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Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity

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Abstract

A new multicentered effective group potential (EGP) is obtained for η6-benzene. Applications on \([\hbox{Ru}_{4}(\hbox{H})_{4}(\hbox{C}_{6}\hbox{H}_{6})_{4}]^{n+}\) clusters (n = 0 or 2) are in excellent agreement with reference DFT studies in terms of geometries, energies and electronic structures. In particular, the small singlet–triplet energy difference (3.8 kcal mol−1) in [Ru4(H)4(C6H6)4]2+ is very well reproduced. This new EGP is nevertheless not free from the limitations associated to this first generation of molecular pseudopotentials. A cautious analysis of the nature and exact role of this EGP is made, which provides new directions for the elaboration of the next generation of EGPs. In addition, the η5-cyclopentadienyl EGP has been used to perform a constrained dynamical simulation for the reaction of Cp2LaH with H2. The energy conservation during the simulation as well as the activation barrier extracted from the simulation clearly demonstrate the good behavior of this EGP in the context of molecular dynamics. Anharmonic effects on this reaction are underlined, further demonstrating the high accuracy of the potential energy surface obtained with EGPs. From a more general point of view, such EGPs are expected to provide accurate albeit low-cost ligand-field effects in organometallic clusters or nanoparticles and to allow dynamical studies at the surface of such compounds.

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Acknowledgments

We thank the CALcul en MIdi-Pyrénées (CALMIP) for generous allocations of computer time. Laurent Maron is member of the Institut Universitaire de France (IUF). Financial support by the CNRS and the ANR (SIDERUS project, ANR-08-BLAN-0010-01 and ANR-08-BLAN-0010-02) is gratefully acknowledged. This work is dedicated to the memory of Dr Jean-Pierre Daudey, who was affectionately called by us “Ze Guru”. EGP extractions and applications for benzene, as well as the corresponding sections of this article were essentially achieved during a wonderful week in the département of Ardèche, in April 2009. Je me souviens [76, 77] d’une fameuse fondue au LPQ autour de la table à saucissons. Je me souviens des rires et des doutes existentiels et scientifiques. Je me souviens du xylophone à roulettes d’Emilie que tu faisais tintinabuler pour nous convier à prendre le thé. Je me souviens de la trousse Babar qui t’accompagnait à chaque réunion. Je me souviens des impulsions scientifiques décisives que tu as données à ces travaux, après tant d’autres. Je me souviens de ta mélancolie.

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Authors and Affiliations

  1. Université de Toulouse, INSA, UPS, LPCNO, IRSAMC, 135 avenue de Rangueil, 31077, Toulouse, France

    Iker del Rosal, Franck Jolibois, Laurent Maron & Romuald Poteau

  2. CNRS, UMR 5215 (IRSAMC), 31077, Toulouse, France

    Iker del Rosal, Franck Jolibois, Laurent Maron & Romuald Poteau

  3. Institut Charles Gerhardt, CNRS 5253, Université Montpellier 2, CC 1501 Place Eugène Bataillon, 34095, Montpellier, France

    Christophe Raynaud

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  1. Christophe Raynaud
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Correspondence to Romuald Poteau.

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Dedicated to the memory of Professor Jean-Pierre Daudey and published as part of the Daudey Memorial Issue.

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Raynaud, C., del Rosal, I., Jolibois, F. et al. Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity. Theor Chem Acc 126, 151–163 (2010). https://doi.org/10.1007/s00214-009-0615-z

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