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The infrared excitation and photodesorption of carbon monoxide (CO) and water-containing ices have been investigated using the FEL-2 free-electron laser light source at the FELIX laboratory, Radboud University, The Netherlands. CO-water mixed ices grown on a gold-coated copper substrate at 18 K were investigated. No CO photodesorption was observed, within our detection limits, following irradiation with light resonant with the C-O vibration (4.67 μm). CO photodesorption was seen as a result of irradiation with infrared light resonant with water vibrational modes at 2.9 μm and 12 μm. Changes to the structure of the water ice, which modifies the environment of the CO in the mixed ice, were also seen subsequent to irradiation at these wavelengths. No water desorption was observed at any wavelength of irradiation. Photodesorption at both wavelengths is due to a single-photon process. Photodesorption arises due to a combination of fast and slow processes of indirect resonant photodesorption (fast), and photon-induced desorption resulting from energy accumulation in the librational heat bath of the solid water (slow) and metal-substrate-mediated laser-induced thermal desorption (slow). Estimated cross-sections for the slow processes at 2.9 μm and 12 μm were found to be ∼7.5 × 10 -18 cm 2 and ∼4.5 × 10 -19 cm 2 , respectively.

ConspectusMolecular deposition on solid surfaces forms crystalline or amorphous/glassy thin solid films. Intermolecular interactions govern the packing and dynamics of these films. The connection between molecular structure and intermolecular interactions is based on understanding electrostatic forces, dispersion forces and hydrogen bonding. Recently, an entire class of dipolar molecular species have demonstrated counterintuitive self-organization such that the dipole moments of individual molecules are oriented in thin films. This leads to the spontaneous generation of polarized molecular films manifesting a polarization charge equivalent to tens to hundreds of volts in strength at the film-vacuum interface, relative to the film-substrate interface. These voltages, and the corresponding electric fields present in such films, result from a collective and spontaneous orientation of molecular dipoles throughout the film during film growth and represent a metastable state of polarized material. The existence of these materials should encourage reconsideration of the importance of solid-state intermolecular electrostatic interactions.This account will detail observations of the spontaneous electric fields in molecular solids, provide insights into the dynamics and structure of molecular materials that the emergence of these electric fields can facilitate, and present a dipole-alignment based mean-field model that reproduces the temperature dependence of the electric field strength. Species as diverse as carbon monoxide, nitrous oxide, freons, simple alcohols, and cis -methyl formate have been demonstrated to spontaneously generate electric fields. We have reported electric fields more than 10 8 V m -1 , have shown how field strength varies with the film deposition temperature, and have reported temperature-dependent Stark shifts observable in both infrared and ultraviolet absorption spectra. The latter has led to the reporting of large Wannier-Mott excitons in wide band gap molecular materials, such as solid carbon monoxide and ammonia.Changes in the field strength with time, at specific temperatures, can be related to the structural dynamics of glassy molecular solids. Measurement of surface potentials is a very sensitive technique by which to observe the rotation and translation of molecular species buried in thin films. This is particularly true for polarized, supercooled molecular glasses, where surface potentials have been used to report on secondary relaxation processes that have hitherto been hidden from measurement.Characterizing spontaneously electric molecular films, and understanding their behavior, requires the inclusion of nonlocal and nonlinear effects. The mean-field model that we present describes the data by connecting the energy of interaction of an average dipole with the mean effective field in the film, where this field is itself a function of the degree of polarization. This feedback loop produces a smooth function with a nonintuitive, discontinuous differential. The condensation of thin molecular films is an important means by which molecular solids are generated in the interstellar medium and represents a key pathway for the generation of organic optically and electrically active materials. It may also be possible to manipulate chemistry with the intense, localized electric fields acting as or acting on catalysts. The repercussions of the spontaneous generation of bound surface charges and the presence of electric fields in molecular solids will be discussed in these contexts.

The use of PPE has drastically increased because of the SARS-CoV-2 (COVID-19) pandemic as disposable surgical face masks made from non-biodegradable polypropylene (PP) polymers have generated a significant amount of waste. In this work, a low-power plasma method has been used to degrade surgical masks. Several analytical techniques (gravimetric analysis, scanning electron microscopy (SEM), attenuated total reflection-infra-red spectroscopy (ATR-IR), x-ray photoelectron spectroscopy (XPS), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) and wide-angle x-ray scattering (WAXS)) were used to evaluate the effects of plasma irradiation on mask samples. After 4 h of irradiation, an overall mass loss of 63 ± 8%, through oxidation followed by fragmentation, was observed on the non-woven 3-ply surgical mask, which is 20 times faster than degrading a bulk PP sample. Individual components of the mask also showed different degradation rates. Air plasma clearly represents an energy-efficient tool for treating contaminated PPE in an environmentally friendly approach., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

Spontaneous dipole orientation is studied for a set of simulated porous ASW ice films on a substrate held at temperatures ranging from 10 K to 140 K. It is found that the water dipoles in the films obtained at the lower temperatures are oriented such that a negative electric field with a magnitude of 10 8 -10 9 V m -1 is obtained. The magnitude of the field increases approximately linearly with height above the substrate, akin to experimental observations, although the magnitude of our field increases faster. A strong temperature dependence of the surface potential resulting from the spontelectric field is found, where the surface potential decreases when the substrate temperature increases. The surface potential finally becomes close to zero for temperatures around and above 110 K.

A reflection-absorption optical (RAO) spectrometer, operating across the ultra-violet/visible (UV/visible) wavelength region, has been developed that allows simultaneous measurements of optical properties and thickness of thin solid films at cryogenic temperatures in ultrahigh vacuum. The RAO spectrometer enables such measurements to be made after ice deposition, as opposed to most current approaches which make measurements during deposition. This allows changes in the optical properties and in the thickness of the film to be determined subsequent to thermal, photon or charged particle processing. This is not possible with current techniques. A data analysis method is presented that allows the wavelength dependent n and k values for ices to be extracted from the reflection-absorption spectra. The validity of this analysis method is shown using model data from the literature. New data are presented for the reflection UV/visible spectra of amorphous and crystalline single component ices of benzene, methyl formate and water adsorbed on a graphite surface. These data show that, for benzene and methyl formate, the crystalline ice has a larger refractive index than amorphous ice, reflecting changes in the electronic environment occurring in the ice during crystallisation. For water, the refractive index does not vary with ice phase.

Correction for 'Surface heterogeneity and inhomogeneous broadening of vibrational line profiles' by Skandar Taj et al., Phys. Chem. Chem. Phys., 2017, 19, 7990-7995.

Spontaneous orientation of molecular dipoles has been observed to produce bulk electric fields, termed 'spontelectric' fields, in a broad variety of molecular solid thin films formed by condensation from the gas phase. Such spontelectric fields are found in cis-methyl formate (cis-MF) and the present work combines observation of these fields with high quality ab initio studies of cis-MF monomers and dimers. This enables a prediction of the structural motif within the unit cell of the crystalline phase of solid cis-MF, showing it to be a non-polar dimer. Dimer formation at deposition temperatures of >90 K is therefore cited to contribute to the observed collapse of the spontelectric field at these temperatures. This is the first time that such a structural prediction has been made using observations of spontelectric behaviour as a key indicator.

We present a novel UV/visible reflection-absorption spectrometer for determining the refractive index, n, and thicknesses, d, of ice films. Knowledge of the refractive index of these films is of particular relevance to the astrochemical community, where they can be used to model radiative transfer and spectra of various regions of space. In order to make these models more accurate, values of n need to be recorded under astronomically relevant conditions, that is, under ultra-high vacuum (UHV) and cryogenic cooling. Several design considerations were taken into account to allow UHV compatibility combined with ease of use. The key design feature is a stainless steel rhombus coupled to an external linear drive (z-shift) allowing a variable reflection geometry to be achieved, which is necessary for our analysis. Test data for amorphous benzene ice are presented as a proof of concept, the film thickness, d, was found to vary linearly with surface exposure, and a value for n of 1.43 ± 0.07 was determined.

Temperature-programmed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS) are used to probe the effect of atomic and molecular oxygen (O and O 2 ) beams on amorphous silica (aSiO 2 ) and water (H 2 O) surfaces (porous-amorphous solid water; p-ASW, compact amorphous solid water; c-ASW, and crystalline solid water; CSW). Altering the deposition method of O 2 is shown to result in different desorption energies of O 2 due to differences in O 2 film morphology when deposited on the aSiO 2 surface. O 2 enthalpy of formation is dissipated into the aSiO 2 substrate without changes in the silica network. However, on the H 2 O surfaces, O 2 formation enthalpy release is dissipated into the H-bonded matrix leading to morphological changes, possibly compacting p-ASW into c-ASW while CSW appears to undergo amorphisation. The enthalpy release from O 2 formation is, however, not enough to result in reactive desorption of O 2 or H 2 O under the current experimental circumstances. Further to this, O 2 formation on sub-monolayer quantities of H 2 O leads to enhanced de-wetting and a greater degree of H-bond reconnection in H 2 O agglomerates. Lastly, O 3 is observed from the O + O 2 reaction on all surfaces studied.

Using reflection-absorption infrared spectroscopy (RAIRS), we show that solids displaying spontaneous dipole orientation possess quite general non-local and non-linear characteristics, exemplified through their internal electric fields. The most graphic illustration of this, uncovered originally through electron beam studies, may be found in films of cis-methyl formate (cis-MF), for which data demonstrated the counter-intuitive property that the degree of dipole order in the film does not monotonically decrease as the temperature of deposition rises, but rather increases sharply above ∼77 K. Here we show how RAIRS provides independent evidence to support this conclusion. These new data confirm (i) that the behaviour of spontelectrics is governed by an expression for the degree of dipole orientation, which is continuous in temperature, but with a discontinuity in the derivative, and (ii) that the temperature of deposition associated with this discontinuity matches the temperature above which dipole order switches from the expected reduction with temperature to an increase with temperature.

The absorption of light to create Wannier-Mott excitons is a fundamental feature dictating the optical and photovoltaic properties of low band gap, high permittivity semiconductors. Such excitons, with an electron-hole separation an order of magnitude greater than lattice dimensions, are largely limited to these semiconductors but here we find evidence of Wannier-Mott exciton formation in solid carbon monoxide (CO) with a band gap of >8  eV and a low electrical permittivity. This is established through the observation that a change of a few degrees K in deposition temperature can shift the electronic absorption spectra of solid CO by several hundred wave numbers, coupled with the recent discovery that deposition of CO leads to the spontaneous formation of electric fields within the film. These so-called spontelectric fields, here approaching 4×10^{7}  V m^{-1}, are strongly temperature dependent. We find that a simple electrostatic model reproduces the observed temperature dependent spectral shifts based on the Stark effect on a hole and electron residing several nm apart, identifying the presence of Wannier-Mott excitons. The spontelectric effect in CO simultaneously explains the long-standing enigma of the sensitivity of vacuum ultraviolet spectra to the deposition temperature.

The control of drinking water quality is critical in preventing fluorosis. In this study humic substances (HS) are considered as representative of natural organic matter (NOM) in water. We show that when HS aggregate the response of fluoride ion selective electrodes (ISE) may be perturbed. Dynamic light scattering (DLS) results of both synthetic solutions and natural water sample suggest that low pH and high ionic strength induce HS aggregation. In the presence of HS aggregates, fluoride concentration measured by ISE has a reduction up to 19%. A new "open cage" concept has been developed to explain this reversible phenomenon. The interference of HS aggregation on fluoride measurement can be effectively removed by centrifugation pretreatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)