Astronomy & Astrophysics manuscript no.

EA ©ESO 2024
October 17, 2024

Infrared Spectra of Solid-State Ethanolamine: Laboratory Data in

Support of JWST Observations
T. Suhasaria1 , S. M. Wee1 , R. Basalgète2 , S. A. Krasnokutski2 , C. Jäger2 , G. Perotti1 and Th. Henning1

1
Max Planck Institute für Astronomie, Königstuhl 17, 69117, Heidelberg, Germany
e-mail: [email protected]
2
Laboratory Astrophysics Group of the Max Planck Institute for Astronomy at the Friedrich Schiller University Jena, Institute of
Solid State Physics, Helmholtzweg 3, 07743, Jena, Germany
arXiv:2410.12235v1 [astro-ph.GA] 16 Oct 2024

October 17, 2024

ABSTRACT

Context. Ethanolamine (NH2 CH2 CH2 OH, EA) has been identified in the gas phase of the interstellar medium within molecular
clouds. Although EA hasn’t been directly observed in the molecular ice phase, a solid-state formation mechanism has been proposed.
However, the current literature lacks an estimation of the infrared band strengths of EA ices, which are crucial data for quantifying
potential astronomical observations and laboratory findings related to their formation or destruction via energetic processing.
Aims. We conducted an experimental investigation of solid EA ice at low temperatures to ascertain its infrared band strengths, phase
transition temperature, and multilayer binding energy. Since the refractive index and the density of EA ice are unknown, the commonly
used laser interferometry method was not applied. Infrared band strengths were determined using three distinct methods. Besides the
evaluation of band strengths of EA, we also tested the advantages and disadvantages of different approaches used for this purpose.
The obtained lab spectrum of EA was compared with the publicly available MIRI MRS James Webb Space Telescope observations
toward a low mass protostar.
Methods. We used a combination of Fourier-transform transmission infrared spectroscopy and quadrupole mass spectrometry.
Results. The phase transition temperature for EA ice falls within the range of 175 to 185 K. Among the discussed methods, the
simple pressure gauge method provides a reasonable estimate of band strength. We derive a band strength value of about 1 × 10−17
cm molecule−1 for the NH2 bending mode in the EA molecules. Additionally, temperature-programmed desorption analysis yielded a
multilayer desorption energy of 0.61±0.01 eV. By comparing the laboratory data documented in this study with the JWST spectrum
of the low mass protostar IRAS 2A, an upper-limit for the EA ice abundances was derived.
Conclusions. This study addresses the lack of quantitative infrared measurements of EA at low temperatures, crucial for understanding
its astronomical and laboratory presence and formation routes. Our approach presents a simple, yet effective method for determining
the infrared band strengths of molecules with a reasonable level of accuracy.
Key words. astrochemistry – methods: laboratory: solid state - techniques: spectroscopic - ISM: molecules

1. Introduction has also been found in the Almahata Sitta meteorite (Glavin et al.
2010).
Aminoalcohols are an interesting class of organic compounds One of the potential pathways for the formation of EA in
that contain both amino (NH2 ) and hydroxy (OH) functional space is through the hydrogenation of the aminoketene molecule
groups. These molecules, due to their biological relevance, can (Rivilla et al. 2021). In a recent study, aminoketene was shown
play an important role in the context of the origin of life. to be formed efficiently at 10 K without the input of energy by
Ethanolamine (NH2 CH2 CH2 OH, hereafter denoted as EA), also the reaction of C atoms with CO and NH3 , which could po-
known as β-aminoethanol or glycinol, is the simplest head group tentially result in high abundances of aminoketene and EA in
of phospholipids and is also considered a precursor of the sim- the solid state (Krasnokutski 2021; Krasnokutski et al. 2022).
plest amino acid, glycine. Additionally, α, β-amino alcohol moi- Aminoketene may also polymerize, resulting in the formation
eties can be found in various other biomolecules, including of peptide chains that could potentially have a catalytic func-
aminosugars, sphingolipids, and glycoproteins, playing crucial tion, aiding the formation of complex organic or even biological
roles in the functions of biosystems (Sladkova et al. 2014). molecules (Krasnokutski et al. 2024, 2022). This pathway begins
with the reaction between C and NH3 leading to the formation of
Recently, EA was identified in the interstellar medium in the HCNH2 and H2 CNH products. This differs from a recently pub-
molecular cloud G+0.693-0.027, situated within the Sagittarius lished work, which proposes that the reaction of C atoms with
B2 complex in the Galactic Center, through rotational transition an NH3 molecule in ice forms a weakly bound complex, namely
observations as reported by Rivilla et al. (2021). Although EA CNH3 (Molpeceres et al. 2024).
was observed exclusively in the gas phase and not within in- An alternative route to EA is the UV irradiation of molecular
terstellar ices, it has been proposed that the gas-phase detection ice as demonstrated by laboratory experiments on the photolysis
may be attributed to the erosion of icy mantles caused by the low- of H2 O:CH3 OH:NH3 :HCN ices, with a 20:2:1:1 mixture (Bern-
velocity shocks typically found in massive molecular clouds. EA stein et al. 2002). In these experiments, EA is produced along
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 A&A proofs: manuscript no. EA

with other prebiotic species like the amino acids glycine, ala- νa
0 .2 νs (N H ) s (C H )
nine, and serine. However, the amount of EA formed in these νs (O H )
νa s (N H )
experiments was very small and it was detected after a chemi- νs (C H )

cal treatment. Therefore, the presence of EA, with its multiple * *

δ( C H )
functional groups, in molecular ice could lead to the formation
of more complex species when exposed to energetic processing, δ( N H )
*

O p tic a l d e p th
some of which might even have astrobiological significance. E x p e r im e n t * *
0 .0
Infrared spectroscopy stands out as the primary method for
identifying molecules in extraterrestrial solids, particularly in ice
on interstellar and solar system objects. The identification pro-
cess involves comparing astronomical data to reference measure-
ments from terrestrial laboratories and, in some cases, allows for -0 .2
both identification and quantification of molecular abundances
based on IR detections. This method relies on assigning specific C a lc u la tio n
IR bands to molecules, integrating them, and comparing the re-
sults to intrinsic IR band strengths determined in laboratories.
To our knowledge, there are no quantitative IR measure- 4 0 0 0 3 5 0 0 3 0 0 0 2 5 0 0 2 0 0 0 1 5 0 0 1 0 0 0
ments of EA ices. This study concentrates on conducting IR
spectroscopy on amorphous EA ice at low temperatures and as- W a v e n u m b e r (c m -1 )
signing the IR bands based on theoretical calculations. The ther-
mal variation of EA infrared features is also shown. The phase Fig. 1. Experimental and theoretical mid-IR spectrum of EA. The upper
one shows about 200 monolayers (ML) EA condensed on KBr at 10
transition temperatures have been identified and the IR spectra of K. The infrared bands marked with asterisks are due to a mixture of
crystalline EA have been highlighted. In addition, experimental different vibrational modes. For the latter, calculations were performed
band strengths of amorphous EA ice have been determined. at MP2/Aug-cc-pVTZ level.

2. Experimental methods
Experiments were conducted in the Laboratory Astrophysics Temperature programmed desorption (TPD) experiments were
group at Jena in the INterStellar Ice Dust Experiment (INSIDE) performed by linear ramping of the sample temperature with a
chamber. The setup has been extensively detailed in prior work rate of 10 K minute−1 in a temperature range between 10 and 300
(Potapov et al. 2019). Here, we provide only a brief overview K. The error of the temperature measurements was determined
of the setup which is relevant to this study. The measurements to be ± 1 K.
were done in an ultrahigh vacuum (UHV) chamber, maintaining The molecular geometry and anharmonic vibrational spec-
a base pressure better than 8×10−10 mbar, which is equipped with trum of one of the conformers of EA were obtained using
a closed-cycle helium cryostat that can cool the sample down to the second-order Møller–Plesset (MP2) perturbation theory and
10 K. The temperature is measured by a diode which is fixed on Aug-cc-pVTZ basis set. Quantum chemical calculations were
the sample holder very close to the sample. In our experiments, a performed using the Gaussian09 software package (Frisch et al.
potassium bromide (KBr) window was affixed as a substrate on 2016).
the cold finger of the cryostat.
Liquid NH2 CH2 CH2 OH (Sigma Aldrich, ≥99.0%) and
CH3 OH (Sigma Aldrich, ≥99.0%) were purified through mul- 3. Results and discussion
tiple freeze-pump-thaw cycles and deposited onto the substrate 3.1. Infrared spectrum of EA ice
as pure vapor through a gas inlet system attached to the UHV
chamber in different experiments. The gas inlet system has two Experimental IR spectra of EA in both its liquid and the gas
separate lines. The first line allows mixing of upto five different phases have been reported in the literature (Silva et al. 1999, and
gases. NH2 CH2 CH2 OH and CH3 OH were deposited individu- references therein). Additionally, the adsorption behavior of EA
ally from the first line. The second gas line is kept for corrosive on TiO2 at temperatures of 35◦ and 275◦ C has been investigated
gases. Ammonia (NH3 , Linde, 5.5 grade purity) gas was also de- (Tseng et al. 2010). However, to date, a comprehensive study
posited as a pure component through the second gas line of the of EA ices at low temperatures has not been conducted. Matrix-
same inlet system without any further purification. Gases are de- isolated infrared spectra of EA at 13 K were measured in the
posited onto the substrate through two 0.5 mm diameter capillary laboratory, focusing only on the spectral regions between 3800-
tubes. The chamber is equipped with a Fourier transform infrared 3300 and 600-200 cm−1 (Räsänen et al. 1983). Figure 1 illus-
(FTIR) spectrometer (Bruker Vertex 80v) fitted with a Mercury trates the IR spectrum of EA deposited on a blank KBr substrate
Cadmium Telluride (MCT) detector for in situ measurement of at 10 K. To aid in the assignment of the fundamental vibration
the ice phase. Infrared spectra were collected in the temperature modes associated with this spectrum, a fully anharmonic infrared
interval between 10 and 300 K, before and during the warming- spectrum of a single EA molecule was computed. The computed
up, in transmittance mode in the spectral range from 6000 to 400 infrared spectrum is also shown in Figure 1. Since the formation
cm−1 with a resolution of 1 cm−1 . For the irradiation experiment of ice significantly alters the spectrum of EA, especially in the
at 10 K, 256 scans were taken while during the warming-up ex- stretching vibration region, the assignment of absorption bands
periment, only 32 scans were taken each time. is also based on previous laboratory data and is shown in Table
During the low temperature and warming up experiments, 1. Although the computed spectrum agrees well with the experi-
a quadrupole mass spectrometer (QMS; HXT300M, Hositrad) ment in the fingerprint region (i. e. low wavenumber side), there
attached to the UHV chamber monitors the gas phase inside the are a few discrepancies in the higher wavenumber side. Notably,
chamber to detect molecules desorbing from the sample surface. the O-H stretching band of EA in the experiment deviates signif-
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 Suhasaria et al.: Infrared spectra of solid state Ethanolamine

1.6

1.4

1.2
220K 220K
1.0
2SWLFDOGHSWK

190K
0.8 190K
185K
180K 185K
0.6
180K
175K
0.4 170K 175K
170K
0.2 75K
75K
10K 10K
0.0
3400 3200 3000 2800 2600 2400 1500 1400 1300 1200 1100 1000 900
:DYHQXPEHUFP 1)
Fig. 2. A series of mid-IR spectra of EA is shown at different temperatures and two different spectral regions. About 200 ML of EA were initially
condensed on the KBr surface at 10 K and warmed up to 250 K with a linear heating ramp. Spectra are shifted in ordinate for clarity. The spectrum
at 190 K is made bold to indicate the complete phase transition from amorphous to crystalline.

2.00 3.2. Thermal variation of Infrared spectrum of EA ice

1.75 H2 O A pure EA ice grown at 10 K was heated with a continuous lin-

ear ramp of 10 K min−1 up to 140 K. The spectral changes were
1.50 monitored with FTIR. After 140 K, the sample was heated in
CH3OH
increments of 5 K with the same ramp. After reaching each heat-
1.25
2SWLFDOGHSWK

ing step, heating was paused for an IR measurement and then

1.00 resumed until a final temperature of 250 K was reached. While
NH3 the phase transition was observed between 175 and 185 K, EA
0.75 sublimation started at 220 K, well above the water sublimation
temperature, and continued until 240 K. The reproducibility was
0.50
confirmed through a subsequent experiment. It is worth men-
0.25 EA (190 K) tioning at this point that the maximum desorption temperature
for the EA multilayer (about 200 ML) is 40 K higher than that
0.00 EA (10 K) measured for small coverages (a few MLs) by the TPD method
4000 3500 3000 2500 2000 1500 1000 described in the next section. Figure 2 shows the spectra at dif-
:DYHQXPEHUFP 1 ferent temperatures during the annealing process of EA.
Features of interest are mostly located within these two
Fig. 3. Mid-infrared spectra of pure EA and reference molecules NH3 ranges: 3600 – 2500 cm−1 and 1600 – 800 cm−1 . For the higher
and CH3 OH at 10 K. The spectrum of H2 O (common interstellar ice wavenumber range, the band observed at 3351 cm−1 , associated
component) at 15 K is taken from the Leiden Ice Database for Astro- with asymmetric NH2 stretching, sharpens with increasing tem-
chemistry (LIDA). Bands selected for band strength estimation are in- perature, and the peak is eventually red-shifted to 3338 cm−1
dicated by the shaded areas. at 145 K. The band then remains unchanged until 170 K. During
the phase transition, the 3338 cm−1 band begins to disappear and
is replaced by a sharp 3322 cm−1 band. With further temperature
increase, the 3322 cm−1 band blue-shifts to 3327 cm−1 until the
complete desorption of EA. Meanwhile, the band at 3286 cm−1 ,
ascribed to symmetric NH2 stretching, grows sharper until the
sample reaches 175 K but without a change in the peak posi-
icantly from results obtained using computations. The possible tion. During the phase transition, the 3286 cm−1 vanishes and a
cause of deviation is the presence of an extended H-bond net- new band centered at 3271 cm−1 appears. The band assigned to
work that exists in EA ice which was not considered for free OH stretching at 3185 cm−1 blue-shifts to 3200 cm−1 and grows
hydroxy and amino groups in the computation. sharper up to 180 K. Beyond that the 3200 peak starts to disap-
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pear and a new band is formed at 3182 cm−1 , which is closer to

the original band but better resolved. A shoulder peak at 3055 1
Z
cm−1 on the lower wavenumber side of the OH stretching band A= τ(ν)dν (1)
becomes prominent while heating the ice beyond 100 K. The N
peak then remains unchanged until 175 K before broadening. where N is the column density of the molecule in molecules
For the asymmetric CH2 stretching band at 2928 cm−1 , although cm−2 , τ the optical depth of the absorption band (unitless), and
no change in the peak position was observed, the peak becomes ν the wavenumber frequency in cm−1 . To determine the band
sharper by heating up to 175 K. After this, the peak starts to dis- strength, the column density of the molecule has to be mea-
appear and instead, a new band is formed with a peak centered sured. In the case of the first method, we considered that the
at 2939 cm−1 . On the other hand, a symmetric CH2 stretch band column density will depend on the gas pressure difference (∆p)
at 2857 cm−1 shifts up to 2864 cm−1 at 170 K. The peak then measured in the gas inlet system during the molecule deposi-
disappears and also forms a new band with a peak at 2875 cm−1 . tion. The pressure difference is measured via the capacitance di-
Apart from the bands mentioned in Table 1, there were a few aphragm vacuum gauge (Pfeiffer Vacuum, CCR 364). The gas
small peaks centered around 2777 cm−1 , 2718 cm−1 and 2653 pressure obtained this way is independent of the gas type and
cm−1 observed at 10 K which remained at the same position even the concentration. Therefore, assuming an ideal gas equation and
after annealing until 170 K. All these peaks resolve upon anneal- considering that all the other parameters remain unchanged from
ing and show a considerable shift of up to 15 cm−1 beyond 180 one measurement to the other, N would be proportional to ∆p in
K. Two new peaks appear in EA ice spectrum beyond 180 K at the gas inlet system. A similar dependence has been shown pre-
2565 cm−1 and 2522 cm−1 . Close to the desorption temperature, viously (González Díaz et al. 2022). For this method of band
the 2565 cm−1 disappears while the 2522 cm−1 peak shifts to strength estimation of EA, we use a reference molecule and re-
2510 cm−1 . arrange Equation 1 as the following:
Simultaneously, for the lower wavenumber range, the 1607
cm−1 band assigned to NH2 bending shows no change in peak
∆pre f τEA (ν)dν
R
position until about 175 K. Between 175 and 185 K, 1607 peak AEA = Are f (2)
∆pEA τre f (ν)dν
R
disappears and instead, two new features appear – a strong band
at 1614 cm−1 and a weak band at 1668 cm−1 . Similarly, the 1458
cm−1 peak assigned to CH2 bending gradually smears out until The integrated band areas for EA and the reference
175 K, and beyond that, during the phase transition, it forms a molecules were evaluated from the infrared spectra. We have
strong band at 1486 cm−1 and a weak band at 1450 cm−1 . We used CH3 OH and NH3 as reference molecules. Bands of CH3 OH
also notice a peak emerging at 1467 cm−1 which eventually be- and NH3 selected for the integrated optical depth estimations are
comes a shoulder to the 1486 cm−1 peak. The 1395 cm−1 band shown with shaded regions in Figure 3 and the respective abso-
shows almost no change in the peak position until 175 K, while lute band strengths are listed in Table 3. In the case of NH3 ’s
between 175 and 185 K, the peak shifts to 1380 cm−1 . On the 1071 cm−1 peak, the absolute band strength was calculated us-
other hand, 1360 cm−1 peak becomes sharp but remain around ing the imaginary part of the optical constants k(ν) given as a
1357 cm−1 until 175 K; beyond that the peak splits into a strong function of wavenumbers that was obtained from NASA Cos-
1346 cm−1 and a weak 1366 cm−1 . After 185 K, both the peaks mic Ice Laboratory database1 . The optical constants in turn al-
start to disappear gradually. The 1253, 1175, 1082, and 1033 low one to determine the absolute absorption coefficient α for
cm−1 bands show no change in the peak position until 175 K. each wavenumber using the relation α = 4πνk and generate a
During the phase transition, we see peak shifting to 1160 cm−1 computed IR spectrum. The integration of the 1071 cm−1 peak
in the case of 1175 cm−1 band while 1082 and 1033 cm−1 bands can then be used to eventually derive the absolute band strengths
show splitting to 1100 and 1063 cm−1 peaks for the former and using the following equation (Hudson et al. 2014):
1038 and 1030 cm−1 peaks for the latter. Two new peaks at 970
and 1313 cm−1 start to appear as we start to heat the EA ice and M
Z
remain unchanged until 175 K. During the phase transition, 970 A= α(ν)dν (3)
cm−1 peak splits into 982 and 960 cm−1 peaks. After 185 K, a ρNA band
new peak appears at 870 cm−1 . where M is the molar mass, NA the Avogadro constant, and ρ
the density of the molecule. ρNH3 = 0.68 g cm−3 was used for the
calculation (Hudson et al. 2022) which ultimately yields ANH3 =
3.3. Band strength estimation
22.3 × 10−18 cm mol−1 .
In the laboratory, optical laser interferometry is frequently paired To test how well this method works, we calculated the abso-
with complementary techniques to determine the infrared band lute band strength of NH3 using CH3 OH as a reference and vice
strengths of solid molecules (Bouilloud et al. 2015; Hudson et al. versa. In both cases, a set of two different ∆p values were taken
2022, and references therein). The precise estimation of absolute into consideration for each molecule. In the former case, ANH3 =
band strengths relies on prior knowledge of the refractive index 26±6 × 10−18 cm mol−1 while for the latter, ACH3 OH = 15±3 ×
and density of the molecule under study, which laser techniques 10−18 cm mol−1 was obtained. Within the errors, the deviation is
can help with. In the present work, we have determined the in- around 10%. The estimated values of EA band strength for the
frared band strengths of EA by three different methods, none of three different integrated ranges by the two reference molecules
which involve laser interferometry. The band strengths derived are well within errors and they are summarized in Table 2. One
by the first two methods require one to compare the absorption standard deviation was used for the error calculation.
spectra of molecules with known reference band strengths while The second method employed QMS measurements during
for the last method, one doesn’t require such a comparison. TPD to obtain the column density of the molecules desorbed
from the surface for band strength estimation. The species used
Infrared band strength (A, cm molecule−1 ) of any absorption
1
band of a molecule is given by: https://science.gsfc.nasa.gov/691/cosmicice/constants.html

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 Suhasaria et al.: Infrared spectra of solid state Ethanolamine

were monitored through their primary mass fragment: m/z = 31 when considering the actual 1.6 ML TPD curve to correspond to
(CH3 OH) and m/z = 30 (EA). It is worth mentioning that NH3 1 ML. This results in a 38% uncertainty. Note that we have only
was excluded as a reference molecule in the second method due used a few monolayer coverage equivalent of EA on the cold sur-
to the uncertainties associated with the relative transmission ef- face for band strength estimation by the three methods described
ficiency of the QMS between the m/z = 30 (EA) and m/z = 17 above.
(NH3 ). Such uncertainty can be neglected when using CH3 OH
as the reference molecule for Method 2 since the m/z ratios The advantage of Method 1 is the ease of band strength mea-
monitored are similar (m/z = 31 for CH3 OH and m/z = 30 for surements of unknown molecules without the need for a dedi-
EA). The integrated QMS signal measured during the TPD of a cated experimental setup and the time for undertaking the exper-
molecule is proportional to N and depends on several other pa- iment. This is especially suitable for larger organic molecules
rameters as highlighted by Maté et al. (2023). The band strength that are unstable and can undergo polymerization with time. The
of EA in comparison to CH3 OH can then be expressed as: major advantage of Method 3 is that one can easily obtain the
binding energy of the molecule of interest together with the band
strength. On the other hand, the inconsistent variation of band
Ire f σEA fEA τEA (ν)dν
R
strength estimation with Method 2 highlights the need for mea-
AEA = Are f (4) suring parameters such as the ionization cross-section, the frag-
IEA σre f fre f τre f (ν)dν
R
mentation factor, and the transmission efficiency of molecules
where I is the integrated QMS signal, σ the ionization cross- in the laboratory through the QMS. Many researchers use an al-
section for the first ionization of the species at 70 eV electron ternative approach, which involves laser interferometry. How-
energy employed in the QMS, and f the fragmentation factor, ever, this method requires additional equipment and knowledge
which is the fraction of the primary fragment mass with respect of the refractive index mass density of the ice formed. Further-
to all the other fragment masses. The σ values for the two species more, it assumes that the ice layer on the substrate is perfectly
are σCH3 OH = 4.49 Å2 (Hudson et al. 2003) and σEA = 13.255 flat with zero porosity, which is not always the case. Therefore,
this method can only be recommended when Method 1 cannot
Å2 based on complex scattering potential-ionization contribu-
be applied, such as when measuring substances with low vapor
tion (CSP-ic) method (Chakraborty et al. 2024). The f values
pressures. Based on the discussion in the paper we think that the
are fCH3 OH = 0.404,and fEA = 0.648 (NIST database). The trans-
mission efficiency can be considered equal. Considering all these three measurement approaches taken in this paper can all be used
correction parameters, the estimated EA band strength values de- in ways described in the paper. From the comparison of the band
viate significantly from the values obtained by Method 1 as seen strength values obtained from three methods, we think the direct
in Table 2. The possible cause for such deviation could be due to method based on mass spectrometer and indirect method based
the uncertainty in the determination of different parameters used on pressure gauge would provide a reliable determination of the
in Equation 4. band strengths.
The last method that we used (Method 3) consists of a series Furthermore, alongside the three aforementioned methods,
of Temperature Programmed Desorption (TPD) measurements, we have included absolute infrared band strengths derived from
which is a well-known technique in laboratory astrophysics (e.g. theoretical calculations in Table 1. A satisfactory agreement ex-
Burke & Brown 2010; Doronin et al. 2015). EA ices are grown ists between experimental and theoretical values for the NH2
at 100 K by exposing a KBr substrate to a partial pressure be- bending mode at 1607 cm−1 , considering the inherent approx-
tween 10−9 and 10−8 Torr of EA for a few minutes. Then the imations in both experimental and theoretical approaches. While
substrate is warmed up to 250 K using a ramp of 10 K min−1 this method may be effective for estimating individual vibration
and the thermal desorption of EA is probed as a function of modes, it may not be suitable when considering combinations of
the substrate temperature by following the m/z = 30 channel of various modes.
the QMS. Figure 4 shows the TPD curves for different deposi-
tions of EA ices. According to the Polanyi-Wigner description The observed double peak structure in the TPD could arise
of thermal desorption, we estimate the monolayer (ML) cover- from two potential causes. Firstly, it may result from some de-
age of EA from these TPD curves. For multi-layer depositions gree of non-uniformity in film growth across the substrate during
(red curves), the TPD curves display a common leading edge at EA deposition using a 0.5 mm diameter capillary tube (Potapov
the start of the desorption kinetics, from 165 K to 175 K, whereas et al. 2019). Secondly, the presence of minor hydroxyl group
for monolayer or sub-monolayer depositions (blue curves), this contamination on KBr could induce H-bonding interactions with
leading edge differs for each deposition. Based on those con- EA, thereby contributing to the observed double peak structure.
siderations and assuming that depositions are homogeneous and For multilayer desorption, with the coincident leading edge be-
that the TPD integral is linear with the coverage, we estimate the haviour seen in the TPD trace, the desorption energy was then
EA coverage as shown in the legend of Figure 4. Infrared mea- determined using an Arrhenius analysis of the leading edge re-
surements are also taken after each deposition before the onset gion for the 3.4 ML curve as described previously in details
of the TPD measurements. A good signal-to-noise ratio could (Suhasaria et al. 2015). The method yields the multilayer des-
only be obtained in the IR spectrum for coverages greater than orption energy of 0.61±0.01 eV and the pre-exponential factor of
3.4 ML. Therefore, we used that in the determination of the in- 0.5×1027 molecule cm−2 s−1 . In the literature, the binding energy
frared band strength. Knowing the ice thickness associated with of EA from carbon and water surface has been predicted via ma-
this IR spectrum, we therefore deduced the band strengths as dis- chine learning to be around 0.7±0.2 eV (Villadsen et al. 2022).
played in Table 2 (Method 3). The evaluated band strength values Although one cannot compare the values directly, the binding en-
show less deviation than Method 2. In Method 3, there could be ergy of EA from pure EA ice seems to be in good agreement with
uncertainties in the accurate determination of monolayer cover- the predicted values within the errors. For systems with more
age, which could explain the deviation between Method 1 and complex desorption kinetics, transition state theory can be em-
Method 3. The error in Method 3 is computed from the relative ployed as a method to derive the pre-exponential factor (Thrower
difference obtained on the coverage of the 3.4 ML TPD curve et al. 2013; Suhasaria et al. 2015).
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Table 1. IR band positions of EA from experiment and calculation.

Experimental Calculated Assignment Calculated A’

3351 3656 ν1 (asymm. NH2 ) 3.47 × 10−18
3286 3438 ν2 (symm. NH2 ) 1.20 × 10−18
3185 ν3 (OH)
2928 2958 ν4 (asymm. CH2 ) 16.75 × 10−18
2857 2888 ν5 (symm. CH2 ) 9.64 × 10−18
1607 1580 δ6 (NH2 ) 8.31 × 10−18
1458 1460 δ7 (CH2 ) 0.81 × 10−18
1395 1380 ν8 (CC)+ δ9 (OH, CH) 2.58 × 10−18
1360 1356 τ10 (NH, OH) 2.95 × 10−18
1253 1230 Skeletal vibrations* 0.90 × 10−18
1175 1138 Skeletal vibrations* 2.53 × 10−18
1082 1090 ν11 (CN, CO) +δ12 (OH)+ τ13 (CC) 6.97 × 10−18
1033 976 ν14 (CO)+ δ15 (NH, CH)+ τ16 (CC) 6.63 × 10−18

Notes. Mode assignments in the lower wavenumbers are based on the calculation. The calculated band strengths (A’, cm molecules−1 ) have been
added in the last column. Vibration modes have been denoted by Greek letters: stretching (ν), bending (δ) and twisting (τ). Assignments marked
with asterisks (*) arise due to strong coupling between stretching and bending modes of different atoms in the EA.

Table 2. Estimated IR band strengths of EA ice at 10 K using three different methods.

Method 1 Method 2 Method 3

Integrated region
Mode NH3 CH3 OH CH3 OH EA
cm−1 ×10−18 cm molecules−1
ν1 +ν2 +ν3 +ν4 +ν5 3650 – 2450 463 ± 65 528 ± 137 202 ± 61 386 ± 145
δ6 1690 – 1550 10.2 ± 0.3 12 ± 3 5±2 7.8 ± 2.9
δ7 +ν8 +δ9 +τ10 1550 – 1285 17.3 ± 0.4 20 ± 4 9±3 16 ± 6
Notes. Note that there are large uncertainties in the determination of band strengths by Method 2. The possible reasons are discussed in the text.

Table 3. IR band strengths for reference and molecules with functional group similar to EA

Molecule Band position Assignment Integrated region Band strengths

cm−1 cm−1 cm molecule−1
NH3 a 1071 umbrella 1300 – 950 22.3 × 10−18
CH3 OHb 1030 ν (CO) 1066 – 967 16.8 × 10−18
CH3 NH2 (Methylamine)c 1600 δ (NH2 ) 4.3 × 10−18
CH3 NHCH2 OH(N-methylaminomethanol)d 1414 δ(CH)+δ(NH) 6 × 10−19
CH3 CH=NH(ethanimine)e 1650 ν (C=N) 4.4 × 10−18
CH2 =C=NH(Ketenimine)f 7.2 × 10−17
NH2 CH(CH3 )OH(α-aminoethanol)g 1413 δ (CH) 1.4 × 10−18
CH3 CH2 OH(ethanol)h 1050 ν (CO) 1067 – 1011 14.1 × 10−18

Notes. a We have calculated the absolute band strength of ammonia based on the apparent value estimated by Hudson et al. (2022), b Gerakines &
Hudson (2020), c Holtom et al. (2005), d Vinogradoff et al. (2013), e Canta et al. (2023), f Hudson & Moore (2004), g Duvernay et al. (2010) and h
Hudson (2017)

4. Astrophysical implications providing at least an upper limit in different conditions is there-

fore crucial for gaining reliable insights.
EA has been identified in both the interstellar medium and mete- The gas-phase molecular column density of EA toward the
orites (Rivilla et al. 2021; Glavin et al. 2010), indicating its likely G+0.693 molecular cloud in the SgrB2 complex in the Galac-
origin in space and its potential delivery to early Earth. This sug- tic Center was estimated at 1.5 × 1013 cm−2 . This suggests an
gests a possible role for EA in the formation of crucial prebiotic estimated abundance ranging from 0.9 to 1.4 × 10−10 relative
molecules like amino acids, potentially contributing to the emer- to molecular hydrogen and the EA/H2 O abundance ratio of the
gence of life (Rivilla et al. 2021). Furthermore, since EA can be order of 10−6 (Rivilla et al. 2021). In the Almahata Sitta mete-
formed via aminoketene, a link between EA and peptides, which orite, the ratio EA/H2 O was also found to be of the same order
are also produced through aminoketene, may exist (Krasnokut- (Glavin et al. 2010). While ice signatures of EA have not been
ski et al. 2022). Therefore, the detection of EA in both gas and detected, it is reasonable to assume that the EA abundance is sig-
solid phases across various sources such as molecular clouds and nificantly higher in the solid state than the gas phase given the
protoplanetary disks could indicate chemical processes essential various solid-state pathways suggested on grains (Rivilla et al.
for the origin of life. Accurately determining EA abundance or 2021). In the gas phase, EA molecules might easily dissociate
Article number, page 6 of 8
 Suhasaria et al.: Infrared spectra of solid state Ethanolamine

2 0 ing solid EA in various astrophysical environments in the future.

1 8
3 .4 M L Figure 5 illustrates a comparison of the pure EA ice spectrum at
2 .2 M L 10 K with an observed JWST spectra of the low mass protostar
T o rr)

1 6 1 .6 M L IRAS 2A taken with the MRS MIRI (Rocha et al. 2024). As can
1 M L be seen from Figure 5, the NH2 deformation mode of EA co-
-6

1 4
0 .8 M L incides with the strong features observed in the JWST spectra.
m /z 3 0 Q M S s ig n a l (1 0

1 2 0 .5 M L However, many other molecules with NH2 and even C=C bands
0 .4 M L can contribute to the same feature. Figure 3 shows the spectrum
1 0
of pure amorphous and crystalline EA ice along with the spec-
8 tra of some of the common polar interstellar ice components.
All of the EA ice features overlap with the common interstellar
6
ices and it could be challenging to significantly constrain the EA
4 abundance. However, within environments where grain temper-
atures exceed the water desorption temperature (T d ∼ 160 K),
2
the majority of volatile components within the ice mantle will
0 sublimate. This process would result in an elevated concentra-
1 6 0 1 7 0 1 8 0 1 9 0 2 0 0 2 1 0 2 2 0 tion of EA (T d > 180 K) in the solid state. In this case, the band
T e m p e ra tu re (K ) at 1607 cm−1 assigned to NH2 bending can be used to deter-
Fig. 4. Thermal desorption signal of EA from pure EA ices deposited at mine the column density of EA. Moreover, within astrophysical
100 K, and using a ramp of 10 K min−1 . The coverage associated with environments characterized by elevated temperatures (> 170 K),
each curve is based on the considerations as explained in the text. such as those found in protoplanetary disks, EA ice may manifest
in a crystalline state. This crystalline form displays distinct sharp
characteristics that distinguish it from other types of refractory
W a v e n u m b e r (c m -1
) ice. Finally, even at low temperatures (< 150 K) where volatile
2 0 0 0 1 8 1 8 1 6 6 7 1 5 3 8 1 4 2 9 1 3 3 3 1 2 5 0 ice exists, it is possible to subtract the spectral features of known
components such as NH3 , CH3 OH, H2 O, and even silicates to
-IR A S 2 A 3
detect EA. This process may result in a loss of sensitivity, but it
8 -IR A S 2 A _ s u b will not prevent the detection or estimation of the upper limit of
- E A la b d a ta * 2 0 2
the abundance of EA.
O p tic a l d e p th w ith o ffs e t

In this work, we have estimated the upper limit of EA by

6 1 comparing the laboratory data with the observed spectrum. The
spectrum from IRAS 2A with water:silicate features subtracted
0 was used to constrain the EA upper limit abundance. The EA
4 1 6 0 7 c m -1
5 .4 5 .7 6 .0 6 .3 6 .6
feature at 1607 cm−1 (6.22 µm) marked with vertical dashed line
was used for this purpose. The column density upper limit (N,
in cm−2 ) of EA can be estimated using the following relation
2
described in detail in Rachid et al. (2021):

τν × FWHM
NEA ≤ (5)
0 A
where, A = 1 × 10−17 cm molecule−1 is the band strength
5 .0 5 .5 6 .0 6 .5 7 .0 7 .5 8 .0 and FWHM = 50.5 cm−1 for the 1607 cm−1 EA feature. τν is
the maximum optical depth of the water:silicate subtracted peak
W a v e le n g th (μm )
where the EA peak centered at 1607 cm−1 fits. The inset to Fig-
Fig. 5. Comparison of the JWST/MIRI MRS spectra of IRAS 2A (blue ure 5 shows the procedure for obtaining the maximum optical
curve) and IRAS 2A with water:silicate features subtracted (red curve) depth. Using this method, an upper limit of ≤ 4.4×1018 cm−2 was
to the laboratory-measured EA ice profile at 10 K. For clearer compar- estimated, which corresponds to about 15% with respect to H2 O,
ison, all spectra are vertically shifted, with the laboratory spectrum in- assuming a column density of 3 × 1019 cm−2 for water (Rocha
tensity is multiplied by 20, and the EA band at 1607 cm−1 is indicated by et al. 2024). An abundance of EA this high seems improbable,
dashed line. The inset provides a closer examination of the water:silicate and as previously noted, the 1607 cm−1 EA feature used for es-
subtracted IRAS 2A spectrum alongside the fitted EA profile for upper timating abundance could also originate from other molecules.
limit estimation.
Apart from the upper limit estimation, the band strength estima-
tion is also needed for the quantitative estimation of the pho-
tolysis products of EA. Improving the accuracy with which we
under UV photon irradiation due to their predominantly single know the initial concentration of the starting material will help
bonds and relatively small size, making them more fragile and us to better calculate the product yield.
less capable of dissipating energy. Conversely, higher stability In Table 3 we have listed the band strengths of the reference
and potentially consequential reactions are expected for EA in molecules (NH3 and CH3 OH) used for band strength estimation
the solid state. of EA and of some other molecules that could potentially exist in
The enhanced sensitivity of the Medium Resolution Spectro- interstellar medium and have one or both the functional groups
graph (MRS) (Wells et al. 2015) of the Mid-InfraRed Instrument (saturated and unsaturated) present in EA. Although one cannot
(MIRI) (Rieke et al. 2015; Wright et al. 2015) onboard the JWST directly compare the band strength values, a closer look indicates
compared to its predecessors raises the possibility of identify- that the order of magnitude is similar to other molecules listed.
Article number, page 7 of 8
 A&A proofs: manuscript no. EA

5. Conclusions Räsänen, M., Aspiala, A., Homanen, L., & Murto, J. 1983, J. Mol. Struct., 96,
81
Solid EA was deposited on KBr substrate at 10 K and infrared Rieke, G. H., Wright, G., Böker, T., et al. 2015, PASP, 127, 584
spectra of the amorphous ice have been measured. Band assign- Rivilla, V. M., Jiménez-Serra, I., Martín-Pintado, J., et al. 2021, PNAS, 118,
ments have been made by comparison with the calculated spec- e2101314118
Rocha, W., van Dishoeck, E., Ressler, M., et al. 2024, A&A, 683, A124
tra. The EA ice was then annealed up to 250 K. Transmission Silva, C. F., Duarte, M. L. T., & Fausto, R. 1999, J. Mol. Struct., 482, 591
spectra were recorded over the entire temperature range. Be- Sladkova, A. A., Lisovskaya, A. G., Sosnovskaya, A. A., Edimecheva, I. P., &
tween 175 and 185 K, the amorphous EA phase undergoes a Shdyro, O. I. 2014, Radiat. Phys. Chem., 96, 229
transition to the crystalline phase. Infrared band strengths were Suhasaria, T., Thrower, J., & Zacharias, H. 2015, MNRAS, 454, 3317
Thrower, J. D., Friis, E. E., Skov, A. L., et al. 2013, J. Phys. Chem. C, 117, 13520
measured for amorphous EA ice. Three different methods were Tseng, C.-L., Chen, Y.-K., Wang, S.-H., Peng, Z.-W., & Lin, J.-L. 2010, J. Phys.
used to derive the band strengths. One of the three methods Chem. C, 114, 11835
used a complete set of TPDs for EA from submonolayer cov- Villadsen, T., Ligterink, N. F., & Andersen, M. 2022, A&A, 666, A45
erage to the multilayer regime. The multilayer binding energy Vinogradoff, V., Duvernay, F., Danger, G., et al. 2013, A&A, 549, A40
and the pre-exponential factor were determined experimentally. Wells, M., Pel, J.-W., Glasse, A., et al. 2015, PASP, 127, 646
Wright, G., Wright, D., Goodson, G., et al. 2015, PASP, 127, 595
For those gases whose pressure can be precisely measured in the
gas line, the first tested method of determining absorption band
strengths seems to be the simplest, giving satisfactory measure-
ment accuracy, and can be recommended for use in laboratories.
The second method requires precise knowledge of ion transport
in the mass spectrometer, which is often missed and the third
method provides more additional information but is relatively
time-consuming and has also uncertainties. A comparison be-
tween the laboratory data of pure EA and the the JWST MIRI
spectrum of the low-mass protostar IRAS 2A enabled us to de-
rive an upper-limit for the EA ice abundances with respect to
solid H2 O.
Acknowledgements. The authors are grateful to W.R.M. Rocha and E.F. van
Dishoeck for providing the MIRI MRS JWST data. This work has been sup-
ported by the European Research Council under the Horizon 2020 Framework
Program via the ERC Advanced Grant Origins 83 24 28. We would also like
to acknowledge funding through the DeutscheForschungsgemeinschaft (DFG)
project No. JA 2107/11-1. S.A.K. is grateful for the support from DFG (grant
no. KR 3995/4-2). The authors also acknowledge support from the NanoSpace
COST action (CA21126 – European Cooperation in Science and Technology).

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