Photoelectron angular distributions (PADs) from the liquid-water surface and from bulk liquid water are reported for water oxygen-1s ionization. Although less so than for the gas phase, the measured PADs from the liquid are remarkably anisotropic, even at electron kinetic energies lower than 100 eV, when elastic scattering cross sections for the outgoing electrons with other water molecules are large. The PADs reveal that theoretical estimates of the inelastic mean free path are likely too long at low kinetic energies, and hence the electron probing depth in water, near threshold ionization, appears to be considerably smaller than so far assumed.

The effect of hydration on the lowest vertical ionization energy (VIE) of phenol and phenolate solvated in bulk water was characterized using the equation-of-motion ionization potential coupled-cluster (EOM-IP-CCSD) and effective fragment potential (EFP) methods (referred to as EOM/EFP), and determined experimentally by valence photo-emission measurements using microjets and synchrotron radiation. The computed solvent-induced shifts in VIEs (ΔVIE) are −0.66 eV and +5.72 eV for phenol and phenolate, respectively. Our best estimates of the absolute values of VIEs (7.9 and 7.7 eV for phenol and phenolate) agree reasonably well with the respective experimental values (7.8±0.1 eV and 7.1±0.1 eV). The EOM/EFP scheme was benchmarked against full EOM-IP-CCSD using micro-solvated phenol and phenolate clusters. A protocol for calculating redox potentials with EOM/EFP was developed based on linear response approximation (LRA) of free energy determination. The oxidation potentials of phenol and phenolate calculated using LRA and EOM/EFP are 1.32 V and 0.89 V, respectively; they agree well with experimental values.

Identifying the initial products of the interaction of high-energy radiation with liquidwater is essential for understanding the yield and patterns of damage in aqueous condensed matter, including biological systems. Up until now several fast reactions induced by energetic particles in water could not be observed on their characteristic timescales, and hence some of the reaction intermediates involved, particularly those requiring nuclear motion, have not been considered in describing radiation chemistry.Here, through a combined experimental and theoretical study, we elucidate the ultrafast proton dynamics in the first few femtoseconds after X-ray core-level ionization of liquid water. We show through isotope analysis of the Auger-spectra that proton-transfer dynamics occurs on the same timescale as electron autoionization. Proton transfer leads to formation of a Zundel-type intermediate [HO*··H··OH 2 ] + , which further ionizes, forming a so-far unnoticed type of di-cationic, charge-separated species with high internal energy. We call the process proton-transfer mediated charge separation.The primary processes in water initiated by X-radiation are poorly understood despite their paramount importance in different fields. Understanding the energy and charge redistribution in water upon X-ray photon absorption is vital for a design of more efficient radio-oncology schemes, 1-2 for disentangling the physical basis of genotoxic effects on living tissues, [3][4][5] for minimizing the damage of biological samples during X-ray diffraction 2 experiments, 6 as well as for controlling the performance of nuclear reactors under operating conditions. 7 Current understanding of electron-initiated processes in aqueous systems, following energy deposition, and the subsequent radical chemistry have been recently reviewed. 8 An explicit consideration of radicals and molecular species formed via multiple ionization processes of water, involving for instance atomic oxygen and hydrogen peroxide, can be found in the radiolysis literature, e.g. in refs. 7,9 However, the knowledge of the ultrafast processes and mechanisms in water radiolysis remains to large extent unexplored.In the present work we focus on the processes following O1s core-level ionization of water. The highly excited species formed by the core ionization relaxes primarily via Augerelectron decay. As shown in Figure 1b, Auger decay of a water molecule involves refilling the water core-hole by one of the valence electrons, and the simultaneous emission of another valence electron, the Auger electron, from the same water molecule. The resulting highly reactive doubly ionized H 2 O 2+ (aq) molecule, with both vacancies (holes) located at the same site (denoted here as 2h state), then undergoes ultrafast Coulomb explosion, forming dominantly O + 2H + . [10][11] In recent years a set of novel non-local autoionization processes has been identified to play an important role in weakly bonded atomic and molecular systems. [12][13][14] One such relaxation process is Intermolecu...

Photoelectron spectroscopy and density functional molecular dynamics simulations are combined to quantify and characterize the redox properties of Ru(bpy)32+/3+ and Ru(H2O)62+/3+ in aqueous solution. We report the energy-resolved photoelectron spectrum of aqueous Ru(bpy)32+ at 200 eV photon energy. From the peak position of the highest molecular orbital at 6.81 eV, an experimental value for the single-ion reorganization free energy of Ru(bpy)33+ is determined to be 1.21 +/- 0.04 eV. Density functional molecular dynamics calculations give a value of 0.84-1.20 eV for Ru(bpy)33+ and 1.92-2.42 eV for Ru(H2O)63+ depending on the method used to extrapolate the results to the infinite dilution limit. Since linear response is an excellent approximation for these systems, we report the same reorganization free energies for the divalent ions. The relatively small reorganization free energy of Ru(bpy)33+ is a consequence of the small changes in the Ru-N bond lengths upon reduction (0.04 eV inner sphere contribution) and of the large hydrophobic cavity formed by the bulky bipyridine ligands, which effectively reduces the dipolar response of the solvent in qualitative agreement with continuum theory. The large difference in redox potential between Ru(bpy)32+/3+ and Ru(H2O)62+/3+ (1 eV) is mainly associated with the difference in reorganization free energy rather than vertical ionization energy. Finally, the measured photoelectron spectrum of Ru(bpy)32+ is compared with the Kohn-Sham density of states for interpretation of occupied as well as computed virtual energy levels. This computational approach, in conjunction with first-ever photoelectron spectroscopy measurements of an aqueous transition metal ion, provides a quantitative benchmark for understanding the effect of water on metal redox potential and lays the groundwork for future studies of redox properties.

The valence orbital electron binding energies of water and of embedded solutes are crucial quantities for understanding chemical reactions taking place in aqueous solution, including oxidation/reduction, transition-metal coordination, and radiation chemistry. Their experimental determination based on liquid-photoelectron spectroscopy using soft X-rays is described, and we provide an overview of valence photoelectron spectroscopy studies reported to date. We discuss principal experimental aspects and several theoretical approaches to compute the measured binding energies of the least tightly bound molecular orbitals. Solutes studied are presented chronologically, from simple electrolytes, via transition-metal ion solutions and several organic and inorganic molecules, to biologically relevant molecules, including aqueous nucleotides and their components. In addition to the lowest vertical ionization energies, the measured valence photoelectron spectra also provide information on adiabatic ionization energies and reorganization energies for the oxidation (ionization) half-reaction. For solutes with low solubility, resonantly enhanced ionization provides a promising alternative pathway.

We demonstrate the presence of a symbiotic stability reinforcement effect between bioentities and crystalline ZIFs, where the ZIF protects biomolecules from denaturation and the biomolecules improve the acid resistance of the ZIF framework. The strategy provides a potential route for stabilizing MOFs for diverse technological and industrial applications.

Characterization of the structure and properties of matter would be incomplete without the detailed knowledge of electronic structure, and yet, for aqueous solutions, not even the binding energies of the valence electrons are generally known. Thus, fundamental interactions between solute electronic structure and water, essentially the key to chemical reactivity, have remained poorly understood. This work describes how, by the development of the vacuum liquid microjet technique for X-ray photoelectron spectroscopy, electronic structure measurements from aqueous solutions have advanced to date. Direct and resonant second-order electron emission processes are discussed in light of the specific electron structure information accessible from aqueous solutions. Several examples of solutes in their natural aqueous environment will be presented along with future research directions and prevailing challenges in the field.

A comparison of different catalysts (Ni, Co, Fe/Mo) has been performed in order to minimize the growth temperature for single-walled carbon nanotubes (SWCNTs). Dense SWCNT networks have been synthesized by thermal chemical vapor deposition (CVD) at temperatures as low as 600 °C using Ni catalyst layers of approximately 0.2 nm thickness. The dependence of the SWCNT growth on the most important parameters will be discussed exemplarily on the Ni catalyst system. On the basis of experimental observations, a phenomenological growth model for CVD synthesis of SWCNTs is proposed which is based on the interactions between the catalyst and its support. Further, it is suggested that only surface diffusion of hydrocarbons on the catalyst support or along the CNTs can explain the fast growth rates of SWCNTs during CVD synthesis.