Double-layer structure of the Pt(111)-aqueous electrolyte interface.

We present detailed measurements of the double-layer capacitance of the Pt(111)-electrolyte interface close to the potential of zero charge (PZC) in the presence of several different electrolytes consisting of anions and cations that are considered to be nonspecifically adsorbed. For low electrolyte concentrations, we show strong deviations from traditional Gouy-Chapman-Stern (GCS) behavior that appear to be independent of the nature of the electrolyte ions. Focusing on the capacitance further away from PZC and the trends for increasing ion concentration, we observe ion-specific capacitance effects that appear to be related to the size or hydration strength of the ions. We formulate a model for the structure of the electric double layer of the Pt(111)-electrolyte interface that goes significantly beyond the GCS theory. By combining two existing models, namely, one capturing the water reorganization on Pt close to the PZC and one accounting for an attractive ion-surface interaction not included in the GCS model, we can reproduce and interpret the main features the experimental capacitance of the Pt(111)-electrolyte interface. The model suggests a picture of the double layer with an increased ion concentration close to the interface as a consequence of a weak attractive ion-surface interaction, and a changing polarizability of the Pt(111)-water interface due to the potential-dependent water adsorption and orientation.

Best practices of modeling complex materials in electrocatalysis, exemplified by oxygen evolution reaction on pentlandites.

Pentlandites are natural ores with structural properties comparable to that of [FeNi] hydrogenases. While this class of transition-metal sulfide materials - (Fe,Ni)9S8 - with a variable Fe : Ni ratio has been proven to be an active electrode material for the hydrogen evolution reaction, it is also discussed as electrocatalyst for the alkaline oxygen evolution reaction (OER), corresponding to the bottleneck of anion exchange membrane electrolyzers for green hydrogen production. Despite the experimental evidence for the use of (Fe,Ni)9S8 as an OER catalyst, a detailed investigation of the elementary reaction steps, including consideration of adsorbate coverages and limiting steps under anodic polarizing conditions, is still missing. We address this gap in the present manuscript by gaining atomistic insights into the OER on an Fe4.5Ni4.5S8(111) surface through density functional theory calculations combined with a descriptor-based analysis. We use this system to introduce best practices for modeling this rather complex material by pointing out hidden pitfalls that can arise when using the popular computational hydrogen electrode approach to describe electrocatalytic processes at the electrified solid/liquid interface for energy conversion and storage.

Quantum Monte Carlo calculations on dissociative chemisorption of H2 + Al(110): Minimum barrier heights and their comparison to DFT values.

Reactions of molecules on metal surfaces are notoriously difficult to simulate accurately. Density functional theory can be utilized to generate a potential energy surface, but with presently available functionals, the results are not yet accurate enough. To provide benchmark barrier heights with a high-quality method, diffusion Monte Carlo (DMC) is applied to H2 + Al(110). Barrier heights have been computed for six geometries. Our present goal is twofold: first, to provide accurate barrier heights for the two lowest lying transition states of the system, and second, to assess whether density functionals are capable of describing the variation of barrier height with molecular orientation and impact site through a comparison with DMC barriers. To this end, barrier heights computed with selected functionals at the generalized gradient approximation (GGA) and meta-GGA levels are compared to the DMC results. The comparison shows that all selected functionals yield a rather accurate description of the variation of barrier heights with impact site and orientation, although their absolute values may not be accurate. RPBE-vdW-DF and BEEF-vdW were found to perform quite well even in terms of absolute numbers. Both functionals provided barrier heights for the energetically lowest lying transition state that are within 1 kcal/mol of the DMC value.

Selective control over fragmentation reactions in polyatomic molecules using impulsive laser alignment.

We investigate the possibility of using molecular alignment for controlling the relative probability of individual reaction pathways in polyatomic molecules initiated by electronic processes on the few-femtosecond time scale. Using acetylene as an example, it is shown that aligning the molecular axis with respect to the polarization direction of the ionizing laser pulse does not only allow us to enhance or suppress the overall fragmentation yield of a certain fragmentation channel but, more importantly, to determine the relative probability of individual reaction pathways starting from the same parent molecular ion. We show that the achieved control over dissociation or isomerization pathways along specific nuclear degrees of freedom is based on a controlled population of associated excited dissociative electronic states in the molecular ion due to relatively enhanced ionization contributions from inner valence orbitals.

Unraveling the Origin of the Repulsive Interaction between Hydrogen Adsorbates on Platinum Single-Crystal Electrodes.

Hydrogen adsorption on platinum (Pt) single-crystal electrodes has been studied intensively in both experiments and computations. Yet, the precise origin and nature of the repulsive interactions observed between hydrogen adsorbates (Hads) have remained elusive. Here, we use first-principles density functional theory calculations to investigate in detail the interactions between Hads on Pt(111), Pt(100), and Pt(110) surfaces. The repulsive interaction between Hads on Pt(111) is deconvoluted into three different physical contributions, namely, (i) electrostatic interactions, (ii) surface distortion effect, and (iii) surface coordination effect. The long-range electrostatic interaction, which is generally considered the most important source of repulsive interactions in surface adsorption, was found to contribute less than 30% of the overall repulsive interaction. The remaining >70% arises from the other two contributions, underscoring the critical influence of surface-mediated interactions on the adsorption process. Surface distortion and coordination effects are found to strongly depend on the coverage and adsorption geometry: the effect of surface distortion dominates when adsorbates reside two or more Pt atoms apart; the effect of surface coordination dominates if hydrogen is adsorbed on neighboring adsorption sites. The above effects are considerably less pronounced on Pt(100) and Pt(110), therefore resulting in weaker interactions between Hads on these two surfaces. Overall, the study highlights the relevance of surface-mediated effects on adsorbate-adsorbate interactions, such as the often-overlooked surface distortion. The effect of these interactions on the hotly debated adsorption site for the adsorbed hydrogen intermediate in the hydrogen evolution reaction is also discussed.

Best-of-Both-Worlds Predictive Approach to Dissociative Chemisorption on Metals.

Predictive capability, accuracy, and affordability are essential features of a theory that is capable of describing dissociative chemisorption on a metal surface. This type of reaction is important for heterogeneous catalysis. Here we present an approach in which we use diffusion Monte Carlo (DMC) to pin the minimum barrier height and construct a density functional that reproduces this value. This predictive approach allows the construction of a potential energy surface at the cost of density functional theory while retaining near DMC accuracy. Scrutinizing effects of energy dissipation and quantum tunneling, dynamics calculations suggest the approach to be of near chemical accuracy, reproducing molecular beam sticking experiments for the showcase H2 + Al(110) system to ∼1.4 kcal/mol.

Simulating Highly Activated Sticking of H2 on Al(110): Quantum versus Quasi-Classical Dynamics.

We evaluate the importance of quantum effects on the sticking of H2 on Al(110) for conditions that are close to those of molecular beam experiments that have been done on this system. Calculations with the quasi-classical trajectory (QCT) method and with quantum dynamics (QD) are performed using a model in which only motion in the six molecular degrees of freedom is allowed. The potential energy surface used has a minimum barrier height close to the value recently obtained with the quantum Monte Carlo method. Monte Carlo averaging over the initial rovibrational states allowed the QD calculations to be done with an order of magnitude smaller computational expense. The sticking probability curve computed with QD is shifted to lower energies relative to the QCT curve by 0.21 to 0.05 kcal/mol, with the highest shift obtained for the lowest incidence energy. Quantum effects are therefore expected to play a small role in calculations that would evaluate the accuracy of electronic structure methods for determining the minimum barrier height to dissociative chemisorption for H2 + Al(110) on the basis of the standard procedure for comparing results of theory with molecular beam experiments.

Attosecond-recollision-controlled selective fragmentation of polyatomic molecules.

Control over various fragmentation reactions of a series of polyatomic molecules (acetylene, ethylene, 1,3-butadiene) by the optical waveform of intense few-cycle laser pulses is demonstrated experimentally. We show both experimentally and theoretically that the responsible mechanism is inelastic ionization from inner-valence molecular orbitals by recolliding electron wave packets, whose recollision energy in few-cycle ionizing laser pulses strongly depends on the optical waveform. Our work demonstrates an efficient and selective way of predetermining fragmentation and isomerization reactions in polyatomic molecules on subfemtosecond time scales.

Time-Resolved Local pH Measurements during CO2 Reduction Using Scanning Electrochemical Microscopy: Buffering and Tip Effects.

The electrochemical reduction of CO2 is widely studied as a sustainable alternative for the production of fuels and chemicals. The electrolyte's bulk pH and composition play an important role in the reaction activity and selectivity and can affect the extent of the buildup of pH gradients between the electrode surface and the bulk of the electrolyte. Quantifying the local pH and how it is affected by the solution species is desirable to gain a better understanding of the CO2 reduction reaction. Local pH measurements can be realized using Scanning Electrochemical Microscopy (SECM); however, finding a pH probe that is stable and selective under CO2 reduction reaction conditions is challenging. Here, we have used our recently developed voltammetric pH sensor to perform pH measurements in the diffusion layer during CO2 reduction using SECM, with high time resolution. Using a 4-hydroxylaminothiophenol (4-HATP)/4-nitrosothiophenol (4-NSTP) functionalized gold ultramicroelectrode, we compare the local pH developed above a gold substrate in an argon atmosphere, when only hydrogen evolution is taking place, to the pH developed in a CO2 atmosphere. The pH is monitored at a fixed distance from the surface, and the sample potential is varied in time. In argon, we observe a gradual increase of pH, while a plateau region is present in CO2 atmosphere due to the formation of HCO3 - buffering the reaction interface. By analyzing the diffusion layer dynamics once the sample reaction is turned "off", we gain insightful information on the time scale of the homogeneous reactions happening in solution and on the time required for the diffusion layer to fully recover to the initial bulk concentration of species. In order to account for the effect of the presence of the SECM tip on the measured pH, we performed finite element method simulations of the fluid and reaction dynamics. The results show the significant localized diffusion hindrance caused by the tip, so that in its absence, the pH values are more acidic than when the tip is present. Nonetheless, through the simulation, we can account for this effect and estimate the real local pH values across the diffusion layer.

Density Functional Theory for Molecule-Metal Surface Reactions: When Does the Generalized Gradient Approximation Get It Right, and What to Do If It Does Not.

While density functional theory (DFT) is perhaps the most used electronic structure theory in chemistry, many of its practical aspects remain poorly understood. For instance, DFT at the generalized gradient approximation (GGA) tends to fail miserably at describing gas-phase reaction barriers, while it performs surprisingly well for many molecule-metal surface reactions. GGA-DFT also fails for many systems in the latter category, and up to now it has not been clear when one may expect it to work. We show that GGA-DFT tends to work if the difference between the work function of the metal and the molecule's electron affinity is greater than ∼7 eV and to fail if this difference is smaller, with sticking of O2 on Al(111) being a spectacular example. Using dynamics calculations we show that, for this system, the DFT problem may be solved as done for gas-phase reactions, i.e., by resorting to hybrid functionals, but using screening at long-range to obtain a correct description of the metal. Our results suggest the GGA error in the O2 + Al(111) barrier height to be functional driven. Our results also suggest the possibility to compute potential energy surfaces for the difficult-to-treat systems with computationally cheap nonself-consistent calculations in which a hybrid functional is applied to a GGA density.

Dielectric Decrement for Aqueous NaCl Solutions: Effect of Ionic Charge Scaling in Nonpolarizable Water Force Fields.

We investigate the dielectric constant and the dielectric decrement of aqueous NaCl solutions by means of molecular dynamic simulations. We thereby compare the performance of four different force fields and focus on disentangling the origin of the dielectric decrement and the influence of scaled ionic charges, as often used in nonpolarizable force fields to account for the missing dynamic polarizability in the shielding of electrostatic ion interactions. Three of the force fields showed excessive contact ion pair formation, which correlates with a reduced dielectric decrement. In spite of the fact that the scaling of charges only weakly influenced the average polarization of water molecules around an ion, the rescaling of ionic charges did influence the dielectric decrement, and a close-to-linear relation of the slope of the dielectric constant as a function of concentration with the ionic charge was found.

Quantum Monte Carlo Calculations on a Benchmark Molecule-Metal Surface Reaction: H2 + Cu(111).

Accurate modeling of heterogeneous catalysis requires the availability of highly accurate potential energy surfaces. Within density functional theory, these can-unfortunately-depend heavily on the exchange-correlation functional. High-level ab initio calculations, on the other hand, are challenging due to the system size and the metallic character of the metal slab. Here, we present a quantum Monte Carlo (QMC) study for the benchmark system H2 + Cu(111), focusing on the dissociative chemisorption barrier height. These computationally extremely challenging ab initio calculations agree to within 1.6 ± 1.0 kcal/mol with a chemically accurate semiempirical value. Remaining errors, such as time-step errors and locality errors, are analyzed in detail in order to assess the reliability of the results. The benchmark studies presented here are at the cutting edge of what is computationally feasible at the present time. Illustrating not only the achievable accuracy but also the challenges arising within QMC in such a calculation, our study presents a clear picture of where we stand at the moment and which approaches might allow for even more accurate results in the future.

Diffusion Monte Carlo for Accurate Dissociation Energies of 3d Transition Metal Containing Molecules.

Transition metals and transition metal compounds are important to catalysis, photochemistry, and many superconducting systems. We study the performance of diffusion Monte Carlo (DMC) applied to transition metal containing dimers (TMCDs) using single-determinant Slater-Jastrow trial wavefunctions and investigate the possible influence of the locality and pseudopotential errors. We find that the locality approximation can introduce nonsystematic errors of up to several tens of kilocalories per mole in the absolute energy of Cu and CuH if Ar or Mg core pseudopotentials (PPs) are used for the 3d transition metal atoms. Even for energy differences such as binding energies, errors due to the locality approximation can be problematic if chemical accuracy is sought. The use of the Ne core PPs developed by Burkatzki et al. (J. Chem. Phys. 2008, 129, 164115), the use of linear energy minimization rather than unreweighted variance minimization for the optimization of the Jastrow function, and the use of large Jastrow parametrizations reduce the locality errors. In the second section of this article, we study the general performance of DMC for 3d TMCDs using a database of binding energies of 20 TMCDs, for which comparatively accurate experimental data is available. Comparing our DMC results to these data for our results that compare best with experiment, we find a mean unsigned error (MUE) of 4.5 kcal/mol. This compares well with the achievable accuracy in CCSDT(2)Q (MUE = 4.6 kcal/mol) and the best all-electron DFT results (MUE = 4.5 kcal/mol) for the same set of systems (Truhlar et al. J. Chem. Theory Comput. 2015, 11, 2036-2052). The mean errors in DMC depend less on the exchange-correlation functionals used to generate the trial wavefunction than the corresponding mean errors in the underlying DFT calculations. Furthermore, the QMC results obtained for each molecule individually vary less with the functionals used. These observations are relevant for systems such as molecules interacting with transition metal surfaces where the DFT functionals performing best for molecules (hybrids) do not yield improvements in DFT. Overall, the results presented in this article yield important guidelines for both the assessment of the achievable accuracy with DMC and the design of DMC calculations for systems including transition metal atoms.