Gas-phase study on uridine: Conformation and X-ray photofragmentation

Fragmentation of RNA nucleoside uridine, induced by carbon 1s core ionization, has been studied. The measurements by combined electron and ion spectroscopy have been performed in gas phase utilizing synchrotron radiation. As uridine is a combination of d-ribose and uracil, which have been studied earlier with the same method, this study also considers the effect of chemical environment and the relevant functional groups. Furthermore, since in core ionization the initial core hole is always highly localized, charge migration prior to fragmentation has been studied here. This study also demonstrates the destructive nature of core ionization as in most cases the C 1s ionization of uridine leads to concerted explosions producing only small fragments with masses ≤43 amu. In addition to fragmentation patterns, we found out that upon evaporation the sugar part of the uridine molecule attains hexagonal formFinancial support from the Academy of Finland, the European COST Action XLIC CM1204 and the EU Transnational Access to Research Infrastructures programme. Computational resources from the FGI project (Finland) are acknowledged. D.T.H. acknowledges the Finnish Cultural Foundation for funding and the MINECO Project No. FIS2013-42002- R. E.R. acknowledges funding from the Swedish Research Council (VR

Solvothermal synthesis derived Co-Ga codoped ZnO diluted magnetic degenerated semiconductor nanocrystals

Authors kindly acknowledge to the Estonian Research Council ( PUT1096 , IUT2-25 , PUT735 ), the Estonian Centre of Excellence in Research project “Advanced materials and high-technology devices for sustainable energetics, sensorics and nanoelectronics (TK141), and the financial support of HZB. We are grateful to the staff of BESSY II for the assistance and co-operation during the synchrotron-based measurements.Here we are reporting solvothermal synthesis derived diluted magnetic and plasmonic Co-Ga co-doped ZnO nanocrystals with high magnetization values (from 1.02 to 4.88 emu/g) at room temperature. Co-Ga co-doped ZnO nanocrystals show up to 2 fold increase in saturation magnetization compared to Co doped ZnO nanocrystals at the same Co concentration, with the observed room temperature magnetization higher than previously reported values for multifunctional magnetic and plasmonic nanocrystals, and the effect of Ga suggesting some role of the correspondingly introduced itinerant charge. While at the lowest Ga content the nanoparticles appear homogeneously doped, we note that already a moderate Ga content of several percent triggers a fraction of Co to segregate in metallic form in the bulk of the nanoparticles. However, the amount of segregated Co is not sufficient to account for the total effect, whereas a dominating contribution to the observed magnetism has to be related to itinerant charge mediated exchange interactions.Eesti Teadusagentuur IUT2-25,PUT1096,PUT735; Estonian Centre of Excellence in Research TK141; HZB; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Facile synthesis of magnetically separable CoFe2O4/Ag2O/Ag2CO3 nanoheterostructures with high photocatalytic performance under visible light and enhanced stability against photodegradation

Riga Technical University supported the preparation of this manuscript from the Scientific Research Project Competition for Young Researchers No. ZP-2016/7. The authors wish to kindly acknowledge the financial support of HZB, Estonian Research Council (PUT1096, PUT735 and IUT2-25) and Estonian Centre of Excellence in Research Project “Advanced materials and high-technology devices for sustain-able energetics, sensorics and nanoelectronics” TK141 (2014–2020.4.01.15-0011).We have developed magnetically separable and reasonably stable visible light active photocatalysts containing CoFe2O4 and mixture of Ag2O/Ag2CO3 nanoheterostructures. Obtained ternary nanoheterostructures outperform previously reported magnetically separable visible light photocatalysts, showing one of the highest visible light photocatalytic dye degradation activities in water by a magnetically separable photocatalyst. Photocatalytically active part is Ag2O/Ag2CO3 whereas the CoFe2O4 mainly has stabilizing and magnetic separation functions. The Ag2CO3 phase junction on Ag2O nanoparticle surface were obtained by straightforward phase transformation from silver oxide to silver carbonate in air due to ambient CO2. The phase transformation was followed using X-ray diffraction (XRD), and hard X-ray photoelectron spectroscopy (HAXPES) measurements.Riga Technical University No. ZP-2016/7; Estonian Research Council (PUT1096, PUT735 and IUT2-25); Estonian Centre of Excellence in Research TK141 (2014–2020.4.01.15-0011); Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

Density functional simulation of resonant inelastic X-ray scattering experiments in liquids : acetonitrile

In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.In this paper we report an experimental and computational study of liquid acetonitrile (H3C-C equivalent to N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C-C equivalent to NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.Peer reviewe

Gas-phase endstation of electron, ion and coincidence spectroscopies for diluted samples at the FinEstBeAMS beamline of the MAXIV 1.5GeV storage ring

Since spring 2019 an experimental setup consisting of an electron spectrometer and an ion time-of-flight mass spectrometer for diluted samples has been available for users at the FinEstBeAMS beamline of the MAXIV Laboratory in Lund, Sweden. The setup enables users to study the interaction of atoms, molecules, (molecular) microclusters and nanoparticles with short-wavelength (vacuum ultraviolet and X-ray) synchrotron radiation and to follow the electron and nuclear dynamics induced by this interaction. Test measurements of N-2 and thiophene (C4H4S) molecules have demonstrated that the setup can be used for many-particle coincidence spectroscopy. The measurements of the Ar3p photoelectron spectra by linear horizontal and vertical polarization show that angle-resolved experiments can also be performed. The possibility to compare the electron spectroscopic results of diluted samples with solid targets in the case of Co2O3 and Fe2O3 at the Co and Fe L-2,L-3-absorption edges in the same experimental session is also demonstrated. Because the photon energy range of the FinEstBeAMS beamline extends from 4.4eV up to 1000eV, electron, ion and coincidence spectroscopy studies can be executed in a very broad photon energy range

Ionization-site effects on the photofragmentation of chloro- and bromoacetic acid molecules

Fragmentation of gas-phase chloro- and bromoacetic acid samples, particularly its dependency on the atomic site of the initial core ionization, was studied in photoelectron-photoion-photoion coincidence (PEPIPICO) measurements. The fragmentation was investigated after ionizing carbon 1s and bromine 3d or chlorine 2p core orbitals. It was observed that the samples had many similar fragmentation pathways and that their relative weights depended strongly on the initial ionization site. Additional Auger PEPIPICO measurements revealed a clear dependence of fragment pair intensities on the kinetic energy of the emitted Auger electrons. The modeled and measured Auger electron spectra indicated that the average internal energy of the molecule was larger following the carbon 1s core-hole decay than after the decay of the halogen core hole. This difference in the internal energies was found to be the source of the site-dependent photofragmentation behavior.</p

Internal energy dependence in x-ray-induced molecular fragmentation: An experimental and theoretical study of thiophene

A detailed experimental and theoretical investigation of the dynamics leading to fragmentation of doubly ionized molecular thiophene is presented. Dissociation of double-ionized molecules was induced by S 2p core photoionization and the ionic fragments were detected in coincidence with Auger electrons from the core-hole decay. Rich molecular dynamics was observed in electron-ion-ion coincidence maps exhibiting ring breaks accompanied by hydrogen losses and/or migration. The probabilities of various dissociation channels were seen to be very sensitive to the internal energy of the molecule. Theoretical simulations were performed by using the semiempirical self-consistent charge-density-functional tight-binding method. By running thousands of these simulations, the initial conditions encountered in the experiment were properly taken into account, including the systematic dependencies on the internal (thermal) energy. This systematic approach, not affordable with first-principle methods, provides a good overall description of the complex molecular dynamics observed in the experiment and shows good promise for applicability to larger molecules or clusters, thus opening the door to systematic investigations of complex dynamical processes occurring in radiation damageThis work was supported by a grant of the Academy of Finland, Finnish Cultural Foundation, MICINN Project No. FIS2010-15127 and ERA-Chemistry Project No. PIM2010EEC-00751, the MINECO Projects No. FIS2013- 42002-R and No. CTQ2013-43698-P, the European COST Action No. CM1204 XLIC, an Advanced Grant of the European Research Council XCHEM No. 290853, the CAM Project NANOFRONTMAG, and the European Grant MCITN CORIN

Molecular dynamics of photodissociation: towards more complex systems

We present a combined experimental and theoretical study of the photodissociation of thiophene mole-cule using energy-resolved electron-ion-ion coincidence technique and self-consistent charge density functional tight-binding theory combined with a statistical approach. The observed complex molecular dynamics with many internal-energy-dependent fragmentation pathways is successfully described by the theoretical simulation