Michael D. Bronshtein

Submolecular Electronic Mapping of Single Cysteine Molecules by in Situ Scanning Tunneling Imaging

We have used L-cysteine (Cys) as a model system to study the surface electronic structures of single molecules at the submolecular level in aqueous buffer solution by a combination of electrochemical scanning tunneling microscopy (in situ STM), electrochemistry including voltammetry and chronocoulometry, and density functional theory (DFT) computations. Cys molecules were assembled on single-crystal Au(110) surfaces to form a highly ordered monolayer with a periodic lattice structure of c(2x2) in which each unit contains two molecules; this conclusion is confirmed by the results of calculations based on a slab model for the metal surface. The ordered monolayer offers a platform for submolecular scale electronic mapping that is an issue of fundamental interest but remains a challenge in STM imaging science and surface chemistry. Single Cys molecules were mapped as three electronic subunits contributed mainly from three chemical moieties: thiol (-SH), carboxylic (-COOH), and amine (-NH2) groups. The contrasts of the three subunits depend on the environment (e.g., pH), which affects the electronic structure of adsorbed species. From the DFT computations focused on single molecules, rational analysis of the electronic structures is achieved to delineate the main factors that determine electronic contrasts in the STM images. These factors include the molecular orientation, the chemical nature of the elements or groups in the molecule, and the interaction of the elements with the substrate and tip. The computational images recast as constant-current-height profiles show that the most favorable molecular orientation is the adsorption of cysteine as a radical in zwitterionic form located on the bridge between the Au(110) atomic rows and with the amine and carboxyl group toward the solution bulk. The correlation between physical location and electronic contrast of the adsorbed molecules was also revealed by the computational data. The present study shows that cysteine packing in the adlayer on Au(110) from the liquid environment is in contrast to that from the ultrahigh-vacuum environment, suggesting solvent plays a role during molecular assembly.

Interplay between solvent effects of different nature in interfacial bond breaking electron transfer.

Solvent dynamics effects on electroreduction of peroxodisulphate anion on mercury electrode (a typical bond breaking electron transfer reaction) are explored in the framework of the Sumi-Marcus model. The reaction three-dimensional free energy surface is constructed using the Anderson model Hamiltonian. A new interpretation of short- and long-time survival times is presented as well. Since the reduction is assumed to proceed from aqueous sucrose and glucose solutions of different concentrations (which are used to vary the solution viscosity), unavoidable changes in the Pekar factor (static effect) are also taken into account. The results of model calculations are employed to interpret challenging experimental data on nonmonotonous constant rate vs solution viscosity dependence reported earlier (in part, appearance of an ascent plot). The influence of mixed solvent composition on the reaction rate and transfer coefficient is explained in terms of the saddle point avoidance in the vicinity of activationless discharge. Splitting of the reaction coordinates into slow (solvent) and fast (intramolecular) ones is argued to be crucial, as the most important reaction features cannot be described by means of more simplified models, even if both static and dynamic effects are addressed.

Adiabatic electron transfer reaction on semiconducting electrodes

Theoretical treatments of electrochemical reactions at semiconductors are usually based on theories that presume a weak interaction between the reactant and the electrode. Herein a theory is developed that is valid for arbitrary interaction strengths, and its consequences are explored within a simple coupling scheme. This model can be used as a framework for the investigation of specific catalytic reactions including photoelectrocatalysis.