Transition-State Searches in Metal Clusters by First-Principle Methods

Cruz-Olvera, Domingo; Vasquez, Alejandra de la Trinidad; Geudtner, Gerald; Vásquez-Pérez, José Manuel; Calaminici, Patrizia; Köster, Andreas M.

doi:10.1021/jp506121f

Cited by 9 publications

(8 citation statements)

References 59 publications

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“…Interpolation Algorithms: One intuitive approach to find the transition state between intermediates is to construct a "chain-of-states" along the MEP by interpolating coordinates between the known reaction intermediates. 698 Interpolative schemes optimize a series of static chemical configurations referred to as images along the PES between the reactants and products to create a 2D energy profile; the resolution (and expense) of interpolation schemes is a function of the number of images as well as the chemical system, and their convergence relies on having a well-converged description of the starting materials and products. 699 Still, constructing a chain-of-states both reduces computational cost by limiting the degrees of freedom to sample, and ensures extracted geometries belong to the appropriate reaction coordinate.…”

Section: Kinetics and Transition State Searchesmentioning

confidence: 99%

Electronic Structure Modeling of Metal–Organic Frameworks

et al. 2020

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Owing to their molecular building blocks, yet highly crystalline nature, metal−organic frameworks (MOFs) sit at the interface between molecule and material. Their diverse structures and compositions enable them to be useful materials as catalysts in heterogeneous reactions, electrical conductors in energy storage and transfer applications, chromophores in photoenabled chemical transformations, and beyond. In all cases, density functional theory (DFT) and higher-level methods for electronic structure determination provide valuable quantitative information about the electronic properties that underpin the functions of these frameworks. However, there are only two general modeling approaches in conventional electronic structure software packages: those that treat materials as extended, periodic solids, and those that treat materials as discrete molecules. Each approach has features and benefits; both have been widely employed to understand the emergent chemistry that arises from the formation of the metal−organic interface. This Review canvases these approaches to date, with emphasis placed on the application of electronic structure theory to explore reactivity and electron transfer using periodic, molecular, and embedded models. This includes (i) computational chemistry considerations such as how functional, k-grid, and other model variables are selected to enable insights into MOF properties, (ii) extended solid models that treat MOFs as materials rather than molecules, (iii) the mechanics of cluster extraction and subsequent chemistry enabled by these molecular models, (iv) catalytic studies using both solids and clusters thereof, and (v) embedded, mixed-method approaches, which simulate a fraction of the material using one level of theory and the remainder of the material using another dissimilar theoretical implementation.

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Section: Kinetics and Transition State Searchesmentioning

confidence: 99%

Electronic Structure Modeling of Metal–Organic Frameworks

et al. 2020

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“…Clusters bridge the disciplines of physics, chemistry, biology, materials science, and medicine. Many books, − conference proceedings, ,− and review articles − …”

Section: Introductionmentioning

confidence: 97%

Super Atomic Clusters: Design Rules and Potential for Building Blocks of Materials

2018

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Atomic clusters, consisting of a few to a few thousand atoms, have emerged over the past 40 years as the ultimate nanoparticles, whose structure and properties can be controlled one atom at a time. One of the early motivations in studying clusters was to understand how the properties of matter evolve as a function of size, shape, and composition. Over the past few decades, more than 200 000 papers have been published in this field. These studies have not only led to a considerable understanding of this evolution from clusters to crystals, but also have revealed many unusual size-specific properties that make cluster science an interdisciplinary field on its own, bridging physics, chemistry, materials science, biology, and medicine. More importantly, the possibility of creating a new class of materials, composed of clusters instead of atoms as building blocks, has fueled the hope that one can synthesize materials from the bottom-up with unique and tailored properties. This Review focuses on the properties that set clusters apart from their corresponding bulk. Furthermore, this Review describes how different electron-counting rules can lead to the design of stable clusters, mimicking the chemistry of atoms. We highlight the potential of these "superatoms" as building blocks of cluster-assembled materials. Specifically, we emphasize cluster-inspired materials for energy applications. The concluding section includes a summary of the salient features of clusters, potential challenges that remain, and an outlook for the future of cluster science.

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“…To this end a robust and reliable hierarchical transition state search algorithm has been developed. The here employed hierarchical transition state algorithm combines the so-called double ended saddle interpolation method with the uphill trust region method. , The hierarchical transition state search algorithm has been extensively applied to small test reactions, to Diels–Alder show case reactions, to Pd 13 oxidation, to conformational rearrangements in glycerol, and to reactions of pure metal clusters . The saddle interpolation method is used for obtaining a starting point for the local transition state (TS) search which is performed by the uphill trust region method with eigenvector following.…”

Section: Introductionmentioning

confidence: 99%

Isomerization Reactions of the Cu₁₅V⁺ Cluster: A Density Functional Theory Study

2022

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The investigation of the chemical reactivity of complex systems such as transition metal clusters is a very complicated task because often the structures of the corresponding transition states are far from being intuitive. Bimetallic transition metal clusters represent a particular class of complex systems. In this work, density functional theory (DFT) is applied to study the isomerization reactions of the Cu15V+ cluster. Full geometry optimizations of dozens of initial structures taken along Born–Oppenheimer molecular dynamics (BOMD) trajectories were performed using a quasi-Newton method in a reduced space Cartesian coordinate system that works considering the internal degrees of freedom. Harmonic frequencies calculations were performed at the optimized structures. To study the isomerization reactions between the obtained stable isomers, a hierarchical transition state algorithm has been applied to locate the transition states of this cluster. The found transition states were than connected with the corresponding minimum structures by calculating the intrinsic reaction coordinates. This work demonstrates the capability of the applied method to study non-intuitive rearrangement mechanisms in complex finite systems and to create networks between minima and transition state structures on their potential energy surface.

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Transition-State Searches in Metal Clusters by First-Principle Methods

Cited by 9 publications

References 59 publications

Electronic Structure Modeling of Metal–Organic Frameworks

Electronic Structure Modeling of Metal–Organic Frameworks

Super Atomic Clusters: Design Rules and Potential for Building Blocks of Materials

Isomerization Reactions of the Cu₁₅V⁺ Cluster: A Density Functional Theory Study

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Transition-State Searches in Metal Clusters by First-Principle Methods

Cited by 9 publications

References 59 publications

Electronic Structure Modeling of Metal–Organic Frameworks

Electronic Structure Modeling of Metal–Organic Frameworks

Super Atomic Clusters: Design Rules and Potential for Building Blocks of Materials

Isomerization Reactions of the Cu15V+ Cluster: A Density Functional Theory Study

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Product

Resources

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Isomerization Reactions of the Cu₁₅V⁺ Cluster: A Density Functional Theory Study