There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Diamond-like carbon (DLC) is a metastable form of amorphous carbon with significant sp3 bonding. DLC is a semiconductor with a high mechanical hardness, chemical inertness, and optical transparency. This review will describe the deposition methods, deposition mechanisms, characterisation methods, electronic structure, gap states, defects, doping, luminescence, field emission, mechanical properties and some applications of DLCs. The films have widespread applications as protective coatings in areas, such as magnetic storage disks, optical windows and micro-electromechanical devices (MEMs).

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Diamond-like amorphous carbon

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Moller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr_2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.

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Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

cp2k has become a versatile open-source tool for the simulation of complex systems on the nanometer scale. It allows for sampling and exploring potential energy surfaces that can be computed using a variety of empirical and first principles models. Excellent performance for electronic structure calculations is achieved using novel algorithms implemented for modern and massively parallel hardware. This review briefly summarizes the main capabilities and illustrates with recent applications the science cp2k has enabled in the field of atomistic simulation.

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cp2k: atomistic simulations of condensed matter systems

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.

RESEARCH ARTICLE Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Photoemission from Liquid Aqueous Solutions

The valence band photoelectron spectra of liquid water (H2O and D2O) are studied in the photon energy range from hν = 60 to 120 eV. The experiments use a 6 μm diameter liquid-jet free vacuum surface at the MBI undulator beamline of the synchrotron radiation facility BESSY. Photoelectron emission from all four valence molecular orbitals (MOs) is observed. In comparison to those of the gas phase, the peaks are significantly broadened and shifted to lower binding energies by about 1.5 eV. This is attributed primarily to the electronic polarization of the solvent molecules around an ionized water molecule. Energy shifts, peak broadening, and relative peak intensities for the four MOs differ because of their specific participation in the hydrogen bonding in liquid water. Relative photoionization cross sections for MOs were measured for hν = 60, 80, and 100 eV. The main difference for liquid water, as compared to the gas phase, is the relative intensity decrease of the 1b2 and 3a1 orbitals, reflecting changes o...

Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation

Solvated electrons in liquid water are one of the seemingly simplest, but most important, transients in chemistry and biology, but they have resisted disclosing important information about their energetics, binding motifs and dynamics. Here we report the first ultrafast liquid-jet photoelectron spectroscopy measurements of solvated electrons in liquid water. The results prove unequivocally the existence of solvated electrons bound at the water surface and of solvated electrons in the bulk solution, with vertical binding energies of 1.6 eV and 3.3 eV, respectively, and with lifetimes longer than 100 ps. The unexpectedly long lifetime of solvated electrons bound at the water surface is attributed to a free-energy barrier that separates surface and interior states. Beyond constituting important energetic and kinetic benchmark and reference data, the results also help to understand the mechanisms of a number of very efficient electron-transfer processes in nature.

Binding energies, lifetimes and implications of bulk and interface solvated electrons in water

The surfaces of aqueous solutions are traditionally viewed as devoid of inorganic ions. Molecular simulations and surface-selective spectroscopic techniques show, however, that large polarizable anions and hydronium cations can be found (and even enhanced) at the surface and are involved in chemistry at the air/water interface. Here, we review recent studies of ions at the air/water interface and compare from this perspective water with other polar solvents. For water, we focus in particular on the surface behavior of its ionic product (i.e., hydronium and hydroxide ions). We also investigate the feasibility of dielectric models for the description of the protein/water interface, in analogy to the air/water interface. Little correlation is found between these two interfaces in terms of ion segregation. Therefore, we suggest a local model of pairing of ions from the solution with charged and polar groups at the protein surface. We also describe corresponding results of experimental studies on aqueous model systems.

Bernd Winter

Papers

Photoemission from Liquid Aqueous Solutions

Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation

Binding energies, lifetimes and implications of bulk and interface solvated electrons in water

Ions at aqueous interfaces: from water surface to hydrated proteins.

Photoelectron spectroscopy of liquid water and aqueous solution: Electron effective attenuation lengths and emission-angle anisotropy