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Formamide (NH 2 C(O)H) has been observed both in the interstellar medium (ISM), being identified as a potential precursor of prebiotic molecules in space, and in the Earth's atmosphere. In these environments where temperature is very distinct, hydroxyl (OH) radicals may play an important role in the degradation of NH 2 C(O)H. Thus, in this work, we report for the first time the experimental study of the temperature dependence of the gas-phase removal of OH in the presence of NH 2 C(O)H over the 11.7-353 K range. In the lowest temperature range (11.7-177.5 K), of interest for the ISM chemistry, the kinetic study was performed using a pulsed CRESU (French acronym for Reaction Kinetics in a Uniform Supersonic Flow) apparatus, while a thermostatized slow-flow reactor was employed in the kinetic study of the OH + NH 2 C(O)H reaction over the 273-353 K range, of interest in the Earth's troposphere below room temperature. The pulsed laser photolysis at 248 nm of a suitable OH-precursor (hydrogen peroxide, tert -butyl hydroperoxide, or acetylacetone) was used to generate OH radicals in the reactor. The temporal evolution of OH was monitored by laser-induced fluorescence at 310 nm. An almost independent k ( T ) between 273 and 353 K (temperatures of the Earth's troposphere extended to T > 298 K) is reported, being the OH + NH 2 C(O)H reaction the major degradation route with an atmospheric lifetime of around 1 day. At lower temperatures of interest in the ISM (11.7-177.5 K), the potential formation of NH 2 C(O)H dimers was evaluated. Thermodynamically, under equilibrium conditions, formamide would be fully converted into the dimer in that T range. However, the qualitative agreement of the observed increase of k ( T ) with computational studies on the OH + NH 2 C(O)H reaction down to 200 K let us to report, between 177.5 and 106.0 K, the following parameters commonly used in astrochemical modeling: α = (3.76 ± 0.62) × 10 -12 cm 3 s -1 , β = (3.07 ± 0.11), and γ = 0. At 11.7 K, a kinetic model reproducing the experimental data indicates that formamide dimerization could be important, but the OH-reaction with the monomer would be fast, 4 × 10 -10 cm 3 s -1 , and the OH-reaction with the dimer, relatively slow [(0.1-1.0) × 10 -11 cm 3 s -1 ]. Despite that, the impact of the gas-phase OH + NH 2 C(O)H in the relative abundances of NH 2 C(O)H in a dense molecular cloud ( T ∼ 10 K) and after the warm-up phase in the surroundings of hot cores/corinos (here, 10-400 K) appears to be negligible., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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.

The adsorption of up to ∼100 helium atoms on cations of the planar polycyclic aromatic hydrocarbons (PAHs) anthracene, phenanthrene, fluoranthene, and pyrene was studied by combining helium nanodroplet mass spectrometry with classical and quantum computational methods. Recorded time-of-flight mass spectra reveal a unique set of structural features in the ion abundance as a function of the number of attached helium atoms for each of the investigated PAHs. Path-integral molecular dynamics simulations were used with a polarizable potential to determine the underlying adsorption patterns of helium around the studied PAH cations and in good general agreement with the experimental data. The calculated structures of the helium-PAH complexes indicate that the arrangement of adsorbed helium atoms is highly sensitive toward the structure of the solvated PAH cation. Closures of the first solvation shell around the studied PAH cations are suggested to lie between 29 and 37 adsorbed helium atoms depending on the specific PAH cation. Helium atoms are found to preferentially adsorb on these PAHs following the 3 × 3 commensurate pattern common for graphitic surfaces, in contrast to larger carbonaceous molecules like corannulene, coronene, and fullerenes that exhibit a 1 × 1 commensurate phase.

The Belousov-Zhabotinsky (BZ) reaction is an example of a homogeneous, nonequilibrium reaction used commonly as a model for the study of biological structure and morphogenesis. We report the experimental effects of temperature on spontaneously nucleated trigger waves in a quasi-two-dimensional BZ reaction-diffusion system, conducted isothermally at temperatures between 9.9 and 43.3 °C. Novel application of filter-coupled circle finding and localized pattern analysis is shown to allow the highly accurate extraction of average radial wave velocity and nucleation period. Using this, it is possible to verify a strong Arrhenius dependence of average wave velocity with temperature, which is used to find the effective activation energy of the reaction in accordance with predictions elaborated from the widely used Oregonator model of the BZ reaction. On the basis of our experimental results and existing theoretical models, the value for activation energy of the important self-catalyzed step in the Oregonator model is determined to be 86.58 ± 4.86 kJ mol -1 , within range of previous theoretical prediction.

Building on the success of Quantum Monte Carlo techniques such as diffusion Monte Carlo, alternative stochastic approaches to solve electronic structure problems have emerged over the past decade. The full configuration interaction quantum Monte Carlo (FCIQMC) method allows one to systematically approach the exact solution of such problems, for cases where very high accuracy is desired. The introduction of FCIQMC has subsequently led to the development of coupled cluster Monte Carlo (CCMC) and density matrix quantum Monte Carlo (DMQMC), allowing stochastic sampling of the coupled cluster wave function and the exact thermal density matrix, respectively. In this Article, we describe the HANDE-QMC code, an open-source implementation of FCIQMC, CCMC and DMQMC, including initiator and semistochastic adaptations. We describe our code and demonstrate its use on three example systems; a molecule (nitric oxide), a model solid (the uniform electron gas), and a real solid (diamond). An illustrative tutorial is also included.

We report the observation of sequential encounters of fullerenes with C atoms in an extremely cold environment. Experiments were performed with helium droplets at 0.37 K doped with C60 molecules and C atoms derived from a novel, pure source of C atoms. Very high-resolution mass spectra revealed the formation of carbenes of the type C60(C:)n with n up to 6. Bridge-type bonding of the C adatoms to form the known dumbbell C60═C═C60 also was observed. Density functional theory calculations were performed that elucidated the carbene character of the C60(C:)n species and their structures. Mass spectra taken in the presence of water impurities and in separate experiments with added H2 also revealed the formation of the adducts C60C(n)(H2O)n and C60C(n)(H2)n probably by H-OH and H-H bond insertion, respectively, and nonreactivity for the dumbell. So C adatoms that form carbenes C60(C:)n can endow pristine C60 with a higher chemical reactivity.

Tetraphenyldibenzoperiflanthene (DBP) is a promising candidate as a component of highly efficient organic photovoltaic cells and organic light-emitting diodes. The structural properties of thin films of this particular lander-type molecule on Ag(111) were investigated by complementary techniques. Highly ordered structures were obtained, and their mutual alignment was characterized by means of low-energy electron diffraction (LEED). Scanning tunneling microscopy (STM) images reveal two slightly different arrangements within the first monolayer (ML), both describable as specific herringbone patterns with two molecules per unit cell whose dibenzoperiflanthene framework is parallel to the surface. In contrast, single DBP molecules in the second ML were imaged with much higher intramolecular resolution, resembling the shape of the frontier orbitals in the gas phase as calculated by means of density functional theory (DFT). Further deposition leads to the growth of highly ordered bilayer islands on top of the first ML with identical unit cell dimensions and orientation but slightly inclined molecules. This suggests that the first ML acts as a template for the epitaxial growth of further layers. Simultaneously, a significant number of second-layer molecules mainly located at step edges or scattered over narrow terraces do not form highly ordered aggregates.

We have studied the reactions of iron atoms and clusters with oxygen, acetylene, and water molecules in superfluid He droplets at T = 0.37 K. For all systems, the formation of weakly bound adducts was found, but the insertion reaction of iron into existing molecular bonds could not be observed. The formation of FeOH2 and FeC2H2 complexes was evidenced by mass spectrometry. However, it was found that the reaction of iron atoms with oxygen molecules under similar conditions leads to the stabilization of an intermediate reaction product, the weakly bound linear FeOO adduct, which undergoes complete dissociation upon electron impact ionization. All reactions observed are not expected to proceed in the gas phase. The R2PI spectrum of the y5D4 0 ← a5D4 atomic transition of Fe solvated in helium droplets was recorded. A relatively small blue shift of ∼ 120 cm(-1) with respect to the gas phase position was found.

The doping of He droplets by Al atoms and their reactions with H(2)O and O(2) at T = 0.37 K was investigated. It was found that at high doping concentrations, the incorporated Al atoms do not aggregate to form clusters. They rather remain as separated atoms inside of the He droplets. Mass spectrometry and the recently developed depletion method have been applied to study the reactions. It was found that single Al atoms react with single O(2) molecules. The dominant product of this reaction occurring inside of the He droplets is AlO(2). The reaction between Al and O(2) clusters has also been detected. The Al clusters react with single H(2)O molecules or clusters. While single Al atoms react with H(2)O clusters, no reaction of single Al atoms with a single water molecule was found.

The reaction between Si and O(2) was studied in liquid He droplets at low temperature (T = 0.37 K) by monitoring the energy release during the reaction. Additionally, the reactions of Si atoms and clusters with the oxidation agents H(2)O and O(2) have been studied by mass spectrometry. It was found that Si atoms react fast with O(2) molecules. On the other hand, Si atoms and clusters do not react with H(2)O molecules. The energy released during the chemical reaction leads to the ejection of the products from small He droplets. In contrast, large He droplets (N(He) > 20000) are capable of keeping part of the reaction products in their interior. The observation of SiO(2) products with the mass spectrometer reveals that the He droplet can stabilize intermediate products in the exit channel.

The reaction of magnesium atoms and clusters with oxygen molecules has been investigated in liquid helium droplets at T = 0.37 K. The energy released during the reaction predominantly leads to the ejection of the reaction products out of the He droplets. The product molecules Mg(2)O, Mg(2)O(2), Mg(3)O, Mg(3)O(2), and Mg(4)O(2) were detected by mass spectrometry. With more than one Mg atom picked up per He droplet, chemiluminescence (CL) light could be detected. This CL results from electronically and vibrationally excited reaction products (Mg(n)O(2), n > or = 2) which left the He droplets. For large He droplets with diameter d > 13 nm, the intensity of the CL light decreases linearly with increasing He droplet diameter. No evidence for chemical reaction was found for d > 50 nm. A considerable time delay between chemical reaction and light emission was observed. It was found that the chemical reaction is unexpectedly fast and has a first-order reaction rate larger than 5 x 10(4) s(-1).

The jet-cooled ultraviolet direct absorption spectrum of the amino acid tryptophan is reported. The spectrum measured by cavity ring-down laser absorption spectroscopy covers the region where the origin bands of the S(1) <-- S(0) transitions of six conformers (A to F) are located. Tryptophan was transferred into the gas phase by two different methods, namely, thermal heating and laser vaporization. The latter technique allowed us to obtain higher densities of tryptophan in the jet at the time when it was probed for spectroscopy. It also avoided thermal decomposition of the sample. On the other hand, a higher signal-to-noise ratio was obtained with thermal heating. Measurements were carried out by laser-induced fluorescence as well. The comparison of the absorption and excitation spectra reveals a higher fluorescence yield and a shorter radiative lifetime for the S(1) state of conformer A relative to the other conformers. Moreover, the comparison of our spectra with each other and with literature data led us to assign a band to a new conformer, which we named G. Finally, the theoretical structure and vibrational frequencies obtained from density functional theory based calculations confirm that the progression observed in the S(1) <-- S(0) spectrum of conformer A is consistent with a torsional motion of the amino acid side chain relative to the indole chromophore.