Petr Kubelík

High-energy chemistry of formamide: A unified mechanism of nucleobase formation

Significance This paper addresses one of the central problems of the origin of life research, i.e., the scenario suggesting extraterrestrial impact as the source of biogenic molecules. Likewise, the results might be relevant in the search of biogenic molecules in the universe. The work is therefore highly actual and interdisciplinary. It could be interesting for a very broad readership, from physical and organic chemists to synthetic biologists and specialists in astrobiology. The coincidence of the Late Heavy Bombardment (LHB) period and the emergence of terrestrial life about 4 billion years ago suggest that extraterrestrial impacts could contribute to the synthesis of the building blocks of the first life-giving molecules. We simulated the high-energy synthesis of nucleobases from formamide during the impact of an extraterrestrial body. A high-power laser has been used to induce the dielectric breakdown of the plasma produced by the impact. The results demonstrate that the initial dissociation of the formamide molecule could produce a large amount of highly reactive CN and NH radicals, which could further react with formamide to produce adenine, guanine, cytosine, and uracil. Based on GC-MS, high-resolution FTIR spectroscopic results, as well as theoretical calculations, we present a comprehensive mechanistic model, which accounts for all steps taking place in the studied impact chemistry. Our findings thus demonstrate that extraterrestrial impacts, which were one order of magnitude more abundant during the LHB period than before and after, could not only destroy the existing ancient life forms, but could also contribute to the creation of biogenic molecules.

HNC/HCN ratio in acetonitrile, formamide, and BrCN discharge.

Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH(3)CN), and formamide (HCONH(2)). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v(1) were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms. The rate constant determined using the kinetic model from the present data for this reaction is 1.13 (±0.2) × 10(-13) cm(3) s(-1).

Laser spark formamide decomposition studied by FT-IR spectroscopy.

High-resolution FT-IR spectroscopy was used for the analysis of the products of formamide dissociation using a high-energy Asterix laser. In the experiment, the detected products of the formamide LIDB dissociation were hydrogen cyanide, ammonia, carbon monoxide, carbon dioxide, nitrous oxide, hydroxylamine, and methanol. The molecular dynamics of the process was simulated with the use of a chemical model. The chemistry shared by formamide and the products of its dissociation is discussed with the respect to the formation of biomolecules.

Na I spectra in the 1.4–14 micron range: transitions and oscillator strengths involving f-, g-, and h-states

Context. Compared with the visible and ultraviolet ranges, fewer atomic and ionic lines are available in the infrared spectral region. Atlases of stellar spectra often provide only a short list of identified lines, and modern laboratory-based spectral features for wavelengths longer than 1 micron are not available for most elements. For the efficient use of the growing capabilities of infrared (IR) astronomy, detailed spectroscopical information on atomic line features in the IR region is needed. Aims. Parts of the infrared stellar (e.g., solar) spectra in the 1200–1800 cm −1 (5.6–8 μm) range have never been observed from the ground because of heavy contamination of the spectrum by telluric absorption lines. Such an infrared spectrum represents a great challenge for laboratory observations of new, unknown infrared atomic transitions involving the atomic levels with high orbital momentum and their comparison with the available spectra. Methods. The vapors of excited Na I atoms are produced during the ablation of the salt (sodium iodide, Na I) targets by a highrepetition rate (1.0 kHz) pulsed nanosecond ArF laser ExciStar S-Industrial V2.0 1000, pulse length 12 ns, λ = 193 nm, output energy of 15 mJ, fluence about 2–20 J/cm 2 inside a vacuum chamber (average pressure 10 −2 Torr). The time-resolved emission spectrum of the neutral atomic potassium (Na I) was recorded in the 700–7000 cm −1 region using the Fourier transform infrared spectroscopy technique with a resolution of 0.02 cm −1 .T hef -values calculated in the quantum-defect theory approximation are presented for the transitions involving the reported Na I levels. Results. This study reports precision laboratory measurements for 26 Na I lines in the range of 700–7000 cm −1 (14–1.4 μm), including 20 lines not measured previously in the laboratory. This results in newly observed 7h, 6h, and 6g levels, and improved energy determination for ten previously known levels. The doublet structure of the 4f level has been observed for the first time. For transitions between the observed levels, we report calculated f -values that agree reasonably well with experiment. Conclusions. The recorded Na I line features agree with the data from the available solar spectrum atlases. The energy values of Na I 4s, 4p, 5p, 6p, 4f, 5f, and 5g levels extracted from our spectra have lower uncertainties as compared to the values reported several decades ago, but the latter values slightly differ from ours.

Potassium spectra in the 700–7000 cm-1 domain: Transitions involving f-, g-, and h-states

Context. The infrared (IR) range is becoming increasingly important to astronomical studies of cool or dust-obscured objects, such as dwarfs, disks, or planets, and in the extended atmospheres of evolved stars. A general drawback of the IR spectral region is the much lower number of atomic lines available (relative to the visible and ultraviolet ranges). Aims. We attempt to obtain new laboratory spectra to help us identify spectral lines in the IR. This may result in the discovery of new excited atomic levels that are difficult to compute theoretically with high accuracy, hence can be determined solely from IR lines. Methods. The K vapor was formed through the ablation of the KI (potassium iodide) target by a high-repetition-rate (1.0 kHz) pulsed nanosecond ArF laser (λ = 193 nm, output energy of 15 mJ) in a vacuum (10 −2 Torr). The time-resolved emission spectrum of the neutral atomic potassium (K i) was recorded in the 700–7000 cm −1 region using the Fourier transform infrared spectroscopy technique with a resolution of 0.02 cm −1 .T hef -values calculated in the quantum-defect theory approximation are presented for the transitions involving the reported K i levels. Results. Precision laboratory measurements are presented for 38 K i lines in the infrared (including 25 lines not measured previously in the laboratory) range using time-resolved Fourier transform infrared spectroscopy. The 6g, 6h, and 7h levels of K i are observed for the first time, in addition to updated energy values of the other 23 K i levels and the f -values for the transitions involving these levels. Conclusions. The recorded wave numbers are in good agreement with the data from the available solar spectrum atlases. Nevertheless, we correct their identification for three lines (1343.699, 1548.559, and 1556.986 cm −1 ).

Formation of nucleobases in a Miller-Urey reducing atmosphere.

Significance The study shows that Miller–Urey experiments produce RNA nucleobases in discharges and laser-driven plasma impact simulations carried out in a simple prototype of reducing atmosphere containing ammonia and carbon monoxide. We carried out a self-standing description of chemistry relevant to hypothesis of abiotic synthesis of RNA nucleobases related to early-Earth chemical evolution under reducing conditions. The research addresses the chemistry of simple-model reducing atmosphere (NH3 + CO + H2O) and the role of formamide as an intermediate of nucleobase formation in Miller–Urey experiment. The explorations combine experiments performed using modern techniques of large, high-power shock wave plasma generation by hall terawatt lasers, electric discharges, and state-of-the-art ab initio free-energy calculations. The Miller–Urey experiments pioneered modern research on the molecular origins of life, but their actual relevance in this field was later questioned because the gas mixture used in their research is considered too reducing with respect to the most accepted hypotheses for the conditions on primordial Earth. In particular, the production of only amino acids has been taken as evidence of the limited relevance of the results. Here, we report an experimental work, combined with state-of-the-art computational methods, in which both electric discharge and laser-driven plasma impact simulations were carried out in a reducing atmosphere containing NH3 + CO. We show that RNA nucleobases are synthesized in these experiments, strongly supporting the possibility of the emergence of biologically relevant molecules in a reducing atmosphere. The reconstructed synthetic pathways indicate that small radicals and formamide play a crucial role, in agreement with a number of recent experimental and theoretical results.

Li I spectra in the 4.65–8.33 micron range: high-L states and oscillator strengths

Context. Infrared (IR) astronomy capacities have rapidly developed in recent years thanks to several ground- and space-based facilities. To take advantage of these capabilities efficiently, a large amount of atomic data (such as line wavenumber, excited-level energy values, and oscillator strengths) are needed. These data are incomplete, in particular, for lithium whose abundances are important for several astrophysical problems. Aims. No laboratory-measured spectra of Li I have been reported for wavelengths longward of 6.6 microns. We aim to find new Li I lines in the 4.65–8.33 microns range due to transitions between states with high orbital momentum (l ≥ 4) and to determine the excitation energies of these states. Methods. The Li I lines were studied using the time-resolved Fourier transform infrared spectroscopy of a plasma created by the laser ablation of a LiF target in a vacuum. The classification of the lines was performed by accounting for oscillator strengths (f -values) calculated using quantum defect theory (QDT). The adequacy of QDT for these calculations was checked by comparison with the available experimental and theoretical results. Results. We report four new Li I lines in the 900–2200 cm –1 range that allow us to extract the excitation energies of the 6g, 6h, and 7h states of Li I, which have not been measured before. We also provide a large list of QDT-calculated f -values for Li I in the range of 1–20 microns.

Low-excited f-, g- and h-states in Au, Ag and Cu observed by Fourier-transform infrared spectroscopy in the 1000?7500 cm?1 region

The infrared emission spectra of Au, Ag and Cu resulting from the laser ablation of metal targets in a vacuum were recorded using time-resolved Fourier-transform spectroscopy in the 1200–1600, 1900–3600, 4100–5000 and 5200–7500 cm−1 ranges with a resolution of 0.017 cm−1. The majority of the observed lines correspond to transitions between low-excited Rydberg (Nd10)nlj states of Cu (N = 3), Ag (N = 4) and Au (N = 5) with a principal quantum number n = 4, ..., 10; the most prominent lines being due to transitions between the states with high orbital momenta l = 3, ..., 5. This study reports 32 new lines of Au, 12 of Ag and 20 of Cu (with uncertainties of 0.0003–0.03 cm−1). From the lines observed here and in our previous works, we extract revised energy values for 85 energy levels (uncertainty 0.01–0.03 cm−1) of which eight levels of Au, three of Ag and four of Cu are reported for the first time. These newly reported levels have high orbital momentum l = 3, 4, 5.

Laser ablation of CsI: time-resolved Fourier-transform infrared spectra of atomic cesium in the 800–8000 cm −1 range

Fourier-transform time-resolved spectroscopy of laser-induced breakdown of Cs vapor in a vacuum has been used for the measurement of atomic Cs emission spectra in the 800–8000  cm−1 range with a resolution of 0.02  cm−1. The 6h and 7h levels of Cs are observed. The dipole transition matrix elements (transition probabilities, oscillator, and line strengths) between the observed levels are calculated using quantum defect theory.

Time-resolved FTIR emission spectroscopy of Cu in the 1800{3800 cm -1 region: Transitions involving f and g states and oscillator strengths

Time-resolved Fourier-transform spectroscopy was applied to the study of the emission spectra of Cu vapours in a vacuum (10−2 Torr) produced in ablation of a Cu metal target by a high-repetition rate (1.0 kHz) pulsed nanosecond ArF laser (λ = 193 nm, output energy of 15 mJ). The time-resolved infrared emission spectrum of Cu was recorded in the 1800–3800 cm−1 spectral region with a resolution of 0.017 cm−1. The time profiles of the measured lines have maxima at 18–20 µs after a laser shot and display non-exponential decay with a decay time of 5–15 µs. This study reports 17 lines (uncertainty 0.0003–0.018 cm−1) of Cu I not previously observed. This results in seven newly-found levels and revised energy values for 11 known levels (uncertainty 0.01–0.03 cm−1). We also calculate transition probabilities and oscillator strengths for several transitions involving the reported Cu levels.