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Density functional theory (DFT) calculations explore the stability of a single platinum atom on various flat, stepped, and defective ceria surfaces, in the context of single-atom catalysts (SACs) for the water-gas shift (WGS) reaction. The adsorption properties and diffusion kinetics of the metal strongly depend on the support termination with large stability on metastable and stepped CeO 2 (100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO 2 (111) and (110) terminations weakly bind the platinum atom and can promote the growth of metallic clusters thanks to fast diffusion kinetics. The adsorption of carbon monoxide on the single platinum atom supported on the various ceria terminations is also sensitive to the surface structure. Carbon monoxide weakly binds to the single platinum atom supported on reduced CeO 2 (111) and (211) terminations. The desorption of the CO 2 formed during the WGS reaction is thus facilitated on the latter terminations. A vibrational analysis underlines the significant changes in the calculated scaled anharmonic CO stretching frequency on these catalysts., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Ligand-decorated metal surfaces play a pivotal role in various areas of chemistry, particularly in selective catalysis. Molecular dynamics simulations at the molecular mechanics level of theory are best adapted to gain complementary insights to experiments regarding the structure and dynamics of such organic films. However, standard force fields tend to capture only weak physisorption interactions. This is inadequate for ligands that are strongly adsorbed such as carboxylates on metal surfaces. To address this limitation, we employ the Gaussian Lennard-Jones (GLJ) potential, which incorporates an attractive Gaussian potential between the surface and ligand atoms. Here, we develop this approach for the interaction between cobalt surfaces and carboxylate ligands. The accuracy of the GLJ approach is validated through the analysis of the interaction of oxygen with two distinct cobalt surfaces. The accuracy of this method reaches a root mean square deviation (RMSD) of about 3 kcal/mol across all probed configurations, which corresponds to a percentage error of roughly 4%. Application of the GLJ force field to the dynamics of the organic layer on these surfaces reveals how the ligand concentration influences the film order, and highlights differing mobility in the x and y directions, attributable to surface corrugation on Co(112̄0). GLJ is versatile, suitable for a broad range of metal/ligand systems, and can, subsequently, be utilized to study the organic film on the adsorption/desorption of reactants and products during a catalytic process., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

In computational surface catalysis, the calculation of activation energies of chemical reactions is expensive, which, in many cases, limits our ability to understand complex reaction networks. Here, we present a universal, machine learning-based approach for the prediction of activation energies for reactions of C-, O-, and H-containing molecules on transition metal surfaces. We rely on generalized Bronsted-Evans-Polanyi relationships in combination with machine learning-based multiparameter regression techniques to train our model for reactions included in the University of Arizona Reaction database. In our best approach, we find a mean absolute error for activation energies within our test set of 0.14 eV if the reaction energy is known and 0.19 eV if the reaction energy is unknown. We expect that this methodology will often replace the explicit calculation of activation energies within surface catalysis when exploring large reaction networks or screening catalysts for desirable properties in the future.

Identifying the surface species is critical in developing a realistic understanding of supported metal catalysts working in water. To this end, we have characterized the surface species present at a Ru/water interface by employing a hybrid computational approach involving an explicit description of the liquid water and a possible pressure of H 2 . On the close-packed, most stable Ru(0001) facet, the solvation tends to favor the full dissociation of water into atomic O and H in contrast with the partially dissociated water layer reported for ultra-high-vacuum conditions. The solvation stabilization was found to reach -0.279 J m 2 , which results in stable O and H species on Ru(0001) in the presence of liquid water even at room temperature. Conversely, introducing even a small H 2 pressure (10 -2 bar) results in a monolayer of chemisorbed H at the interface, a general trend found on the three most exposed facets of Ru nanoparticles. While hydroxyls were often hypothesized as possible surface species at the Ru/water interface, this computational study clearly demonstrates that they are not stabilized by liquid water and are not found under realistic reductive catalytic conditions.

Solvent effects are notoriously difficult to describe for metallic nanoparticles (NPs). Here, we introduce GAL21 which is the first pairwise additive force field that is specifically designed to modulate the near chemisorption energy of water as a function of the coordination numbers of the metallic atoms. We find a quadratic dependence to be most suitable for capturing the dependence of the adsorption energy of water on the generalized coordination number (GCN) of the metal atoms. GAL21 has been fitted against DFT adsorption energies for Cu, Ag, Au, Ni, Pd, Pt, and Co on 500 configurations and validated on about 3000 configurations for each metal, constructed on five surfaces with GCNs varying from 2.5 to 11.25. Depending on the metals, the root mean square deviation is found between 0.7 kcal mol -1 (Au) to 1.6 kcal mol -1 (Ni). Using GAL21, as implemented in the open-source code CP2K, we then evaluate the solvation energy of Au 55 and Pt 55 NPs in water using thermodynamic integration. The solvation free energy is found to be larger for Pt than for Au and systematically larger than 200 kcal mol -1 , demonstrating the large impact of solvent on the surface energetics of NPs. Still, given that the amorphous NPs are both, the most stable and the most solvated ones, we do not predict a change in the preferred morphology between the gas-phase and in water. Finally, based on a linear regression on three sizes of NPs (from 38 to 147), the solvation energy for Au and Pt surface atoms is found to be -5.2 and -9.9 kcal mol -1 , respectively.

Sensorimotor aftereffects have been widely studied after lateral prism adaptation but not after vertical prism adaptation. It is thus well-known that lateral prism adaptation produces aftereffects on visuospatial representation and, recently, on auditory perception. This study aimed to explore the sensorimotor after-effects of vertical prism adaptation as well as its aftereffects on vertical visuospatial representation (Experiment 1) and on auditory frequency representation (Experiment 2). The experimental procedure was similar in both experiments: before and after prism adaptation to an upward or a downward optical deviation, healthy young participants performed an visual open-loop pointing task and a visual (Experiment 1) or an auditory (Experiment 2) perceptual bisection task. In the visual task, the participants had to indicate if they perceived the bisection as higher or lower than the true center of a line. In the auditory task, the participants had to indicate if they perceived the target auditory frequency closer to the low or the high limit of an auditory interval. For sensorimotor aftereffects, pointing errors were computed by means of a vertical touchscreen. For the perceptual bisection task, we measured the percentage of "down" (Experiment 1) or "low" responses (Experiment 2), and we computed the visual (Experiment 1) or the auditory (Experiment 2) subjective center for each participant. Statistical analyses were carried out separately for each optical deviation in each experiment. Sensorimotor aftereffects were observed in both experiments, in the opposite direction to the optical deviation (all p s < 0.01). No significant aftereffects occurred on visuospatial representation (all p s > 0.5), whereas the percentage of "low" responses and the auditory subjective center significantly increased after adaptation to a downward optical deviation (all p s < 0.05). Unlike lateral prism adaptation aftereffects that have been previously shown in both visuospatial horizontal representation and auditory frequency representation, aftereffects of vertical prism adaptation occurred in the auditory frequency representation but not in the vertical visuospatial representation. These results suggest that both vertical and lateral prism adaptations share a common substrate dedicated to the auditory modality (probably the temporal cortex), and that vertical adaptation does not act on the neural substrate of vertical visuospatial representation., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Bonnet, Poulin-Charronnat, Ardonceau, Sirandré, Bard and Michel.)

Objective: Prism adaptation was shown to modify auditory perception. Using a dichotic listening task, which assesses auditory divided attention, benefits of a rightward prism adaptation were demonstrated in neglect patients (i.e., a syndrome following right hemisphere brain damage) by reducing their left auditory extinction. It is currently unknown whether prism adaptation affects auditory divided attention in healthy subjects. In the present study, we investigated the aftereffects of prism adaptation on dichotic listening., Method: A sample of 47 young adults performed a dichotic listening task, in which pairs of words were presented with two words sounded simultaneously, one in each ear. Three parameters were measured: The percentage of recalled words, the percentage of correctly recalled words, and the laterality index (LI)., Results: Prism adaptation to a leftward optical deviation (L-PA) significantly increased the overall percentage of recalled words ( p = .044) and that from the right ear ( p = .002), and the overall LI ( p = .049)., Conclusions: For the first time, these findings demonstrate that L-PA produced an orientation of the auditory divided attention in favor of the right ear in healthy participants. This asymmetrical aftereffect provides a new argument in favor of the cross-modal dimension of prism adaptation, although an acclimatization effect of the dichotic listening task is also discussed. Our study opens up a new avenue for using prism adaptation in the field of auditory rehabilitation requiring a modulation of auditory attention. (PsycInfo Database Record (c) 2022 APA, all rights reserved).

Organic/oxide interfaces play an important role in many areas of chemistry and in particular for lubrication and corrosion. Molecular dynamics simulations are the method of choice for providing complementary insight to experiments. However, the force fields used to simulate the interaction between molecules and oxide surfaces tend to capture only weak physisorption interactions, discarding the stabilizing Lewis acid/base interactions. We here propose a simple complement to the straightforward molecular mechanics description based on "out-of-the-box" Lennard-Jones potentials and electrostatic interactions: the addition of an attractive Gaussian potential between reactive sites of the surface and heteroatoms of adsorbed organic molecules, leading to the Gaussian Lennard-Jones (GLJ) potential. The interactions of four oxygenated and four amine molecules with the typical and widespread hematite and γ-alumina surfaces are investigated. The root mean square deviation (RMSD) for all probed molecules is only 5.7 kcal/mol, which corresponds to an error of 23% over hematite. On γ-alumina, the RMSD is 11.2 kcal/mol using a single parameter for all five chemically inequivalent surface aluminum atoms. Applying GLJ to the simulation of organic films on oxide surfaces demonstrates that the mobility of the surfactants is overestimated by the simplistic LJ potential, while GLJ and other qualitatively correct potentials show a strong structuration and slow dynamics of the surface films, as could be expected from the first-principles adsorption energies for model head groups.

Acceptorless dehydrogenation into carbonyls and molecular hydrogen is an attractive strategy to valorize (biobased) alcohols. Using 2-octanol dehydrogenation as benchmark reaction in a continuous reactor, a library of metal-supported catalysts is tested to validate the predictive level of catalytic activity for combined DFT and micro-kinetic modeling. Based on a series of transition metals, scaling relations are determined as a function of two descriptors, i.e. the surface binding energies of atomic carbon and oxygen. Then, a volcano-shape relation based on both descriptors is derived, paving the way to further optimization of active catalysts. Evaluation of 294 diluted alloys but also a series of carbides and nitrides with the volcano map identified 12 promising candidates with potentially improved activity for alcohol dehydrogenation, which provides useful guidance for experimental catalyst design. Further screening identifies β-Mo 2 N and γ-Mo 2 N exposing mostly (001) and (100) facets as potential candidates for alcohol dehydrogenation., (© 2021. The Author(s).)

We present the open-source python package DockOnSurf which automates the generation and optimization of low-energy adsorption configurations of molecules on extended surfaces and nanoparticles. DockOnSurf is especially geared toward handling polyfunctional flexible adsorbates. The use of this high-throughput workflow allows us to carry out the screening of adsorbate-surface configurations in a systematic, customizable, and traceable way, while keeping the focus on the chemically relevant structures. The screening strategy consists in splitting the exploration of the adsorbate-surface configurational space into chemically meaningful domains, that is, by choosing among different conformers to adsorb, surface adsorption sites, adsorbate anchoring points, and orientations and allowing dissociation of (acidic) protons. We demonstrate the performance of the main features based on varying examples, ranging from CO adsorption on a gold nanoparticle to sorbitol adsorption on hematite. Through the use of the presented program, we aim to foster efficiency, traceability, and ease of use in research within tribology, catalysis, nanoscience, and surface science in general.

Converting biomass into sustainable chemicals and energy feed-stocks requires innovative heterogeneous catalysts, which are able to efficiently work under aqueous conditions. Computational chemistry is a key asset in the design of these novel catalysts, but it has to face two challenges: the large reaction networks and the potential role of hydration. They can be addressed using scaling relations such as Brønsted-Evans-Polanyi (BEP) and solvation models, respectively. In this study, we show that typical reaction and activation energies of alcohol decomposition on Pt(111) are not strongly modified by the inclusion of the water solvent as a continuum model. In contrast, adding a single water molecule strongly favours O-H and C-OH scission and it prevents C-O and to a lesser extent C-C scissions. The resulting BEP relationships partially reflect these changes induced by the solvent. Predicting Pt-catalysed alcohol decomposition in water should thus account for the influence of the solvent on thermodynamics and kinetics. In addition, we found that the reaction energies obtained in the presence of an explicit water molecule scale with the ones obtained in a vacuum. Hence, we reveal that vacuum computations in combination with corrections based on our linear regressions are able to capture the important H-bonding effect.

To better identify the distinctive characteristics of space representation in the radial dimension, we have proposed a new paradigm: the landmarks alignment task where two parallel aluminum bars were radially presented. Children had to move a landmark along one bar and place it at the same location as the reference landmark placed by the examiner on the parallel bar. The major interest of this task was its capacity to assess space representation in the radial dimension when considering a spatial landmark that oriented the subject's attention toward the orthogonal dimension. The most important result showed that in the radial dimension children with dyslexia exhibited a forward bias on the left bar, meaning a mental underrepresentation of the leftward peripersonal space and/or a mental overrepresentation of the rightward peripersonal space. Furthermore, reading discrepancies were correlated with radial forward bias on the left bar. The experiment was also conducted in the lateral axis, showing a pseudoneglect behavior in children without dyslexia. Our landmarks alignment task had the advantage of being able to assess space representation in a complex environment. The forward radial representational bias in children with dyslexia could have implications for spatial orientation in peripersonal workspace in school situations.

Among the best-performing homogeneous catalysts for the direct amination of activated secondary alcohols with electron-poor amine derivatives, metal triflates, such as aluminum triflate, Al(OTf) 3 , stand out. Herein we report the extension of this reaction to electron-rich amines and activated primary alcohols. We provide detailed insight into the structure and reactivity of the catalyst under working conditions in both nitromethane and toluene solvent, through experiment (cyclic voltammetry, conductimetry, NMR spectroscopy), and density functional theory (DFT) simulations. Competition between aniline and benzyl alcohol for Al in the two solvents explains the different reactivities. The catalyst structures predicted from the DFT calculations were validated by the experiments. Whereas a S N 1-type mechanism was found to be active in nitromethane, we propose a S N 2 mechanism in toluene to rationalize the much higher selectivity observed when using this solvent. Also, unlike what is commonly assumed in homogeneous catalysis, we show that different active species may be active instead of only one., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Prism adaptation is a well-known model to study sensorimotor adaptive processes. It has been shown that following prism exposure, after-effects are not only restricted to the sensorimotor level but extend as well to spatial cognition. The main purpose of the present study was to investigate in healthy individuals whether expansion to spatial cognition is restricted to adaptive processes peculiar to prism adaptation or whether it occurs as well following other forms of adaptive process such as adaptation to a novel dynamic environment during pointing movements. Representational after-effects were assessed by the perceptual line bisection task before and after adaptation to a leftward or a rightward force field. The main results showed that adaptation developed at sensorimotor level but did not influence space representation. Our results have therefore a strong methodological impact for prospective investigations focusing on sensorimotor plasticity while sparing space cognition. These methodological considerations will be particulary relevant when addressing sensorimotor plasticity in patients with specific representational feature to preserve. The discussion highlights the differences between prism and dynamic adaptation that could explain the lack of after-effect on space representation following force field adaptation.

We report herein a detailed and accurate study of the mechanism of rhodium-catalysed conversion of glycerol into 1,2-propanediol and lactic acid. The first step of the reaction is particularly debated, as it can be either dehydration or dehydrogenation. It is expected that these elementary reactions can be influenced by pH variations and by the nature of the gas phase. These parameters were consequently investigated experimentally. On the other hand, there was a lack of knowledge about the behaviour of glycerol at the surface of the metallic catalyst. A theoretical approach on a model Rh(111) surface was thus implemented in the framework of density functional theory (DFT) to describe the above-mentioned elementary reactions and to calculate the corresponding transition states. The combination of experiment and theory shows that the dehydrogenation into glyceraldehyde is the first step for the glycerol transformation on the Rh/C catalyst in basic media under He or H(2) atmosphere., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements ((1)H, (31)P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.