On the Influence of Corpuscular Fluxes and of Electron Photoloosening Reaction on the Formation of the D-Layer of the Ionosphere

Effect of corpuscular fluxes and electron photoloosening reaction on formation of ionospheric D laye

Enabling liquid vapor analysis using synchrotron VUV single photon ionization mass spectrometry with a microfluidic interface.

Vacuum ultraviolet (VUV) single photon ionization mass spectrometry (SPI-MS) is a vacuum-based technique typically used for the analysis of gas phase and solid samples, but not for liquids due to the challenge in introducing volatile liquids in a vacuum. Here we present the first demonstration of in situ liquid analysis by integrating the System for Analysis at the Liquid Vacuum Interface (SALVI) microfluidic reactor into VUV SPI-MS. Four representative volatile organic compound (VOC) solutions were used to illustrate the feasibility of liquid analysis. Our results show the accurate mass identification of the VOC molecules and the reliable determination of appearance energy that is consistent with ionization energy for gaseous species in the literature as reported. This work validates that the vacuum-compatible SALVI microfluidic interface can be utilized at the synchrotron beamline and enable the in situ study of gas-phase molecules evaporating off the surface of a liquid, which holds importance in the study of condensed matter chemistry

Velocity map imaging of inelastic and elastic low energy electron scattering in organic nanoparticles.

Electron transport is of fundamental importance and has application in a variety of fields. Different scattering mechanisms affect electron transport in the condensed phase; hence, it is important to comprehensively understand these mechanisms and their scattering cross sections to predict electron transport properties. Whereas electron transport is well understood for high kinetic energy (KE) electrons, there is a discrepancy in the experimental and theoretical values for the Inelastic Mean Free Path (IMFP) in the low KE regime. In this work, velocity map imaging soft X-ray photoelectron spectroscopy is applied to unsupported organic nanoparticles (squalene) to extract experimental values of inelastic and elastic mean free paths (EMFPs). The obtained data are used to calculate corresponding scattering cross sections. The data demonstrate a decrease in the IMFP and increase in the EMFP with increasing electron KE between 10 and 50 eV

To Be or Not To Be a Molecular Ion: The Role of the Solvent in Photoionization of Arginine.

Application of photoionization mass spectroscopy, a technique capable of assessing protonation states in complex molecules in the gas phase, is challenging for arginine due to its fragility. We report photoionization efficiencies in the valence region of aqueous aerosol particles produced from arginine solutions under various pH and vaporization conditions. By using ab initio calculations, we investigate the stability of different conformers. Our results show that neutral arginine fragments upon ionization in the gas phase but solvation stabilizes the molecular ion, resulting in different photoionization dynamics. We also report the valence-band photoelectron spectra of the aerosol solutions obtained at different pH values

Watson–Crick and Sugar-Edge Base Pairing of Cytosine in the Gas Phase: UV and Infrared Spectra of Cytosine·2-Pyridone

While keto-amino cytosine is the dominant species in aqueous solution, spectroscopic studies in molecular beams and in noble gas matrices show that other cytosine tautomers prevail in apolar environments. Each of these offers two or three H-bonding sites (Watson–Crick, wobble, sugar-edge). The mass- and isomer-specific S1 ← S0 vibronic spectra of cytosine·2-pyridone (Cyt·2PY) and 1-methylcytosine·2PY are measured using UV laser resonant two-photon ionization (R2PI), UV/UV depletion, and IR depletion spectroscopy. The UV spectra of the Watson–Crick and sugar-edge isomers of Cyt·2PY are separated using UV/UV spectral hole-burning. Five different isomers of Cyt·2PY are observed in a supersonic beam. We show that the Watson–Crick and sugar-edge dimers of keto-amino cytosine with 2PY are the most abundant in the beam, although keto-amino-cytosine is only the third most abundant tautomer in the gas phase. We identify the different isomers by combining three different diagnostic tools: (1) methylation of the cytosine N1–H group prevents formation of both the sugar-edge and wobble isomers and gives the Watson–Crick isomer exclusively. (2) The calculated ground state binding and dissociation energies, relative gas-phase abundances, excitation and the ionization energies are in agreement with the assignment of the dominant Cyt·2PY isomers to the Watson–Crick and sugar-edge complexes of keto-amino cytosine. (3) The comparison of calculated ground state vibrational frequencies to the experimental IR spectra in the carbonyl stretch and NH/OH/CH stretch ranges strengthen this identification