On the origins of core-electron chemical shifts of small biomolecules in aqueous solution: insights from photoemission and ab initio calculations of glycine(aq).

The local electronic structure of glycine in neutral, basic, and acidic aqueous solution is studied experimentally by X-ray photoelectron spectroscopy and theoretically by molecular dynamics simulations accompanied by first-principle electronic structure and spectrum calculations. Measured and computed nitrogen and carbon 1s binding energies are assigned to different local atomic environments, which are shown to be sensitive to the protonation/deprotonation of the amino and carboxyl functional groups at different pH values. We report the first accurate computation of core-level chemical shifts of an aqueous solute in various protonation states and explicitly show how the distributions of photoelectron binding energies (core-level peak widths) are related to the details of the hydrogen bond configurations, i.e. the geometries of the water solvation shell and the associated electronic screening. The comparison between the experiments and calculations further enables the separation of protonation-induced (covalent) and solvent-induced (electrostatic) screening contributions to the chemical shifts in the aqueous phase. The present core-level line shape analysis facilitates an accurate interpretation of photoelectron spectra from larger biomolecular solutes than glycine.

Auger electron spectroscopy as a probe of the solution of aqueous ions.

Aqueous potassium chloride has been studied by synchrotron-radiation excited core-level photoelectron and Auger electron spectroscopy. In the Auger spectrum of the potassium ion, the main feature comprises the final states where two outer valence holes are localized on potassium. This spectrum exhibits also another feature at a higher kinetic energy which is related to final states where outer valence holes reside on different subunits. Through ab initio calculations for microsolvated clusters, these subunits have been assigned as potassium ions and the surrounding water molecules. The situation is more complicated in the Auger spectrum of the chloride anion. One-center and multicenter final states are present here as well but overlap energetically.

Electronic rearrangement upon the hydrolyzation of aqueous formaldehyde studied by core-electron spectroscopies.

We have combined near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) to study the electronic rearrangement associated with the hydrolyzation of formaldehyde to methanediol in aqueous solution. The spectra are contrasted against those of aqueous formamide and urea, which are structurally similar but do not undergo hydrolysis in solution. We have recently demonstrated that the hydrolyzation of formaldehyde is manifested in the oxygen 1s NEXAFS spectrum by the disappearance of the oxygen 1s --> pi* absorption line. This is a characteristic signature that the C=O double bond has been broken. In the present study we extend our investigation to include carbon 1s NEXAFS and XPS spectra of the three solutions. The carbon NEXAFS spectra show the C 1s --> pi* absorption line for each solute except for formaldehyde. Moreover, the carbon 1s photoelectron spectra exhibit a single peak for each solute. These observations point to a near complete hydrolyzation of formaldehyde, whereas formamide and urea remain intact in the solution. The analysis is further supported by density functional theory (DFT) calculations, showing a C 1s chemical shift of approximately 1.0 eV between hydrolyzed and nonhydrolyzed forms, which would give distinguishable features in the photoemission spectrum, if coexisting forms were present in the solutions.

Fluorine as a pi donor. Carbon 1s photoelectron spectroscopy and proton affinities of fluorobenzenes.

The carbon 1s ionization energies for all of the carbon atoms in 10 fluorine-substituted benzene molecules have been measured by high-resolution photoelectron spectroscopy. A total of 30 ionization energies can be accurately described by an additivity model with four parameters that describe the effect of a fluorine that is ipso, ortho, meta, or para to the site of ionization. A similar additivity relationship describes the enthalpies of protonation. The additivity parameters reflect the role of fluorine as an electron-withdrawing group and as a pi-electron donating group. The ionization energies and proton affinities correlate linearly, but there are four different correlations depending on whether there are 0, 1, 2, or 3 fluorines ortho or para to the site of ionization or protonation. That there are four correlation lines can be understood in terms of the ability of the hydrogens at the site of protonation to act as a pi-electron acceptor. A comparison of the ionization energies and proton affinities, together with the results of electronic structure calculations, gives insight into the effects of fluorine as an electron-withdrawing group and as a pi donor, both in the neutral molecule and in response to an added positive charge.