The rise of an exciton in solid ammonia.

We trace a polymorphic phase change in solid ammonia films through the emergence of a Frenkel exciton at 194.4 nm, for deposition temperatures of 48 K, 50 K and 52 K. Observations on a timescale of hours give unparalleled access to the individual processes of nucleation and the phase change itself. The excitonic transition is forbidden in the low temperature phase, but greater flexing of the solid state structure in the higher temperature phase makes the transition allowed, as the nano-crystals approach ∼30 unit cells through nucleation. We find activation energies of 21.7 ± 0.6 kJ mol-1 for nucleation and 22.8 ± 0.6 kJ mol-1 for the phase change, corresponding to the breaking of two to three hydrogen bonds.

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 2: electron irradiation and thermal processing.

Many experimental parameters determine the chemical and physical properties of interstellar ice analogues, each of which may influence the molecular synthesis that occurs in such ices. In part 1, James et al., RSC Adv., 2020, 10, 37517, we demonstrated the effects that the stoichiometric mixing ratio had on the chemical and physical properties of CO2 : NH3 mixtures and the impact on molecular synthesis induced by thermal processing. Here, in part 2, we extend this to include 1 keV electron irradiation at 20 K of several stoichiometric mixing ratios of CO2 : NH3 ices followed by thermal processing. We demonstrate that not all stoichiometric mixing ratios of CO2 : NH3 ice form the same products. Not only did the 4 : 1 ratio form a different residue after thermal processing, but O3 was observed after electron irradiation at 20 K, which was not observed in the other ratios. For the other ratios, the residue formed from a thermal reaction similar to the work shown in Part 1. However, conversion of ammonium carbamate to carbamic acid was hindered due to electron irradiation at 20 K. Our results demonstrate the need to systematically investigate stoichiometric mixing ratios to better characterise the chemical and physical properties of interstellar ice analogues to further our understanding of the routes of molecular synthesis under different astrochemical conditions.

Crystallites and Electric Fields in Solid Ammonia.

Absorption spectra of vacuum-deposited films of ammonia have been obtained in the range 115 nm to 310 nm for a set of 15 deposition temperatures, Td, between 20 K and 80 K. Results focus upon the region 115 nm to 130 nm in overlapping D, E, F and G←X Rydberg transitions involving Wannier-Mott excitons. We identify two phases of ammonia, showing the solid to be polymorphic. Peak absorption wavelengths in the region of interest are found to shift to the red by 299 cm-1, for Td between 20 K to 50 K, and 1380 cm-1 for Td between 55 K to 80 K. Shifts provide evidence for the presence of spontaneously generated electric fields in these films, of values in excess of 108 V m-1 for Td of 20 K to 50 K to a few times 107 V m-1 for 55 K to 80 K. Results enable us to place a lower limit of 1.58 nm on the size of crystallites in the low temperature regime. This dimension represents 16 unit cells or 64 species, giving a more quantitative description than the nebulous term amorphous, as applied to solid ammonia. We also determine that crystallites formed in the high temperature regime contain, within ±20 %, 1688, 756 and 236 molecules of ammonia, respectively at Td of 65 K, 60 K and 55 K.

Systematic investigation of CO2 : NH3 ice mixtures using mid-IR and VUV spectroscopy - part 1: thermal processing.

The adjustment of experimental parameters in interstellar ice analogues can have profound effects on molecular synthesis within an ice system. We demonstrated this by systematically investigating the stoichiometric mixing ratios of CO2 : NH3 ices as a function of thermal processing using mid-IR and VUV spectroscopy. We observed that the type of CO2 bonding environment was dependent on the different stoichiometric mixing ratios and that this pre-determined the NH3 crystallite structure after phase change. The thermal reactivity of the ices was linked to the different chemical and physical properties of the stoichiometric ratios. Our results provide new details into the chemical and physical properties of the different stoichiometric CO2 : NH3 ices enhancing our understanding of the thermally induced molecular synthesis within this ice system.

VUV spectroscopy of an electron irradiated benzene : carbon dioxide interstellar ice analogue.

We present the first vacuum ultraviolet spectroscopic study of an interstellar ice analogue of a 1 : 100 benzene (C6H6) : carbon dioxide (CO2) mixture which has been energetically processed with 1 keV electrons. We have exploited the fact that benzene has a relatively high photoabsorption cross section in the vacuum ultraviolet region to study this dilute mixture of benzene. Before irradiation with 1 keV electrons, we observed that the benzene electronic transition bands in the C6H6 : CO2 mixture exhibits a blueshift in band position towards energies observed in the gas-phase compared with that of pure, amorphous benzene and we have attributed this to a matrix isolation effect. After irradiation, a lowering in intensity of both the carbon dioxide and benzene electronic transition bands was observed, as well as the formation of the small irradiation product, carbon monoxide. A residue was obtained at 200 K which showed characteristic features of the benzene electronic transition of 1E1u ← 1A1g, but with additional structure suggesting the formation of a benzene derivative.

The optical absorption spectra of spontaneously electrical solids: the case of nitrous oxide.

Absorption spectra of films of N2O, in the range 115-160 nm, are presented for deposition temperatures between 33 K and 64 K. Observed shifts in the absorption energy vs. deposition temperature are analysed in terms of the temperature-dependent spontaneously electrical ('spontelectric') fields present in the films. Using a simple electrostatic theory, we suggest that (i) spectra are associated with Wannier-Mott excitons, (ii) the action of the electric field upon the excitons suffers a blockade at ≤54 K for the C-state and ≤52 K for the D-state of N2O, (iii) the blockade may be attributed to structural defects, which trap excitons, limiting their size and (iv) films form with defect-free regions containing 324 ± 3, 168 ± 46 and 95 ± 1 molecules of N2O at 54 K, 52 K and 50 K respectively, yielding an experimental indication of the scale size of regular periodicity associated with Wannier-Mott excitons. Results demonstrate how the spontelectric effect can be used as a tool for exploring the structure of solids and give a graphic image of the structural changes that take place close to the known phase change at 47 K/48 K.

Probing the interaction between solid benzene and water using vacuum ultraviolet and infrared spectroscopy.

We present results of a combined vacuum ultraviolet (VUV) and infrared (IR) photoabsorption study of amorphous benzene : water mixtures and layers to investigate the benzene-water interaction in the solid phase. VUV spectra of 1 : 1, 1 : 10 and 1 : 100 benzene : water mixtures at 24 K reveal a concentration dependent shift in the energies of the 1B2u, 1B1u and 1E1u electronic states of benzene. All the electronic bands blueshift from pure amorphous benzene towards gas phase energies with increasing water concentration. IR results reveal a strong dOH-π benzene-water interaction via the dangling OH stretch of water with the delocalised π system of the benzene molecule. Although this interaction influences the electronic states of benzene with the benzene-water interaction causing a redshift in the electronic states from that of the free benzene molecule, the benzene-benzene interaction has a more significant effect on the electronic states of benzene. VUV spectra of benzene and water layers show evidence of non-wetting between benzene and water, characterised by Rayleigh scattering tails at wavelengths greater than 220 nm. Our results also show evidence of benzene-water interaction at the benzene-water interface affecting both the benzene and the water electronic states. Annealing the mixtures and layers of benzene and water show that benzene remains trapped in/under water ice until water desorption near 160 K. These first systematic studies of binary amorphous mixtures in the VUV, supported with complementary IR studies, provide a deeper insight into the influence of intermolecular interactions on intramolecular electronic states with significant implications for our understanding of photochemical processes in more realistic astrochemical environments.

Vacuum ultraviolet photoabsorption spectroscopy of crystalline and amorphous benzene.

We present the first high resolution vacuum ultraviolet photoabsorption study of amorphous benzene with comparisons to annealed crystalline benzene and the gas phase. Vapour deposited benzene layers were grown at 25 K and annealed to 90 K under conditions pertinent to interstellar icy dust grains and icy planetary bodies in our solar system. Three singlet-singlet electronic transitions in solid benzene correspond to the 1B2u, 1B1u and 1E1u states, redshifted by 0.05, 0.25 and 0.51 eV respectively with respect to the gas phase. The symmetry forbidden 1B2u ← 1A1g and 1B1u ← 1A1g transitions exhibit vibronic structure due to vibronic coupling and intensity borrowing from the allowed 1E1u ← 1A1g transition. Additionally the 1B2u ← 1A1g structure shows evidence of coupling between intramolecular vibrational and intermolecular lattice modes in crystalline benzene with Davydov crystal field splitting observed. The optically forbidden 0-0 electronic origin is clearly visible as a doublet at 4.69/4.70 eV in the crystalline solid and as a weak broadened feature at 4.67 eV in amorphous benzene. In the case of the 1B1u ← 1A1g transition the forbidden 0-0 electronic origin is only observed in crystalline benzene as an exciton peak at 5.77 eV. Thicker amorphous benzene samples show diffuse bands around 4.3, 5.0 and 5.4 eV that we tentatively assign to spin forbidden singlet-triplet 3B2u ← 1A1g, 3E1u ← 1A1g and 3B1u ← 1A1g transitions respectively, not previously reported in photoabsorption spectra of amorphous benzene. Furthermore, our results show clear evidence of non-wetting or 'islanding' of amorphous benzene, characterised by thickness-dependent Rayleigh scattering tails at wavelengths greater than 220 nm. These results have significant implications for our understanding of the physical and chemical properties and processes in astrochemical ices and highlight the importance of VUV spectroscopy.

Using the C-O stretch to unravel the nature of hydrogen bonding in low-temperature solid methanol-water condensates.

Transmission infrared spectroscopy has been used in a systematic laboratory study to investigate hydrogen bonding in binary mixtures of CH3OH and H2O, vapour deposited at 30 K, as a function of CH3OH/H2O mixing ratio, R. Strong intermolecular interactions are evident between CH3OH and H2O with infrared band profiles of the binary ices differing from that of the pure components and changing significantly with R. Consistent evidence from the O-H and C-H band profiles and detailed analysis of the C-O stretch band reveal two different hydrogen bonding structural regimes below and above R = 0.6-0.7. The vapour deposited solid mixtures were found to exhibit behaviour similar to that of liquids with evidence of inhomogeneity and higher coordination number of hydrogen bonds that are concentration dependent. The C-O stretch band is found to consist of three components around 1039 cm(-1) ('blue'), 1027 cm(-1) ('middle') and 1011 cm(-1) ('red'). The 'blue' and 'middle' components corresponding to environments with CH3OH dominating as a proton donor (PD) and proton acceptor (PA) respectively reveal preferential bonding of CH3OH as a PA and H2O as a PD in the mixtures. The 'red' component is only present in the presence of H2O and has been assigned to the involvement of both lone pairs of electrons on the oxygen atom of CH3OH as a PA to two PD H2O atoms. Cooperative effects are evident with concurrent blue-shifts in the C-H stretching modes of CH3OH below R = 0.6 indicating CH3 group participation in hydrogen bonding.

Morphological study into the temperature dependence of solid ammonia under astrochemical conditions using vacuum ultraviolet and Fourier-transform infrared spectroscopy.

The authors present the results of a morphological study of solid ammonia using both Fourier-transform infrared and vacuum ultraviolet (VUV) spectroscopy. Dramatic changes in the VUV and infrared spectra at temperatures between 65 and 85 K provide a deeper insight into the structure of ammonia ice particularly with the observation of an exciton transition at 194 nm (6.39 eV) in the VUV spectrum, revealing a structure that is composed of crystallites. A complementary structure is observed in the IR spectrum at 1100 cm(-1) which is assigned to the symmetric deformation of ammonia molecules at the surfaces of the crystallites. Such spectral signatures may be used to identify the environment within which the ammonia ice is formed and provide a new route for obtaining information on the physical and chemical conditions occurring within the interstellar medium, on the surfaces of planetary bodies, and in Kuiper belt objects.

Low energy 13C+ and 13C2+ ion irradiation of water ice.

In this paper we report the results of the first experimental study of the irradiation of low temperature water ice (30 and 90 K) using low energy (4 keV) 13C+ and 13C2+ ions. 13CO(2) and H2O(2) were readily formed within the H2O ice with the product yield and growth rate observed to be highly dependent on both the sample temperature and ion charge state.

VUV spectroscopy and photo-processing of astrochemical ices: an experimental study.

In order to understand much of the chemistry that underpins astronomical phenomena (e.g. star and planet formation) it is essential to probe the physico-chemistry of ice surfaces under astronomical conditions. The physical properties and chemical reactivity of such icy surfaces depends upon its morphology. Thus it is necessary to explore how the morphology of astrochemical ices is influenced by their local environment (e.g. temperature and pressure) and the mechanisms by which they are processed. In this paper we report the results of a series of experiments to explore the morphology of a variety of molecular ices using VUV spectroscopy. Spectral signatures are found that may allow the morphology of such ices to be identified.