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Theoretical Chemistry Accounts

, Volume 126, Issue 3–4, pp 151–163 | Cite as

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

  • Christophe Raynaud
  • Iker del Rosal
  • Franck Jolibois
  • Laurent Maron
  • Romuald PoteauEmail author
Regular Article

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.

Keywords

Effective group potentials Ab initio molecular dynamics Organometallic clusters and nanoparticles Chemical reactivity 

Notes

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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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Christophe Raynaud
    • 3
  • Iker del Rosal
    • 1
    • 2
  • Franck Jolibois
    • 1
    • 2
  • Laurent Maron
    • 1
    • 2
  • Romuald Poteau
    • 1
    • 2
    Email author
  1. 1.Université de Toulouse, INSA, UPS, LPCNO, IRSAMCToulouseFrance
  2. 2.CNRS, UMR 5215 (IRSAMC)ToulouseFrance
  3. 3.Institut Charles Gerhardt, CNRS 5253Université Montpellier 2MontpellierFrance

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