DFT-based Theoretical Simulations for Photocatalytic Applications Using TiO2

TiO2 has been shown to be a potential candidate for photoinitiated processes, such as dye sensitized solar cells and water splitting in production of H2. The large band gap of TiO2 can be reduced by functionalizing the oxide by adsorbing dye molecules and/or water reduction/oxidation catalysts, by metal/nonmetal doping, and by mixing with another oxide. Due to these methods, several different TiO2‐based complexes can be constructed having different geometries, electronic structures, and optical characteristics. It is practically impossible to test the photocatalytic activity of all possible TiO2‐based complexes using only experimental techniques. Instead, density functional theory (DFT)‐based theoretical simulations can easily guide experimental studies by screening materials and providing insights into the photoactivity of the complexes. The aim of this chapter is to provide an outlook for current research on DFT‐based simulations of TiO2 complexes for dye sensitized solar cells and water splitting applications and to address challenges of theoretical simulations

Nuclear quantum effects at aqueous metal interfaces captured by molecular dynamics simulations

In this review, we summarize the recent development in modeling nuclear quantum effects at aqueous metal interfaces. First, we review the nuclear quantum effects on the water-metal interface at ultra-high vacuum. Then, we illustrate the nuclear quantum effects at the potential of zero charge conditions. At last, we give some outlook for the perspective work in modeling the nuclear quantum effects at electrochemical interfaces and some practical simulation strategies

Fast evaluation of solid harmonic Gaussian integrals for local resolution-of-the-identity methods and range-separated hybrid functionals

An integral scheme for the efficient evaluation of two-center integrals over contracted solid harmonic Gaussian functions is presented. Integral expressions are derived for local operators that depend on the position vector of one of the two Gaussian centers. These expressions are then used to derive the formula for three-index overlap integrals where two of the three Gaussians are located at the same center. The efficient evaluation of the latter is essential for local resolution-of-the-identity techniques that employ an overlap metric. We compare the performance of our integral scheme to the widely used Cartesian Gaussian-based method of Obara and Saika (OS). Non-local interaction potentials such as standard Coulomb, modified Coulomb and Gaussian-type operators, that occur in range-separated hybrid functionals, are also included in the performance tests. The speed-up with respect to the OS scheme is up to three orders of magnitude for both, integrals and their derivatives. In particular, our method is increasingly efficient for large angular momenta and highly contracted basis sets.Comment: 18 pages, 2 figures; accepted manuscript. v2: supplementary material include

Understanding the role of oxygen-vacancy defects in Cu₂O(111) from first-principle calculations

The presence of defects, such as copper and oxygen vacancies, in cuprous oxide films determines their characteristic carrier conductivity and consequently their application as semiconducting systems. There are still open questions on the induced electronic re-distribution, including the formation of polarons. Indeed, to accurately reproduce the structural and electronic properties at the cuprous oxide surface, very large slab models and theoretical approaches that go beyond the standard generalized gradient corrected density functional theory are needed. In this work we investigate oxygen vacancies formed in proximity of a reconstructed Cu$_{2}$O(111) surface, where the outermost unsaturated copper atoms are removed, thus forming non-stoichiometric surface layers with copper vacancies. We address simultaneously surface and bulk properties by modelling a thick and symmetric slab, to find that hybrid exchange-correlation functionals are needed to describe the oxygen vacancy in this system. Our simulations show that the formation of oxygen vacancies is favoured in the sub-surface layer. Moreover, the oxygen vacancy leads to a splitting and left-shift of the shallow hole states in the gap, which are associated with the deficiency of copper at the surface. These findings suggest that surface electronic structure and reactivity are sensitive to the presence of oxygen vacancies, also when the latter are formed deeper within the film

Low-Frequency Anharmonic Couplings in Crystalline Bromoform: Theory

Theoretical calculations of the low-frequency anharmonic couplings of the beta-phase of crystalline bromoform are presented, based on DFT quantum chemistry calculations. Electrical and mechanical anharmonicities between intra- and intermolecular modes are calculated, revealing that electrical anharmonicity dominates the cross peaks intensities in the 2D Raman-THz response and crystalline, as well as liquid, bromoform. Furthermore, the experimentally observed difference in relative cross peak intensities between the two intramolecular modes of bromoform and intermolecular modes can be explained by orientational averaging, taking into account the double-degeneracy of the lower-frequency intramolecular mode. The good agreement with experimental results provides further evidence for our interpretation that the 2D Raman-THz response of bromoform is indeed related to the anharmonic coupling between intra- and intermolecular modes

Connection between water's dynamical and structural properties: insights from ab initio simulations

Among all fluids, water has always been of special concern for scientists from a broad variety of research fields due to its rich behavior. In particular, some questions remain unanswered nowadays concerning the temperature dependence of bulk and interfacial transport properties of supercooled and liquid water, e.g. regarding the fundamentals of the violation of the Stokes-Einstein relation in the supercooled regime or the subtle relation between structure and dynamical properties. Here we investigated the temperature dependence of the bulk transport properties from ab initio molecular dynamics based on density functional theory, down to the supercooled regime. We determined from a selection of functionals, that SCAN better describes the experimental viscosity and self-diffusion coefficient, although we found disagreements at the lowest temperatures. For a limited set of temperatures, we also explored the role of nuclear quantum effects on water dynamics using ab initio molecular dynamics that has been accelerated via a recently introduced machine learning approach. We then investigated the molecular mechanisms underlying the different functionals performance and assessed the validity of the Stokes-Einstein relation. We also explored the connection between structural properties and the transport coefficients, verifying the validity of the excess entropy scaling relations for all the functionals. These results pave the way to predict the transport coefficients from the radial distribution function, helping to develop better functionals. On this line, they indicate the importance of describing the long-range features of the radial distribution function.Comment: 10 pages, 5 figure

Connection between water’s dynamical and structural properties: Insights from ab initio simulations

Among all fluids, water has always been of special concern for scientists from a wide variety of research fields because of its rich behavior. In particular, some questions remain unanswered today regarding the temperature dependence of bulk and interfacial transport properties of supercooled and liquid water, for example, regarding the fundamentals of the violation of the Stokes–Einstein relation in the supercooled regime, or the subtle relation between structure and dynamical properties. We have studied the temperature dependence of the bulk transport properties from ab initio molecular dynamics based on density functional theory, down to the supercooled regime. We determined, from a selection of functionals, that the SCAN (strongly constrained and appropriately normed) functional best describes the experimental viscosity and self-diffusion coefficient, although we found disagreements at lower temperatures. For a limited set of temperatures, we also explored the role of nuclear quantum effects on water dynamics using ab initio molecular dynamics that was accelerated by a recently introduced machine learning approach. We then investigated the molecular mechanisms underlying the different functionals’ performance and assessed the validity of the Stokes–Einstein relation. We also explored the connection between structural properties and transport coefficients, verifying the validity of the excess entropy scaling relations for all functionals. These results pave the way for the prediction of the transport coefficients from the radial distribution function, thus helping to develop better functionals. In this respect, these results indicate the importance of describing the long-range features of the radial distribution function

Hexagonal boron nitride on transition metal surfaces

We validate a computational setup based on density functional theory to investigate hexagonal boron nitride (h-BN) monolayers grown on different transition metals exposing hexagonal surfaces. An extended assessment of our approach for the characterization of the geometrical and electronic structure of such systems is performed. Due to the lattice mismatch with the substrate, the monolayers can form Moiré-type superstructures with very long periodicities on the surface. Thus, proper models of these interfaces require very large simulation cells (more than 1,000 atoms) and an accurate description of interactions that are modulated with the specific registry of h-BN on the metal. We demonstrate that efficient and accurate calculations can be performed in such large systems using Gaussian basis sets and dispersion corrections to the (semi-)local density functionals. Four different metallic substrates, Rh(111), Ru(0001), Cu(111), and Ni(111), are explicitly considered, and the results are compared with previous experimental and computational studie

In situ spectroelectrochemical probing of CO redox landscape on copper single-crystal surfaces

Electrochemical reduction of CO$_{(2)}$to value-added chemicals and fuels is a promising strategy to sustain pressing renewable energy demands and to address climate change issues. Direct observation of reaction intermediates during the CO$_{(2)}$reduction reaction will contribute to mechanistic understandings and thus promote the design of catalysts with the desired activity, selectivity, and stability. Herein, we combined in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy and ab initio molecular dynamics calculations to investigate the CORR process on Cu single-crystal surfaces in various electrolytes. Competing redox pathways and coexistent intermediates of CO adsorption (*CO$_{atop}$and *CO$_{bridge}$), dimerization (protonated dimer *HOCCOH and its dehydrated *CCO), oxidation (*CO$_{2}$$^{−}$and *CO$_{3}$$^{2−}$), and hydrogenation (*CHO), as well as Cu-O$_{ad}$/Cu-OH$_{ad}$species at Cu-electrolyte interfaces, were simultaneously identified using in situ spectroscopy and further confirmed with isotope-labeling experiments. With AIMD simulations, we report accurate vibrational frequency assignments of these intermediates based on the calculated vibrational density of states and reveal the corresponding species in the electrochemical CO redox landscape on Cu surfaces. Our findings provide direct insights into key intermediates during the CO$_{(2)}$RR and offer a full-spectroscopic tool (40–4,000 cm$^{−1}$) for future mechanistic studies