Molecules at Solid Surfaces: A Personal Reminiscence.

I was fortunate to start my career in physical chemistry at a time when the development of the ultrahigh vacuum technique and of novel physical methods enabled the study of processes on well-defined surfaces at an atomic scale. These investigations included the mechanisms of heterogeneously catalyzed reactions, such as CO oxidation and ammonia synthesis, and phenomena of spatio-temporal self-organization, as described by the concepts of nonlinear dynamics.

John T. Yates, Jr. 1935-2015.

John T. Yates, Jr., professor at the University of Virginia, member of the US National Academy of Sciences, and pioneer of modern surface science passed away at the age of 80 on September 26, 2015. The scientific community has lost an exceptional scientist and gifted communicator, who was also heavily involved with scientific societies and academies, as well as evaluation procedures and conference organization.

Walther Nernst and the development of physical chemistry.

A commemorative symposium took place on the 16th June 2014 in the Magnus House in Berlin on the occasion of the 150th birthday of Walter Nernst. This Essay outlines the important stages in his life and consider the main features in the development of the discipline cofounded by him.

Molecules at surfaces: 100 years of physical chemistry in Berlin-Dahlem.

Scratching the surface: for over 100 years the interactions of molecules at surfaces have been studied at the Fritz Haber Institute of the Max Planck Society, Berlin. Nobel Laureate Gerhard Ertl looks back at some of the key developments in this time, and the people who made them.

Nonequilibrium microstructures in reactive monolayers as soft matter systems.

Chemical systems provide classical examples of nonequilibrium pattern formation. Reactions in weak aqueous solutions, such as the extensively investigated Belousov-Zhabotinsky reaction, demonstrate a rich variety of patterns, ranging from travelling fronts to rotating spiral waves and chemical turbulence. Pattern formation in such systems is based on interplay between the reactions and diffusion. Intrinsically, this puts a restriction on the minimum length scale of the developing structures, which cannot be shorter than the diffusion length of the reactants. However, much smaller nonequilibrium structures, with characteristic lengths reaching down to nanoscales, are also possible. They are found in reactive soft matter, where energetic interactions between molecules are present as well. In these systems, chemical reactions and diffusion interfere with phase transitions, yielding active, stationary or dynamic microstructures. Nonequilibrium soft-matter microstructures are of fundamental importance for biological cells and may have interesting engineering applications. In this Minireview, we focus on the microstructures found in reactive soft-matter monolayers at solid surfaces or liquid-air interfaces.

Edge effects in an electrochemical reaction: HCOOH oxidation on a Pt ribbon.

The use of a ribbon-shaped Pt electrode gives rise to edge effects of the interfacial potential, as is predicted from the potential theory in the form of the corresponding reaction-migration equation. They are studied in the bistable region of formic acid oxidation. Essentially, the edges tend to be more passive than the bulk of the electrode, which also causes a passivation (activation) transition to originate from the edges (center) of the ribbon. The experimental results are in agreement with simulations of the reaction-migration system.

Activation of diatomic molecules at solid surfaces.

The interaction of a diatomic molecule with a well-defined single crystal surface represents the prototype of the elementary processes involved in heterogeneous catalysis, and it can be studied down to atomic length and extremely short (fs) time-scales. Our present understanding is illustrated by examples concerning the activation of hydrogen (including also the breakdown of thermal equilibrium during rapid laser-induced associative desorption), the role of steps as 'active sites' in the dissociative adsorption of NO or N2, and the mechanism and kinetics of the catalytic oxidation of CO.

A comparative study of hydroxide adsorption on the (111), (110), and (100) faces of silver with cyclic voltammetry, ex situ electron diffraction, and in situ second harmonic generation.

Hydroxide adsorption on the (111), (110), and (100) faces of silver electrodes from mixed NaOH/NaF solution is studied using cyclic voltammetry and in situ second harmonic generation (SHG). Cyclic voltammograms for the three low index silver planes in alkaline electrolytes are for the first time compared. They show two pairs of anodic and cathodic peaks in the potential interval below the equilibrium Ag/Ag(2)O potential. These are attributed to the specific adsorption of hydroxide ions followed by submonolayer oxide formation. The differences in the cyclic voltammograms for the (111), (110), and (100) planes are attributed to different (i) work functions, (ii) surface atomic densities, and (iii) corrugation potentials for these surfaces. Ex situ low energy electron diffraction (LEED) and reflection high energy electron diffraction (RHEED) show that disordered adlayers are formed on Ag(111) and Ag(100), in contrast to Ag(110), where ordered structures are produced in the region of the first pair of current peaks. In the region of the second pair of peaks, LEED indicates disordered oxide phases on each crystal plane and RHEED shows the presence of small islands of c(2 x 2) structure at some potentials on (110) and (100). SHG measurements were performed (i) in the potential scan mode at constant rotational angle and (ii) at constant potential as a function of the rotational angle. The isotropic (for the (111), (110), and (100) planes) and anisotropic (for the (110) and (111) planes) contributions to the SHG intensity were calculated by fitting the experimental data and are discussed in terms of their dependence on the charge density at the interface, on hydroxide adsorption, and on submonolayer oxide formation.

Nanoscale probing of adsorbed species by tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy (TERS) is based on the optical excitation of localized surface plasmons in the tip-substrate cavity, which provides a large but local field enhancement near the tip apex. We report on TERS with smooth single crystalline surfaces as substrates. The adsorbates were CN- ions at Au(111) and malachite green isothiocyanate (MGITC) molecules at Au(111) and Pt(110) using either Au or Ir tips. The data analysis yields Raman enhancements of about 4 x 10(5) for CN- and up to 10(6) for MGITC at Au(111) with a Au tip, probing an area of less than 100 nm radius.

Two-dimensional nanoscale self-assembly on a gold surface by spinodal decomposition.

The structure formation upon spinodal decomposition of a two-dimensional model system, a Au adatom gas on a Au(111) surface, was observed in situ by scanning tunneling microscopy (STM). A thermodynamically unstable state was prepared by applying microsecond voltage pulses to the STM tip in an electrochemical system, causing the random dissolution of Au atoms from the uppermost monolayer. Interconnected, labyrinthine island patterns were formed at Au coverages between 0.4 and 0.9 monolayer with dominating length scales lambda(m) of the order of a few nanometers.

Oscillatory thermomechanical instability of an ultrathin catalyst.

Because of the small thermal capacity of ultrathin ( approximately 200 nanometers) metal single crystals, it is possible to explore the coupling of catalytic and thermal action at low pressures. We analyzed a chemothermomechanical instability in this regime, in which catalytic reaction kinetics interact with heat transfer and mechanical buckling to create oscillations. These interacting components are separated and explored through experimentation, mathematical modeling, and scientific computation, and an explanation of the phenomenon emerges from their synthesis.

Pattern formation on the edge of chaos: experiments with CO oxidation on a Pt(110) surface under global delayed feedback.

Experiments with catalytic oxidation of carbon monoxide on Pt(110) show that chemical turbulence in this system can be suppressed by application of appropriate global delayed feedback. Different spatiotemporal patterns, seen near the transition from turbulence to uniform oscillations, are investigated. Such patterns include intermittent turbulence, oscillatory standing waves, cellular structures, and phase clusters. Using a method based on the Hilbert transform, spatial distributions of local phase and amplitude in these patterns are reconstructed from the experimental data.