Experimental and theoretical soft x-ray study of nicotine and related compounds

The valence and core electronic structure of nicotine, nicotinic acid, and nicotinamide have been studied by photoelectron and soft X-ray absorption spectroscopy, supported by theoretical calculations, which take into account conformational isomerism. The core-level photoionization spectra of all molecules have been assigned, and theory indicates that the effects of conformational differences are small, generally less than the natural line widths of the core ionic states. However, in the case of nicotinamide, the theoretical valence ionization potentials of cis and trans conformers differ significantly in the outer valence space, and the experimental spectrum is in agreement with the calculated outer valence cis conformer spectrum. In addition, the C, N, and O K edge near-edge absorption fine structure spectra are reported and interpreted by comparison with reference compounds. We find evidence at the N and O K edges of interaction between the delocalized orbitals of the pyridine ring and the substituents for nicotinic acid and nicotinamide. The strength of the interaction varies because the first is planar, while the second is twisted, reducing the extent of orbital mixing

An experimental and theoretical investigation of XPS and NEXAFS of nicotine, nicotinamide, and nicotinc acid

The electronic structures of nicotine, nicotinic acid and nicotinamide have been studied by valence photoemission spectroscopy (PES), core X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) and interpreted with the aid of quantum chemical calculations. Nicotinamide and nicotinic acid are closely related and show correspondingly similar spectral features, while nicotine is both structurally and spectroscopically diverse

Quantification and speciation of lead in air particulate matter collected from an urban area in Amman, Jordan

Lead (Pb) is a carcinogenic element, and it originates in the atmosphere from various natural and anthropogenic sources. This work aims to provide further insights about the presence of lead in Amman's atmosphere. Air particulate matter (PM) samples were collected in two fractions (PM2.5 and PM10) simultaneously on Teflon filters in an urban area in Amman, Jordan. Elemental quantification and chemical speciation of Pb were performed using particle-induced X-ray emission (PIXE) and X-ray absorption near-edge structure (XANES) techniques, respectively. Elemental quantitative analysis using PIXE showed that Pb concentrations increased during workdays regardless of the aerosol particle size fraction. The average Pb concentration was 2.9 ± 1.7 ng/m3 and 3.9 ± 2.0 ng/m3 in PM2.5 and PM10, respectively. Based on XANES measurements, it was shown that both PM2.5 and PM10 in Amman contain divalent lead (Pb (II)), most likely as PbSO4, PbS and PbO compounds

Chlorination and tautomerism: A computational and UPS/XPS study of 2-hydroxypyridine \u21cc 2-pyridone equilibrium

The prototropic tautomeric equilibrium in 2-hydroxypyridine serves as a prototype model for the study of nucleobases' behaviour. The position of such an equilibrium in parent and chlorine monosubstituted 2-hydroxypyridine compounds in the gas phase was determined using synchrotron based techniques. The lactim tautomer is dominant for the 5- and 6-substituted compounds, whereas the parent, 3- and 4-substituted isomers have comparable populations for both tautomers. Information was obtained by measuring valence band and core level photoemission spectra at the chlorine L-edge and carbon, nitrogen, and oxygen K-edges. The effect of chlorine on the core ionization potentials of the atoms in the heterocycle was evaluated and reasonable agreement with a simple model was obtained. Basic considerations of resonance structures correctly predicts the tautomeric equilibrium for the 5- and 6-substituted compounds. The vibrationally resolved structure of the low energy portion of the valence band photoionization spectra is assigned based on quantum-chemical calculations of the neutral and charged species followed by simulation of the vibronic structure. It is shown that the first ionization occurs from a \u3c0 orbital of similar shape for both tautomers. In addition, the highly distinctive vibronic structure observed just above the first ionization of the lactim, for three of the five species investigated, is assigned to the second ionization of the lactam. This journal i

Experimental and Theoretical Photoemission Study of Indole and Its Derivatives in the Gas Phase

The valence and core-level photoelectron spectra of gaseous indole, 2,3-dihydro-7-azaindole, and 3-formylindole have been investigated using VUV and soft X-ray radiation supported by both an ab initio electron propagator and density functional theory calculations. Three methods were used to calculate the outer valence band photoemission spectra: Outer valence Green function, partial third order, and renormalized partial third order. While all gave an acceptable description of the valence spectra, the last method yielded very accurate agreement, especially for indole and 3-formylindole. The carbon, nitrogen, and oxygen 1s core-level spectra of these heterocycles were measured and assigned. The double ionization appearance potential for indole has been determined to be 21.8 \ub1 0.2 eV by C 1s and N 1s Auger photoelectron spectroscopy. Theoretical analysis identifies the doubly ionized states as a band consisting of two overlapping singlet states and one triplet state with dominant configurations corresponding to holes in the two uppermost molecular orbitals. One of the singlet states and the triplet state can be described as consisting largely of a single configuration, but other doubly ionized states are heavily mixed by configuration interactions. This work provides full assignment of the relative binding energies of the core level features and an analysis of the electronic structure of substituted indoles in comparison with the parent indole