Accurate quantification of the stability of the perylene-tetracarboxylic dianhydride on Au(111) molecule-surface interface.

Studying inorganic/organic hybrid systems is a stepping stone towards the design of increasingly complex interfaces. A predictive understanding requires robust experimental and theoretical tools to foster trust in the obtained results. The adsorption energy is particularly challenging in this respect, since experimental methods are scarce and the results have large uncertainties even for the most widely studied systems. Here we combine temperature-programmed desorption (TPD), single-molecule atomic force microscopy (AFM), and nonlocal density-functional theory (DFT) calculations, to accurately characterize the stability of a widely studied interface consisting of perylene-tetracarboxylic dianhydride (PTCDA) molecules on Au(111). This network of methods lets us firmly establish the adsorption energy of PTCDA/Au(111) via TPD (1.74 ± 0.10 eV) and single-molecule AFM (2.00 ± 0.25 eV) experiments which agree within error bars, exemplifying how implicit replicability in a research design can benefit the investigation of complex materials properties.

Constructing Binder- and Carbon Additive-Free Organosulfur Cathodes Based on Conducting Thiol-Polymers through Electropolymerization for Lithium-Sulfur Batteries.

Herein, the concept of constructing binder- and carbon additive-free organosulfur cathode was proved based on thiol-containing conducting polymer poly(4-(thiophene-3-yl) benzenethiol) (PTBT). The PTBT featured the polythiophene-structure main chain as a highly conducting framework and the benzenethiol side chain to copolymerize with sulfur and form a crosslinked organosulfur polymer (namely S/PTBT). Meanwhile, it could be in-situ deposited on the current collector by electro-polymerization, making it a binder-free and free-standing cathode for Li-S batteries. The S/PTBT cathode exhibited a reversible capacity of around 870 mAh g-1 at 0.1 C and improved cycling performance compared to the physically mixed cathode (namely S&PTBT). This multifunction cathode eliminated the influence of the additives (carbon/binder), making it suitable to be applied as a model electrode for operando analysis. Operando X-ray imaging revealed the remarkable effect in the suppression of polysulfides shuttle via introducing covalent bonds, paving the way for the study of the intrinsic mechanisms in Li-S batteries.

Combined first-principles statistical mechanics approach to sulfur structure in organic cathode hosts for polymer based lithium-sulfur (Li-S) batteries.

Polymer-based batteries that utilize organic electrode materials are considered viable candidates to overcome the common drawbacks of lithium-sulfur (Li-S) batteries. A promising cathode can be developed using a conductive, flexible, and free-standing polymer, poly(4-thiophen-3-yl)benzenethiol) (PTBT), as the sulfur host material. By a vulcanization process, sulfur is embedded into this polymer. Here, we present a combination of electronic structure theory and statistical mechanics to characterize the structure of the initial state of the charged cathode on an atomic level. We perform a stability analysis of differently sulfurized TBT dimers as the basic polymer unit calculated within density-functional theory (DFT) and combine this with a statistical binding model for the binding probability distributions of the vulcanization process. From this, we deduce sulfur chain length ("rank") distributions and calculate the average sulfur rank depending on the sulfur concentration and temperature. This multi-scale approach allows us to bridge the gap between the local description of the covalent bonding process and the derivation of the macroscopic properties of the cathode. Our calculations show that the main reaction of the vulcanization process leads to high-probability states of sulfur chains cross-linking TBT units belonging to different polymer backbones, with a dominant rank around n = 5. In contrast, the connection of adjacent TBT units of the same polymer backbone by a sulfur chain is the side reaction. These results are experimentally supported by Raman spectroscopy.

Highly Heterogeneous Polarization and Solvation of Gold Nanoparticles in Aqueous Electrolytes.

The performance of gold nanoparticles (NPs) in applications depends critically on the structure of the NP-solvent interface, at which the electrostatic surface polarization is one of the key characteristics that affects hydration, ionic adsorption, and electrochemical reactions. Here, we demonstrate significant effects of explicit metal polarizability on the solvation and electrostatic properties of bare gold NPs in aqueous electrolyte solutions of sodium salts of various anions (Cl-, BF4-, PF6-, nitrophenolate, and 3- and 4-valent hexacyanoferrate), using classical molecular dynamics simulations with a polarizable core-shell model for the gold atoms. We find considerable spatial heterogeneity of the polarization and electrostatic potentials on the NP surface, mediated by a highly facet-dependent structuring of the interfacial water molecules. Moreover, ion-specific, facet-dependent ion adsorption leads to considerable alterations of the interfacial polarization. Compared to nonpolarizable NPs, surface polarization modifies water local dipole densities only slightly but has substantial effects on the electrostatic surface potentials and leads to significant lateral redistributions of ions on the NP surface. Besides, interfacial polarization effects cancel out in the far field for monovalent ions but not for polyvalent ions, as anticipated from continuum "image-charge" concepts. Far-field effective Debye-Hückel surface potentials change accordingly in a valence-specific fashion. Hence, the explicit charge response of metal NPs is crucial for the accurate description and interpretation of interfacial electrostatics (e.g., for charge transfer and interfacial polarization in catalysis and electrochemistry).

How the hydroxylation state of the (110)-rutile TiO2 surface governs its electric double layer properties.

The hydroxylation state of an oxide surface is a central property of its solid/liquid interface and its corresponding electrical double layer. This study integrated both a reactive force field (ReaxFF) and a non-reactive potential into a hierarchical framework within molecular dynamics (MD) simulations to reveal how the hydroxylation state of the (110)-rutile TiO2 surface affects the electrical double layer properties. The simulation results obtained in the ReaxFF framework have shown that, while water dissociation occurs only at the under-coordinated Ti5c sites on the pristine TiO2 surface, the presence of point defects on the surface facilitates water dissociation at the oxygen vacancy sites, leading to two protonated oxygen bridge atoms for each vacancy site. As a consequence of enhanced water dissociation at the vacancy sites, water dissociation is quenched at the under-coordinated Ti5c sites resulting in two competitive hydroxylation mechanisms on the (110)-TiO2 surface. Using non-reactive MD simulations with hydroxylation states derived from the ReaxFF analysis, we demonstrate that water dissociation at the vacancy sites is a central mechanism governing the structuring of water near the interface. While the structuring of water near the interface is the main contribution to the electric field, water dissociation at the vacancy site enhances the adsorption of the electrolyte ions at the interface. The adsorbed ions lead to an increase of the effective surface charge as well as surface (zeta) potentials which are in the range of experimental observations. Our work provides a hierarchical multiscale simulation approach, covering a series of results with in-depth discussion for atomic/molecular level understanding of water dissociation and its effect on electric double layer properties of TiO2 to advance water splitting.

Ion-Specific Adsorption on Bare Gold (Au) Nanoparticles in Aqueous Solutions: Double-Layer Structure and Surface Potentials.

We study the solvation and electrostatic properties of bare gold (Au) nanoparticles (NPs) of 1-2 nm in size in aqueous electrolyte solutions of sodium salts of various anions with large physicochemical diversity (Cl-, BF4-, PF6-, Nip- (nitrophenolate), 3- and 4-valent hexacyanoferrate (HCF)) using nonpolarizable, classical molecular dynamics computer simulations. We find a substantial facet selectivity in the adsorption structure and spatial distribution of the ions at the AuNPs: while sodium and some of the anions (e.g., Cl-, HCF3-) adsorb more at the "edgy" (100) and (110) facets of the NPs, where the water hydration structure is more disordered, other ions (e.g., BF4-, PF6-, Nip-) prefer to adsorb strongly on the extended and rather flat (111) facets. In particular, Nip-, which features an aromatic ring in its chemical structure, adsorbs strongly and perturbs the first water monolayer structure on the NP (111) facets substantially. Moreover, we calculate adsorptions, radially resolved electrostatic potentials as well as the far-field effective electrostatic surface charges and potentials by mapping the long-range decay of the calculated electrostatic potential distribution onto the standard Debye-Hückel form. We show how the extrapolation of these values to other ionic strengths can be performed by an analytical Adsorption-Grahame relation between the effective surface charge and potential. We find for all salts negative effective surface potentials in the range from -10 mV for NaCl down to about -80 mV for NaNip, consistent with typical experimental ranges for the zeta potential. We discuss how these values depend on the surface definition and compare them to the explicitly calculated electrostatic potentials near the NP surface, which are highly oscillatory in the ±0.5 V range.

Targeting the TS dimer interface in bifunctional Cryptosporidium hominis TS-DHFR from parasitic protozoa: Virtual screening identifies novel TS allosteric inhibitors.

Effective therapies are lacking to treat gastrointestinal infections caused by the genus Cryptosporidium, which can be fatal in the immunocompromised. One target of interest is Cryptosporidium hominis (C. hominis) thymidylate synthase-dihydrofolate reductase (ChTS-DHFR), a bifunctional enzyme necessary for DNA biosynthesis. Targeting the TS-TS dimer interface is a novel strategy previously used to identify inhibitors against the related bifunctional enzyme in Toxoplasma gondii. In the present study, we target the ChTS dimer interface through homology modeling and high-throughput virtual screening to identifying allosteric, ChTS-specific inhibitors. Our work led to the discovery of methylenedioxyphenyl-aminophenoxypropanol analogues which inhibit ChTS activity in a manner that is both dose-dependent and influenced by the conformation of the enzyme. Preliminary results presented here include an analysis of structure activity relationships and a ChTS-apo crystal structure of ChTS-DHFR supporting the continued development of inhibitors that stabilize a novel pocket formed in the open conformation of ChTS-TS.

Many-body dispersion effects in the binding of adsorbates on metal surfaces.

A correct description of electronic exchange and correlation effects for molecules in contact with extended (metal) surfaces is a challenging task for first-principles modeling. In this work, we demonstrate the importance of collective van der Waals dispersion effects beyond the pairwise approximation for organic-inorganic systems on the example of atoms, molecules, and nanostructures adsorbed on metals. We use the recently developed many-body dispersion (MBD) approach in the context of density-functional theory [Tkatchenko et al., Phys. Rev. Lett. 108, 236402 (2012) and Ambrosetti et al., J. Chem. Phys. 140, 18A508 (2014)] and assess its ability to correctly describe the binding of adsorbates on metal surfaces. We briefly review the MBD method and highlight its similarities to quantum-chemical approaches to electron correlation in a quasiparticle picture. In particular, we study the binding properties of xenon, 3,4,9,10-perylene-tetracarboxylic acid, and a graphene sheet adsorbed on the Ag(111) surface. Accounting for MBD effects, we are able to describe changes in the anisotropic polarizability tensor, improve the description of adsorbate vibrations, and correctly capture the adsorbate-surface interaction screening. Comparison to other methods and experiment reveals that inclusion of MBD effects improves adsorption energies and geometries, by reducing the overbinding typically found in pairwise additive dispersion-correction approaches.

Non-additivity of molecule-surface van der Waals potentials from force measurements.

Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction.

Crystallographic and receptor binding characterization of Plasmodium falciparum macrophage migration inhibitory factor complexed to two potent inhibitors.

We report the crystal structures of two inhibitors of Plasmodium falciparum macrophage migration inhibitory factor (PfMIF) with nanomolar Ki's, analyze their interactions with the active site of PfMIF, and provide explanations regarding their selectivity of PfMIF versus human MIF. These inhibitors were also found to selectively inhibit interactions between PfMIF and the human MIF receptor CD74. The results of this study provide the framework for the development of new therapeutics that target PfMIF.

Understanding Structure and Bonding of Multilayered Metal-Organic Nanostructures.

For organic and hybrid electronic devices, the physicochemical properties of the contained interfaces play a dominant role. To disentangle the various interactions occurring at such heterointerfaces, we here model a complex, yet prototypical, three-component system consisting of a Cu-phthalocyanine (CuPc) film on a 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) monolayer adsorbed on Ag(111). The two encountered interfaces are similar, as in both cases there would be no bonding without van der Waals interactions. Still, they are also distinctly different, as only at the Ag(111)-PTCDA interface do massive charge-rearrangements occur. Using recently developed theoretical tools, we show that it has become possible to provide atomistic insight into the physical and chemical processes in this comparatively complex nanostructure distinguishing between interactions involving local rearrangements of the charge density and long-range van der Waals attraction.

Density-functional theory with screened van der Waals interactions for the modeling of hybrid inorganic-organic systems.

The electronic properties and the function of hybrid inorganic-organic systems (HIOS) are intimately linked to their interface geometry. Here we show that the inclusion of the many-body collective response of the substrate electrons inside the inorganic bulk enables us to reliably predict the HIOS geometries and energies. This is achieved by the combination of dispersion-corrected density-functional theory (the DFT+ van der Waals approach) [Phys. Rev. Lett. 102, 073005 (2009)], with the Lifshitz-Zaremba-Kohn theory for the nonlocal Coulomb screening within the bulk. Our method yields geometries in remarkable agreement (≈0.1 Å) with normal incidence x-ray standing wave measurements for the 3, 4, 9, 10-perylene-tetracarboxylic acid dianhydride (C(24)O(6)H(8), PTCDA) molecule on Cu(111), Ag(111), and Au(111) surfaces. Similarly accurate results are obtained for xenon and benzene adsorbed on metal surfaces.