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Boosting Computational Catalysis and Chemical Reactivity with Artificial Intelligence
Konstantinos D. Vogiatzis,* Clémence Corminboeuf, Ainara Nova, Kjell Jorner, Johannes Kästner, Markus Meuwly, Philippe Schwaller, Victor Böttcher, Maria Drosou, Edvin Fako, Hannes Hoppe, Zarko Ivkovic, Nestor Iwanojko, Dimitrios A. Pantazis, Stefan P. Schmid, Kalman Szenes, Auguste Tetenoire, Markus Reiher* JACS (2026) XXX-XXX
Artificial intelligence (AI) and machine learning (ML) are rapidly reshaping the landscape of computational chemistry, offering new opportunities for accelerating catalyst discovery and deepening our understanding of chemical reactivity. This perspective highlights emerging methodologies ranging from machine learning potentials and reinforcement learning to generative AI and large language models that are poised to transform computational catalysis. We discuss challenges in developing robust molecular representations for transition-metal complexes, bridging mechanistic understanding with AI-driven predictions, and constructing reliable data sets that capture both successful and failed reactivity outcomes. By drawing on the authors’ practical experience across computational, experimental, and AI-driven domains, we emphasize the importance of integrating chemical intuition and methodological expertise with data-driven approaches while remaining open to serendipitous discoveries enabled by automation and self-driving laboratories. Ultimately, the future of computational catalysis lies in balancing human intuition with algorithmic power, leveraging AI not as a replacement but as an accelerator of chemical insight, mechanistic understanding, and catalyst design.
Multipodal Au–C grafting of calix[4]arene molecules on gold nanorods
Auguste Tetenoire, Anna Omelchuk, Volodymyr Malytskyi, Ivan Jabin, Victor Lepeintre, Gilles Bruylants, Yun Luo, Arnaud Fihey, Mikaël Kepenekian* and Corinne Lagrost* Chem. Sci. (2024) 15, 14677 - 14684
The interface robustness and spatial arrangement of functional molecules on metallic nanomaterials play a key part in the potential applications of functional nano-objects. The design of mechanically stable and electronically coupled attachments with the underlying metal is essential to bring specific desirable properties to the resulting hybrid materials. In this context, rigid multipodal platforms constitute a unique opportunity for the controllable grafting of functionality. Herein, we provide for the first time an in-depth description of the interface between gold nanorods and a chemically-grafted multipodal platform based on diazonium salts. Thanks to Raman and X-ray photoelectron spectroscopies and theoretical modeling, we deliver insights on the structural and electronic properties of the hybrid material. More importantly, it allows for the accurate assignment of Raman bands. The combination of experimental and theoretical results establishes the formation of four carbon–gold anchors for the calix[4]arene macrocycle leading to the exceptional stability of the functionalized nano-objects. Our results lay the foundations for the future design of robust and versatile platforms.
Understanding the Photoinduced Desorption and Oxidation of CO on Ru(0001) Using a Neural Network Potential Energy Surface
Ivan Žugec*, Auguste Tetenoire, Alberto S. Muzas, Yaolong Zhang, Bin Jiang, Maite Alducin*, and J. Iñaki Juaristi* JACS Au (2024) 4, 5, 1997–2004
The study of ultrafast photoinduced dynamics of adsorbates on metal surfaces requires thorough investigation of laser-excited electrons and, in many cases, the highly excited surface lattice. While ab initio molecular dynamics with electronic friction and thermostats (Te, Tl)-AIMDEF addresses such complex modeling, it imposes severe computational costs, hindering quantitative comparison with experimental desorption probabilities. In order to bypass this limitation, we utilize the embedded atom neural network method to construct a potential energy surface (PES) for the coadsorption of CO and O on Ru(0001). Our results demonstrate that this PES not only reproduces the short-time ab initio dynamics but is also able to yield statistically significant data for long lasting trajectories that correlate well with experimental findings. Furthermore, the analysis of the laser-induced dynamics reveals the existence of a dynamic trapping state that acts as a precursor for CO desorption, and it is not observed under thermal conditions. Altogether, our results validate the underlying theoretical framework, providing robust support for the description of not only the photoinduced desorption but also the oxidation of CO in terms of nonequilibrated but thermal hot electrons and phonons.
Disentangling the role of electrons and phonons in the photoinduced CO desorption and CO oxidation on (O,CO)-Ru(0001)
Auguste Tetenoire*, J. Iñaki Juaristi*, and Maite Alducin* Front. Chem. (2023) 11, 1235176
The role played by electronic and phononic excitations in the femtosecond laser induced desorption and oxidation of CO coadsorbed with O on Ru(0001) is investigated using ab initio molecular dynamics with electronic friction. To this aim, simulations that account for both kind of excitations and that only consider electronic excitations are performed. Results for three different surface coverages are obtained. We unequivocally demonstrate that CO desorption is governed by phononic excitations. In the case of oxidation the low statistics does not allow to give a categorical answer. However, the analysis of the adsorbates kinetic energy gain and displacements strongly suggest that phononic excitations and surface distortion also play an important role in the oxidation process.
Photoinduced CO Desorption Dominates over Oxidation on Different O + CO Covered Ru(0001) Surfaces
Auguste Tetenoire*, J. Iñaki Juaristi*, and Maite Alducin* J. Phys. Chem. C (2023) 127, 21, 10087–10096
The photoinduced desorption and oxidation of CO on Ru(0001) is simulated using ab initio molecular dynamics with electronic friction that accounts for the nonequilibrated excited electrons and phonons. Different (O,CO) coverages are considered, the experimental room temperature coverage consisting in 0.5 ML-O + 0.25 ML-CO (low coverage), the saturation coverage achieved experimentally at low temperatures (0.5 ML-O + 0.375 ML-CO, intermediate coverage), and the equally mixed monolayer that is stable according to our calculations but not experimentally observed yet (0.5 ML-O + 0.5 ML-CO, high coverage). The results of our simulations for the three coverages are consistent with femtosecond laser experiments showing that the CO photodesorption largely dominates over CO photo-oxidation. These results cannot be explained in terms of the distinct activation energies calculated for the relaxed surfaces. Different (dynamical) factors such as the coupling to the laser-excited electrons and, more importantly, the interadsorbate energy exchange and the strong surface distortions induced in the more crowded surfaces are fundamental to understand the competition between these two processes under the extremely nonequilibrated conditions created by the laser.
Why Ultrafast Photoinduced CO Desorption Dominates over Oxidation on Ru(0001)
Auguste Tetenoire, Christopher Ehlert, J. I. Juaristi, Peter Saalfrank, and M. Alducin* J. Phys. Chem. Lett. (2022) 13, 36, 8516–8521
CO oxidation on Ru(0001) is a long-standing example of a reaction that, being thermally forbidden in ultrahigh vacuum, can be activated by femtosecond laser pulses. In spite of its relevance, the precise dynamics of the photoinduced oxidation process as well as the reasons behind the dominant role of the competing CO photodesorption remain unclear. Here we use ab initio molecular dynamics with electronic friction that account for the highly excited and nonequilibrated system created by the laser to investigate both reactions. Our simulations successfully reproduce the main experimental findings: the existence of photoinduced oxidation and desorption, the large desorption to oxidation branching ratio, and the changes in the O K-edge X-ray absorption spectra attributed to the initial stage of the oxidation process. Now, we are able to monitor in detail the ultrafast CO desorption and CO oxidation occurring in the highly excited system and to disentangle what causes the unexpected inertness to the otherwise energetically favored oxidation.
Insights into the Coadsorption and Reactivity of O and CO on Ru(0001) and Their Coverage Dependence
Auguste Tetenoire*, J. Iñaki Juaristi*, and Maite Alducin* J. Phys. Chem. C (2021) 125, 23, 12614–12627
Using density functional theory and an exchange–correlation functional that includes the van der Waals interaction, we study the coadsorption of CO on Ru(0001) saturated with 0.5 ML of oxygen. Different coexisting CO coverages are considered that are experimentally motivated, the room temperature coverage consisting of 0.5 ML-O + 0.25 ML-CO (low coverage), the saturation coverage achieved at low temperatures (0.5 ML-O + 0.375 ML-CO, intermediate coverage), and the equally mixed monolayer that is stable according to our calculations but not experimentally observed yet (0.5 ML-O + 0.5 ML-CO, high coverage). For each coverage, we study the competition between the desorption and oxidation of CO on the corresponding optimized structure by analyzing their reaction energies and minimum energy reaction paths. The desorption process is endothermic at all coverages, although the desorption energy decreases as the CO coverage increases. The process itself (and also the reverted adsorption) becomes more involved at the intermediate and high coverages because of the appearance of a physisorption well and concomitant energy barrier separating it from the chemisorbed state. Remarkably, the oxidation of CO, which is endothermic at low coverages, turns exothermic at the intermediate and high coverages. In all cases, the minimum reaction path for oxidation, which involves the chemisorbed and physisorbed CO2, is ruled by one of the large energy barriers that protect these molecular states. Altogether, the larger activation energies for oxidation as compared to those for desorption and the extreme complexity of the oxidation against the desorption paths explain that CO desorption dominates over the oxidation in experiments.
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