Surface reactions of radicals play important roles in the formation of complex molecules on interstellar dust grains. Under interstellar conditions, because the coverage of adsorbates on dust is significantly low, surface reactions are often limited by precedent processes, namely, the adsorption and diffusion of reactants. Therefore, to appropriately incorporate dust surface reactions into chemical models, information on the adsorption and diffusion of radicals is crucial. However, it is not easy to follow the behaviour of radicals on surfaces by conventional experimental methods. To monitor radicals on interstellar dust analogues, we have recently succeeded in applying a combination of photostimulated desorption and resonance-enhanced multiphoton ionization methods. In this paper, we briefly review our recent experiments for clarifying radical behaviour on water ice, pure solid CO and diamond-like carbon.

Carbonaceous meteorites contain a large variety of complex organic molecules, including amino acids, nucleobases, sugar derivatives, amphiphiles, and other compounds of astrobiological interest. Photoprocessing of ices condensed on cold grains with ultraviolet (UV) photons was proposed as an efficient way to form such complex organics in astrophysical environments. This hypothesis was confirmed by laboratory experiments simulating photo-irradiation of ices containing H2O, CH3OH, CO, CO2, CH4, H2CO, NH3, HCN, etc., condensed on cold (~10–80 K) substrates. These experiments resulted in the formation of amino acids, nucleobases, sugar derivatives, amphiphilic compounds, and other organics comparable to those identified in carbonaceous meteorites. This work presents results for the formation of sugars, sugar alcohols, sugar acids, and their deoxy variants from the UV irradiation of ices containing H2O and CH3OH in relative proportions 2:1, and their comparison with meteoritic data. The formation mechanisms of these compounds and the astrobiological implications are also discussed.

The multi-photon photodissociation (MPD) action spectrum of the coronene cation $$({{\rm{C}}_{24}}{\rm{H}}_{12}^ + )$$ has been measured as a function of storage time up to 60 s in the cryogenic electrostatic storage ring DESIREE. These measurements reveal not only the intrinsic absorption profile of isolated coronene cations, but also the rate at which hot-band absorptions are quenched by radiative cooling. The cooling rate is interpreted using a Simple Harmonic Cascade model of infrared vibrational emission.

Chondritic meteorites, and especially the most volatile-rich chondrites, the carbonaceous chondrites, preserve a record of the solar protoplanetary disk dust component and how it has been changed both in the disk environment itself and in its asteroidal parent body. Here we review some of the key features of carbonaceous chondrites and report some new data on their organics component. These show that the nebula reached temperature of >10000C, but only very locally, to produce chondrules. Most meteoritic material underwent thermal and/or aqueous processing, but some retain delicate nebular components such as complex organic molecules and amorphous silicates.

Chemistry in the interstellar medium is generally out-of-equilibrium and as such is kinetically controlled by a set of time-dependent equations, both for gas-phase chemistry and solid-state chemistry. The competition between the different possible reactions will determine toward which complex molecules the chemical network is driven to. The formation of complex molecules on the surface of the grains or in the ice mantle covering them is set by the diffusion-reaction equation, which is depending on temperature dependent reaction rate constants and diffusion coefficients. This paper shows how these two parameters can be experimentally determined by laboratory experiments. It also shows how the ice mantle reorganization plays an important role in the trapping and reactivity, which leads to the formation of complex organic molecules.

Experimental evidence for the formation of hydrogenated fullerene molecules is presented. Films of C60 were grown on a highly oriented pyrolytic graphite (substrate) and exposed to a beam of deuterium atoms. Thermal desorption combined with mass spectrometry was used to determine the deuterated fullerene products formed, revealing a maximum degree of deuteration corresponding to C60D36. Release of D2 from the deuterated C60 film occurs at a much higher temperature than for D-saturated graphite.

Cyclopropenylidene,, is a simple hydrocarbon, ubiquitous in astrophysical gases, and possessing a permanent electric dipole moment. Its readily observed multifrequency rotational transitions make it an excellent probe for the physics and history of interstellar matter. The collisional properties of with He are presented here. We computed the full Potential Energy Surfaces, and we perform quantum scattering in order to provide rates of quenching and excitation for low to medium temperature regimes. We discuss issues with the validity of the usual Local Thermodynamical Equilibrium assumption, and also the intricacies of the spectroscopy of an asymmetric top. We present the wide range of actual critical densities, as recently observed.

As observational facilities improve, providing new insights into the chemistry occurring in protoplanetary disks, it is important to develop more complete pictures of the processes that shapes the chemical evolution of materials during this stage of planet formation. Here we describe how primitive meteorites in our own Solar System can provide insights into the processes that shaped planetary materials early in their evolution around the Sun. In particular, we show how this leads us to expect protoplanetary disks to be very dynamic objects and what modeling and laboratory studies are needed to provide a more complete picture for the early chemical evolution that occurs for planetary systems.

The focus of this work is on two topics: (i) formation of complex organic molecules (COMs) and (ii) isotope fractionation. Various COMs, which are C, H-containing molecules consisting of 6 atoms and more, have been detected in the central warm region of protostellar cores. Most of this review is about gas-grain chemical models, which have been constructed to evaluate the mechanisms and efficiency of the COM formation. The relevant physical and chemical processes are investigated in laboratory experiments, as reported in other articles in this volume.

The isotope fractionation of volatile elements is observed in both the interstellar medium (ISM) and Solar system material. While exothermic exchange reactions enrich molecules with heavier isotopes such as Deuterium, the isotope selective photodissociation can be coupled with ice formation to enrich the ice mantle with rare isotopes. The efficiency of this fractionation depends on the photodesorption yields, which has been studied in laboratory experiments.

Debris disks are the natural by-products of the star and planet formation processes. Since the 1980’s several thousands of debris disks have been detected, and the presence of a disk is inferred by the detection of excess emission over the photospheric emission. This thermal emission arises from (micron-sized or slightly bigger) dust grains heated by the central star. However, in the vast majority of cases, these observations are not spatially resolving the radial distribution of the dust, resulting in strong degeneracies in the modeling approach (radial distance vs minimum grain size mostly). Therefore the properties of the small dust grains remained largely unconstrained until the arrival of high angular resolution instruments, especially at optical and near-infrared wavelengths. In these proceeding some of the main results are presented that have been obtained over the past few years on the properties of small dust grains in debris disks, and it is discussed how laboratory experiments contributed to put those results in context.

Isopropyl-cyanide (iso-PrCN) was recently observed in Sagittarius B2 with an abundance higher than its straight-chain structure isomer (n-PrCN). Here we study theoretically by means of [UMP2(full)/aug-cc-pVTZ/Amber] a hybrid ab initio/molecular mechanics methodology, the routes leading to its formation on a formaldehyde doped water ice grain model of the interstellar medium. The reaction path and the energetics are calculated, the mechanism is found to be exothermic by ∼ 30 kcal/mol and the barrier is ∼ 70 kcal/mol. We use the CVT/ZCT semiclassical method to predict the kinetics of the reaction path starting from initially adsorbed HCN and CH2CHCH3 molecules colliding from the gas phase over the temperature range [100–500K].

Understanding the physical structure of the planet formation environment, the protoplanetary disk, is essential for the interpretation of high resolution observations of the dust and future observations of the magnetic field structure. Observations of multiple transitions of molecular species offers a unique view of the underlying physical structure through excitation analyses. Here we describe a new method to extract high-resolution spectra from low-resolution observations, then provide two case studies of how molecular excitation analyses were used to constrain the physical structure in TW Hya, the closest protoplanetary disk to Earth.

Saturn’s moon Titan was explored by the Cassini mission for nearly 13 years. Important discoveries made during the Cassini mission include the observations of stratospheric clouds in Titan’s cold polar regions in which spectral features or organic molecules were detected in the infrared (<100 μm). In particular, benzene (C6H6) ice spectral signatures were recently detected at unexpectedly high altitudes over the South Pole. The combined experimental, modeling and observational effort presented here has been devised and executed in order to interpret these high altitude benzene observations. Our multi-disciplinary approach aims to understand and characterize the microphysics of benzene clouds in Titan’s South Pole.

Electrospray ionisation has revolutionised mass spectrometry. Coupled to high mass resolution, it provides the stoichiometric formula of a lot of molecules in a mixture. The link between the mass spectrometry data and the chemical description relies on an interpretation of the measured masses. We present here the tools and tricks developed to exploit Orbitrap mass spectra. This piece of work focuses on the numerical method to assign a molecular formula to a measured mass. The problem is restrained to the solving of the Diophantine equation where the constant coefficients are stoichiometric groups. Peculiar case of a set of convenient groups is given with the chemical constraints it brings to the problem.

Circumstellar dust analogues can be studied experimentally to determine their collisional behavior and their optical properties. These results affect simulations of circumstellar disks in various, substantial ways: Collision results determine how dust aggregates grow and how their aerodynamic properties change with time. This determines how solids move throughout the disk, how they accumulate, and how planetesimals might be formed. The optical properties determine the observational signature of these effects and allow us to constrain the spatial distribution of dust in disks, the sizes of the aggregates, as well as the temperature and optical depth of the dust emission. In this contribution, it is discussed how theoretical models and their predictions depend on laboratory results and what we learned about disks from high spatial resolution radio interferometry.

VLT instruments and ALMA with their high spatial resolution have revolutionized in the past five years our view and understanding of how disks turn into planetary systems. This talk will briefly outline our current understanding of the physical processes occurring and chemical composition evolving as these disks turn into debris disks and eventually planetary systems like our own solar system. I will especially focus on the synergy between disk structure/evolution modeling and astrochemical laboratory/theoretical work to highlight the most recent advances, and open questions such as (1) how much of the chemical composition in disks is inherited from molecular clouds, (2) the relevance of snowlines for planet formation, and (3) what is the origin of the gas in debris disks and what can we learn from it. For each of the three, I will outline briefly how the combination of theory/lab astrochemistry, astrophysical models and observations are required to advance our understanding.

The emergence of life on Earth may have its origin in organic molecules formed in the interstellar medium. Molecules with amide and isocyanate groups resemble structures found in peptides and nucleobases and are necessary for their formation. Their formation is expected to take place in the solid state, on icy dust grains, and is studied here by far-UV irradiating a CH4:HNCO mixture at 20 K in the laboratory. Reaction products are detected by means of infrared spectroscopy and temperature programmed desorption - mass spectrometry. Various simple amides and isocyanates are formed, showing the importance of ice chemistry for their interstellar formation. Constrained by experimental conditions, a reaction network is derived, showing possible formation pathways of these species under interstellar conditions.

Accurate atomic data for line wavelengths, energy levels, line broadening such as hyperfine structure and isotope structure, and f-values, particularly for the line rich iron group elements, are needed for stellar astrophysics applications, and examples of recent measurements are given. These atomic data are essential for determination of elemental abundances in astronomical objects. With modern facilities, telescopes and spectrographs, access to underexplored regions (IR, UV, VUV), and improved stellar atmosphere models (3D, NLTE), and extremely large datasets, astronomers are tackling problems ranging from studying Galactic chemical evolution, to low mass stars and exoplanets. Such advances require improved accuracy and completeness of the atomic database for analyses of astrophysical spectra.

The Wootton Center for Astrophysical Plasma Properties (WCAPP) is a new center focusing on the spectroscopic properties of stars and accretion disks using “at-parameter” experiments. Currently, these experiments use the X-ray output of the Z machine at Sandia National Laboratories — the largest X-ray source in the world — to heat plasmas to the same conditions (temperature, density, and radiation environment) as those observed in astronomical objects. The experiments include measuring (1) density-dependent opacities of iron-peak elements at solar interior conditions, (2) spectral lines of low-Z elements at white dwarf photospheric conditions, (3) atomic population kinetics of neon in a radiation-dominated environment, and (4) resonant Auger destruction (RAD) of silicon at conditions found in accretion disks around supermassive black holes. In particular, we report on recent results of our experiments involving helium at white dwarf photospheric conditions. We present results showing disagreement between inferred electron densities using the Hβ line and the He I 5876 Å line, most likely indicating incompleteness in our modeling of this helium line.

Syntheses of carbon dust analogues are key experiments in laboratory astrophysics, as an approach to study some chemical and topological features of interplanetary and interstellar carbon dust. We report a comparative experimental study for carbon dust analogues obtained in (1) an atmospheric pressure dielectric barrier discharge (DBD), fed with helium – saturated hydrocarbons gas mixtures, (2) a low pressure radio frequency (RF) discharge and (3) a pulsed laser deposition (PLD) experiment with a Nd:YAG laser and a graphite target. The aliphatic –C–H stretching band, known as the 3.4 micron feature, as well as the CH2/CH3 ratio, the H/C ratio value and the physical appearance at microscopic scale, show a variability that is influenced by the synthesis method and the experimental parameters of each specific technique.