Water dimer in solid neon. Far-infrared spectrum

Infrared spectra of water and deuterated water isolated in neon matrices have been recorded between 20 and 5000 cm(-1). The water concentration has been varied between very low concentrations with only monomers present up to concentrations where pentamers and possibly hexamers are present in significant amounts. The concentration dependencies of the observed absorption bands have been used to assign the dimer spectrum. The matrices studied were on the order of 1 mm thick, which has made it simpler to vary concentrations in a manner which discriminates between higher aggregates. It has also made it possible to avoid the baseline problems which appear when the matrices are only slightly thicker than the wavelengths in the far-infrared part of the spectrum

Far-Infrared Band Strengths in the Water Dimer: Experiments and Calculations.

Most fundamentals modes of the water dimer have been experimentally determined, and the frequencies have been measured in either neon or parahydrogen matrices. The band strengths of all intramolecular and most intermolecular fundamentals of the water dimer have been measured. The results are further corroborated by comparison with the corresponding data for the fully deuterated water dimer. DFT calculations of the mode frequencies and band strength are in qualitative agreement with the experimental observations

CONFORMATIONAL ANALYSIS OF 1-ALKENE SECONDARY OZONIDES BY MEANS OF MATRIX ISOLATION FTIR SPECTROSCOPY

Author Institution: Dept. of General Physics and Spectroscopy, Faculty of Physics, Vilnius University, Sauletekio av. 9 bl. 3, LT-01222, Vilnius, LithuaniaAn ability of ozone to break double C=C bond in olefins is known for more than five decades. Understanding of those reactions is very important in atmospheric chemistry. During different steps of the reaction the primary ozonide (POZ), carbonyl oxide (COX) and the secondary ozonide (SOZ) are formed. Fate of the reaction depends on many parameters such as type of radical, conformation of alkene, temperature of the reaction and environmental effects. Despite of numerous studies of the reaction by different spectroscopic techniques the precise mechanism of the reaction is still unknown. It is experimentally observed that the SOZ is more stable than POZ. Stability of the SOZ depends on the size and configuration of the radical. Unfortunately, it is not much known about the spatial structures of the SOZ es. The aim of this study is to define the geometrical structures and stability of the different conformers of the 1-butene and 1-heptene secondary ozonides by combined analysis of the matrix isolation FTIR spectral data with the results of Density Functional Theory (DFT) calculations

Intermolecular vibrations of the water trimer, a matrix isolation study

Infrared spectra from 25 to 4000 cm(-1) have been recorded of water (H2O, D2O and (H2O)-O-18) matrix isolated in neon, argon, and krypton matrices. Intermolecular absorption bands of different isotopologues of the water trimer and tetramer have been assigned from concentration dependencies and diffusion behavior, using the well-known mid-infrared trimer and tetramer absorption bands as measures of the trimer and tetramer concentrations. The results are compared to ab initio calculations

Microplastics Release from Conventional Plastics during Real Open Windrow Composting

The recycling of bio-waste plays an important role in a circular economy as it transforms bio-waste into a valuable resource (organic fertilizer). However, even separately collected bio-waste can contain some plastic waste, which is usually separated after composting and not before it. Primary studies have confirmed the degradation of plastic during composting, but the release of microplastics from them has not been studied. This article presents a quantification and comparison of the release of microplastics from commonly used plastics during green waste composting. Microplastics were identified by Nile red staining and examination under a fluorescent microscope. Plastic degradation was assessed by weight loss calculation, scanning electron microscope (SEM), and Fourier-transform infrared spectroscopy (FTIR) analysis. On average, 17 to 52 microplastics’ are released from 5-by-5 cm pieces of conventional plastics during composting. The control polylactic acid sample showed the smallest amount of released microplastics: four particles on average. The number of released microplastics depended on the polymer type and thickness of the samples. The results of the current article can be further used for the prediction of microplastic generation and setting a limit on the plastic content in bio-wast

Microplastics release from conventional plastics during real open windrow composting /

The recycling of bio-waste plays an important role in a circular economy as it transforms bio-waste into a valuable resource (organic fertilizer). However, even separately collected bio-waste can contain some plastic waste, which is usually separated after composting and not before it. Primary studies have confirmed the degradation of plastic during composting, but the release of microplastics from them has not been studied. This article presents a quantification and comparison of the release of microplastics from commonly used plastics during green waste composting. Microplastics were identified by Nile red staining and examination under a fluorescent microscope. Plastic degradation was assessed by weight loss calculation, scanning electron microscope (SEM), and Fourier-transform infrared spectroscopy (FTIR) analysis. On average, 17 to 52 microplastics’ are released from 5-by-5 cm pieces of conventional plastics during composting. The control polylactic acid sample showed the smallest amount of released microplastics: four particles on average. The number of released microplastics depended on the polymer type and thickness of the samples. The results of the current article can be further used for the prediction of microplastic generation and setting a limit on the plastic content in bio-waste

Hidden Isomer of Trifluoroacetylacetone Revealed by Matrix Isolation Infrared and Raman Spectroscopy

International audienceEnol forms of trifluoroacetylacetone (TFacac) isolated in molecular and rare gas matrices were studied using infrared (IR) and Raman spectroscopy. Additionally, calculations using DFT B3LYP and M06-2X as well as MP2 methods were performed in order to investigate the possibility of coexistence of more than one stable enol form isomer of TFacac. Calculations predict that both stable enol isomers of TFacac, 1,1,1-trifluoro-4-hydroxy-3-penten-2-one (1) and 5,5,5-trifluoro-4-hydroxy-3-penten-2-one (2), could coexist, especially in matrices where the room temperature population is frozen, 1 being the most stable one. Raman and IR spectra of TFacac isolated in nitrogen (N2) and carbon monoxide (CO) matrices exhibit clear absorption bands, which cannot be attributed to this single isomer. Their relative band positions and intensity profiles match well with the theoretical calculations of 2.This allows us to confirm that in N2 and CO matrices both isomers exist in similar amounts. Careful examination of the spectra of TFacac in argon, xenon, neon, normal, and para-hydrogen (Ar, Xe, Ne, nH2, and pH2 respectively) matrices revealed that both isomers coexist in all the explored matrices, whereas 2 was not considered in the previous spectroscopic works. The amount of the second isomer (2) in the as-deposited samples depends on the host. The analysis of TFacac spectra in the different hosts and under various experimental conditions allows the vibrational characterization of both chelated isomers. The comparison with theoretical predictions is also investigated

Revisiting photoisomerization in fluorinated analogues of acetylacetone trapped in cryogenic matrices

UV-induced processes are commonly studied in acetylacetone analogues. In this contribution, we revisit the existing work on the photoisomerization process in some of the fluorinated analogues of acetylacetone, i.e., trifluoroacetylacetone (F3-acac) and hexafluoroacetylacetone (F6-acac). We performed selective UV laser excitation of these molecules trapped in soft cryogenic matrices, namely neon and para-hydrogen, and probed by vibrational spectroscopy. Clear spectroscopy of 3 isomers of F6-acac and 6 isomers of F3-acac is obtained, including the first characterization of a second open enol isomer of hexafluoroacetylacetone. In addition, we present the electronic absorption spectra of both molecules in cryogenic matrices before and after specific UV irradiations, giving new data on the electronic transitions of photoproducts. Vibrational and electronic experimental results are analyzed and discussed within comparisons with DFT and TD-DFT calculations. Our findings contribute to a deeper understanding of the photoisomerization process in these molecules after electronic excitation in gas and condensed phase

Intramolecular hydrogen tunneling in 2-chloromalonaldehyde trapped in solid para -hydrogen

International audienceInternal dynamics of 2-chloromalonaldehyde (2-ClMA) molecule, possessing strong internal hydrogen bond (IHB) was examined by means of matrix isolation spectroscopy in a soft host: para-hydrogen (pH2). 2-ClMA is a chlorinated derivative of malonaldehyde (MA), a model molecule in hydrogen transfer studies, better suited to low temperature experiments than its parent molecule. The infrared absorption spectra of 2-ClMA isolated in pH2 exhibit temperature dependent structures which are explained as transitions occurring from split vibrational levels induced by hydrogen tunneling. The doublet components associated with higher and lower energy levels are changing reversibly with the increase/decrease of the matrix temperature. The ground state splitting is measured to 7.90.1 cm-1. The presence of oH2 impurities in pH2 matrix close to the neighborhood of the 2-ClMA molecule is found to quench the H tunneling. The data provide a powerful insight into the dynamical picture of intramolecular hydrogen tunneling in a molecule embedded in a very weakly perturbing environment