoeck, E. F., Grant, S., Tabone, B., et al. 2023, Faraday Discussions, 245,
Fedoseev, G., Chuang, K. J., van Dishoeck, E. F., Ioppolo, S., & Linnartz, H. 52
2016, MNRAS, 460, 4297 Wu, Y.-J., Lin, M.-Y., Chou, S.-L., et al. 2010, ApJ, 721, 856
Fedoseev, G., Cuppen, H. M., Ioppolo, S., Lamberts, T., & Linnartz, H. 2015, Yabuta, H., Cody, G. D., Engrand, C., et al. 2023, Science, 379, abn9057
MNRAS, 448, 1288 Zhou, L., Kaiser, R. I., & Tokunaga, A. T. 2009, Planet. Space Sci., 57, 830
Fedoseev, G., Qasim, D., Chuang, K.-J., et al. 2022, ApJ, 924, 110 Zhou, L., Zheng, W., Kaiser, R. I., et al. 2010, ApJ, 718, 1243
Fuentetaja, R., Agúndez, M., Cabezas, C., et al. 2022a, A&A, 667, L4
Fuentetaja, R., Cabezas, C., Agúndez, M., et al. 2022b, A&A, 663, L3
Gerakines, P. A. & Moore, M. H. 2001, Icarus, 154, 372
Guzmán, V. V., Bergner, J. B., Law, C. J., et al. 2021, ApJS, 257, 6
Hänni, N., Altwegg, K., Baklouti, D., et al. 2023, A&A, 678, A22
Hänni, N., Altwegg, K., Balsiger, H., et al. 2021, A&A, 647, A22
Hänni, N., Altwegg, K., Combi, M., et al. 2022, Nature Communications, 13,
3639
Hiraoka, K., Takayama, T., Euchi, A., Handa, H., & Sato, T. 2000, ApJ, 532,
1029
Hopkins, B. J. & Riviere, J. C. 1964, British Journal of Applied Physics, 15, 941
Hudson, R. L., Ferrante, R. F., & Moore, M. H. 2014, Icarus, 228, 276
Ilee, J. D., Walsh, C., Booth, A. S., et al. 2021, ApJS, 257, 9
Ioppolo, S., Fedoseev, G., Lamberts, T., Romanzin, C., & Linnartz, H. 2013,
Review of Scientific Instruments, 84, 073112
Irvine, W. M. & Hjalmarson, A. 1984, Origins of Life, 14, 15
Jiménez-Serra, I., Rodríguez-Almeida, L. F., Martín-Pintado, J., et al. 2022,
A&A, 663, A181
Jo, S. K. & White, J. M. 1991, J. Chem. Phys., 94, 5761
Khlifi, M., Paillous, P., Delpech, C., et al. 1995, Journal of Molecular Spec-
troscopy, 174, 116
Kim, Y. S., Bennett, C. J., Chen, L.-H., O’Brien, K., & Kaiser, R. I. 2010, ApJ,
711, 744
Kim, Y. S. & Kaiser, R. I. 2009, ApJS, 181, 543
Kobayashi, H., Hidaka, H., Lamberts, T., et al. 2017, ApJ, 837, 155
Lee, K. L. K., Loomis, R. A., Burkhardt, A. M., et al. 2021, ApJ, 908, L11
Ligterink, N. F. W., Paardekooper, D. M., Chuang, K. J., et al. 2015, A&A, 584,
A56
Loomis, R. A., Burkhardt, A. M., Shingledecker, C. N., et al. 2021, Nature As-
tronomy, 5, 188
Maity, S., Kaiser, R. I., & Jones, B. M. 2015, Physical Chemistry Chemical
Physics (Incorporating Faraday Transactions), 17, 3081
Martín, S., Mangum, J. G., Harada, N., et al. 2021, A&A, 656, A46
McGuire, B. A., Burkhardt, A. M., Shingledecker, C. N., et al. 2017, ApJ, 843,
L28
Minissale, M., Moudens, A., Baouche, S., Chaabouni, H., & Dulieu, F. 2016,
MNRAS, 458, 2953
Modica, P. & Palumbo, M. E. 2010, A&A, 519, A22
Molpeceres, G. & Rivilla, V. M. 2022, A&A, 665, A27
Nguyen, T., Fourré, I., Favre, C., et al. 2019, A&A, 628, A15
Oba, Y., Tomaru, T., Lamberts, T., Kouchi, A., & Watanabe, N. 2018, Nature
Astronomy, 2, 228
Öberg, K. I., Boogert, A. C. A., Pontoppidan, K. M., et al. 2011, ApJ, 740, 109
Öberg, K. I., Garrod, R. T., van Dishoeck, E. F., & Linnartz, H. 2009, A&A, 504,
891
Pardo, J. R., Cernicharo, J., & Goicoechea, J. R. 2005, ApJ, 628, 275

Article number, page 10 of 12

 G. Fedoseev et al.: Production of linear alkanes by solid-state hydrogenation of interstellar polyynes

Appendix A: QMS-TPD spectra subtraction Temperature, K

50 75 100 125 150 175 200 225

5.0E-12
Figures A.1, A.2, and A.3 show the results of subtraction be-
0.0E+0
tween the mass spectra obtained prior and after hydrogenation of
-5.0E-12
the ice for each of the individual m/z values presented through C4H4 (m/z = 52, CH2CHCCH+)
Figs. 2, 3, and 4. 1.0E-12

Intensity, counts
0.0E+0

-1.0E-12 C4H6 (m/z = 54, CH2CHCHCH2+ or CH3CH2CCH+)

Temperature, K 1.0E-12
50 75 100 125 150 175 200 225
0.0E+0
C2H2 (m/z = 26, HCCH+) C4H8 (m/z = 56, CH2CHCH2CH3+)
1E-9 -1.0E-12

0E+0 5.0E-12

-1E-9 0.0E+0
-5.0E-12 C2H3 (m/z = 27, CH2CH-+ or H13CCH+)
Intensity, counts

5E-12
C4H2 (m/z = 50, HCCCCH+) 50 75 100 125 150 175 200 225
Temperature, K
0E+0

-5E-12 Fig. A.3. Results of subtraction for each of the m/z values presented in
Fig. 4
5E-13 C6H2 (m/z = 74, HCCCCCCH+)

0E+0
Appendix B: Fragmentation pattern comparison

-5E-13
In Fig. B.1, examples of comparison between the m/z signals
registered at 105 and 138 K with the mass spectra available from
50 75 100 125 150 175 200 225 the NIST database are presented. It is shown that the ratio be-
Temperature, K tween m/z≥43 signals demonstrates relatively good agreement
with the NIST spectra of linear n-C4 H10 and n-C6 H14 . However,
Fig. A.1. Results of subtraction for each of the m/z values presented in co-desorption of entrapped C2 H6 (or other species) along with
Fig. 2 the main constituents of the ice is required to account for the
high relative intensity of m/z= 27, 29, 30 signals registered at
these temperatures.

Temperature, K
50 75 100 125 150 175 200 225

5E-11 C2H6 (m/z = 30, CH3CH3+)

0E+0

-5E-11

5E-13 C4H10 (m/z = 58, CH3CH2CH2CH3+)

0E+0
Intensity, counts

-5E-13

1E-11 C2H5-X (m/z = 29, CH3CH2-+)

5E-12
0E+0
-5E-12
-1E-11

C3H7-X (m/z = 43, CH3CH2CH2-+)

5E-12

0E+0

-5E-12

50 75 100 125 150 175 200 225

Temperature, K

Fig. A.2. Results of subtraction for each of the m/z values presented in
Fig. 3

Article number, page 11 of 12

 A&A proofs: manuscript no. aa52210-24corr

Experiment 1.0 Experiment

1.0
C4H10 n-C6H14
C4 H8 C2H6 (trapped)
0.8 0.8
C2H6 (trapped)

Relative intensity
Relative intensity

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
27 29 30 43 56 58 27 29 30 43 56 58

m/z m/z

Fig. B.1. Left: Comparison between the observed intensities of m/z signals at 105 K for 70 eV electron ionization energy of the QMS and the
mass fragmentation patterns of C4 H10 (CH3 CH2 CH2 CH3 ), C4 H8 (CH2 CHCH2 CH3 ), and C2 H6 (CH3 CH3 ) acquired from NIST database. Right:
Similar comparison between intensities obtained at 138 K with the mass fragmentation patterns of C6 H14 (CH3 CH2 CH2 CH2 CH2 CH3 ) and C2 H6
(CH3 CH3 ) acquired from the NIST database. Experimental values are baseline subtracted. Only the selected m/z values with resolved peaks are
presented.

Article number, page 12 of 12