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Polyacenes among other polycyclic aromatic hydrocarbons (PAHs) were suggested to be abundant in the dense regions of the interstellar medium (ISM) and to be responsible for some of the diffuse interstellar bands (DIBs). The identification of DIB carriers requires the laboratory spectra of cold cations for comparison with astrophysical observations. We employed He-tagging spectroscopy to record the spectrum of tetracene cations. In contrast to previous measurements of other polyacene cations, we found very narrow absorption bands of tetracene +. This makes the detection of tetracene+ in the ISM much easier compared to other studied polyacene cations. The four absorption bands of tetracene+ that are the best suited for the detection in observational spectra appeared at 859, 850.9, 838.8, and 827.3 nm. We did not find any DIBs at these positions. However, the observational spectra in this region from ground-based telescopes are heavily contaminated with telluric absorption bands, which greatly complicates the detection of DIBs. Comparison with observations performed by space telescopes is expected to significantly increase the sensitivity of the detection of the DIBs that could potentially be assigned to tetracene+. [ABSTRACT FROM AUTHOR]

The astronomical detection of formamide (NH2CHO) toward various star-forming regions and in cometary material implies that the simplest amide might have an early origin in dark molecular clouds at low temperatures. Laboratory studies have proven the efficient NH2CHO formation in interstellar CO:NH3 ice analogs upon energetic processing. However, it is still under debate, whether the proposed radicalâ€"radical recombination reactions forming complex organic molecules remain valid in an abundant H2O environment. The aim of this work was to investigate the formation of NH2CHO in H2O- and CO-rich ices under conditions prevailing in molecular clouds. Therefore, different ice mixtures composed of H2O:CO:NH3 (10:5:1), CO:NH3 (4:1), and CO:NH3 (0.6:1) were exposed to vacuum ultraviolet photons in an ultra-high vacuum chamber at 10 K. Fourier-transform infrared spectroscopy was utilized to monitor in situ the initial and newly formed species as a function of photon fluence. The infrared spectral identifications are complementarily secured by a temperature-programmed desorption experiment combined with a quadrupole mass spectrometer. The energetic processing of CO:NH3 ice mixtures mainly leads to the formation of NH2CHO, along with its chemical derivatives such as isocyanic acid (HNCO) and cyanate ion (OCNâˆ'). The formation kinetics of NH2CHO shows an explicit dependency on ice ratios and compositions; the highest yield is found in H2O-rich ice. The astronomical relevance of the resulting reaction network is discussed. [ABSTRACT FROM AUTHOR]

The study of the S1(1A1)←S0(1A1) transition of benzo[g,h,i]perylene (BghiP, C22H12) in supersonic jets and solid rare gas matrices is reported. In the jet-cooled spectrum, the origin band position is located at 25 027.1±0.2 cm-1, the assignment being supported by the analysis of vibrational shifts and rotational band contours. Except for the origin band, which is weak, all bands are attributed to the fundamental excitation of nontotally symmetric b1 vibrational modes of S1. The intensity pattern is interpreted as a consequence of the weak oscillator strength of the electronic transition combined with intensity-borrowing through vibronic interaction between the S1(1A1) and S2(1B1) states. The spectra of the S1(1A1)←S0(1A1) and S2(1B1)←S0(1A1) transitions have also been measured for BghiP in solid neon and argon matrices. The comparison of the redshifts determined for either transition reveals that the polarizability of BghiP is larger in its S2 than in its S1 state. Bandwidths of 2.7 cm-1 measured in supersonic jets, which provide conditions relevant for astrophysics, are similar to those of most diffuse interstellar bands. The electronic transitions of BghiP are found to lie outside the ranges covered by present databases. From the comparison between experimental spectra and theoretical computations, it is concluded that the accuracy of empirical and ab initio approaches in predicting electronic energies is still not sufficient to identify astrophysically interesting candidates for spectroscopic laboratory studies. [ABSTRACT FROM AUTHOR]

The adsorption of helium on charged hexabenzocoronene (Hbc, C 42 H 18 ), a planar polycyclic aromatic hydrocarbon (PAH) molecule of D 6 h symmetry, was investigated by a combination of high-resolution mass spectrometry and classical and quantum computational methods. The ion abundance of He n Hbc + complexes versus size n features prominent local anomalies at n = 14, 38, 68, 82, and a weak one at 26, indicating that for these "magic" sizes, the helium evaporation energies are relatively large. Surprisingly, the mass spectra of anionic He n Hbc - complexes feature a different set of anomalies, namely at n = 14, 26, 60, and 62, suggesting that the preferred arrangement of the adsorbate atoms depends on the charge of the substrate. The results of our quantum calculations show that the adsorbate layer grows by successive filling of concentric rings that surround the central benzene ring, which is occupied by one helium atom each on either side of the substrate. The helium atoms are fairly localized in filled rings and they approximately preserve the D 6 h symmetry of the substrate, but helium atoms in partially filled rings are rather delocalized. The first three rings contain six atoms each; they account for magic numbers at n = 14, 26, and 38. The size of the first ring shrinks as atoms are filled into the second ring, and the position of atoms in the second ring changes from hollow sites to bridge sites as atoms are filled into the third ring. Beyond n = 38, however, the arrangement of helium atoms in the first three rings remains essentially frozen. Presumably, another ring is filled at n = 68 for cations and n = 62 for anions. The calculated structures and energies do not account for the difference between charge states, although they agree with the measurements for the cations and show that the first solvation shell of Hbc ± is complete at n = 68. Beyond that size, the adsorbate layer becomes three-dimensional, and the circular arrangement of helium changes to hexagonal.

Helium droplets represent a cold inert matrix, free of walls with outstanding properties to grow complexes and clusters at conditions that are perfect to simulate cold and dense regions of the interstellar medium. At sub-Kelvin temperatures, barrierless reactions triggered by radicals or ions have been observed and studied by optical spectroscopy and mass spectrometry. The present review summarizes developments of experimental techniques and methods and recent results they enabled., (© 2021 The Authors. Mass Spectrometry Reviews published by John Wiley & Sons Ltd.)

Photochemistry in H 2 O:NH 3 :CO 2 cosmic ice analogues was studied at temperatures of 75, 120, and 150 K, relevant to hot cores and warmer regions in protostellar envelopes and planet-forming disks. A combination of two triggers of surface chemistry in cosmic ice analogues, heat and UV irradiation, compared to using either just heat or UV irradiation, leads to a larger variety and an increased production of complex organic molecules, including potential precursors of prebiotic molecules. In addition to complex organic molecules detected in previous studies of H 2 O:NH 3 :CO 2 ices, ammonium carbamate, carbamic acid, ammonium formate and formamide, we detected acetaldehyde, urea, and, tentatively, glycine, the simplest amino acid. Water ice hampers reactions at low temperature (75 K) but allows the parent molecules, CO 2 and NH 3 , to stay in the solid state and react at higher temperatures (120 and 150 K, above their desorption temperatures). The experiments were performed on the surface of KBr substrates and amorphous silicate grains, analogs of cosmic silicate dust. The production of complex molecules on the silicate surface is decreased compared to KBr. This result suggests that the larger surface area and/or surface properties of the silicate grains play a role in controlling the chemistry, preventing it taking place to the same extent as on the flat KBr substrate. This is further evidence of the fact that cosmic dust grains play an important role in the chemistry taking place on their surface.

In a series of experiments devoted to the study of polycyclic aromatic hydrocarbons for astrophysical applications, the S(2)<--S(0) transition of jet-cooled pyrene (C(16)H(10)) at 321 nm has been studied by an absorption technique for the first time. The spectra observed by cavity ring-down spectroscopy closely resemble the excitation spectra obtained earlier by laser-induced fluorescence (LIF) and show the same band clusters arising from the vibronic interaction of S(2) with S(1). We have also investigated pyrene when it was incorporated into 380 mK cold helium droplets. These spectra which were recorded employing LIF and molecular beam depletion spectroscopy are broadened and redshifted by 0.94 nm but retain the essential features of the gas phase spectra.

The conformational structures of 2-deoxyuridine (dU) were investigated using Fourier transform infrared (FTIR) matrix isolation spectroscopy. For the first time the FTIR spectra of dU in Ar matrices were obtained in the range 4000-200 cm(-1). The stabilities of conformers were estimated by the methods HF/3-21G (p), HF/6-31G (d,p) and MP2/6-31G (d,p). Ab initio calculations of the infrared spectra were performed by the methods HF/3-21G (p) and HF/6-31G (d,p). The actual occupancy of conformational isomers in matrix samples was determined. It was shown that anti-conformers of dU are dominant. The ribose rings of the main anti-conformers dU &#95;a0, dU &#95;a1 are in the C2'-endo conformation, but the ribose rings of minor anti-conformers dU&#95;a2, dU&#95;a3 have the C3'-endo conformation, stabilized by intramolecular hydrogen bonds O3'H...O5' and O5'H...O3', accordingly. Syn-conformers of dU are stabilized by the intramolecular hydrogen bond O5'H...O2 and the dominant conformation of the ribose ring is C2'-endo.