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Structure and bonding in WC n (n = 2–5) clusters

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Abstract

Stochastic explorations of the configurational spaces for WC n (n = 2–5) clusters lead to densely populated spin states at each molecularity. We found 8, 16, 42, and 68 well-defined minima for n = 2, 3, 4, 5, respectively, in spin states ranging from singlets to quintuplets. The lowest energy isomers are triplets in all cases, except for n = 2 where there is competition between a quintuplet and a triplet state for the global minimum. The transition from planar to 3D structural preferences occurs between n = 4 and n = 5. For the global minima, the structures may be considered as the result of the interaction between two fragments: a tungsten cation and a covalently bonded anionic carbon chain. We found that spin–orbit (SO) effects reduce energy differences among isomers. Likewise, SO effects diminish as a function of the carbon content in the clusters to the point that for n = 5 they become negligible.

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Acknowledgments

Combined funding for this work from University of Antioquia via “Estrategia de Sostenibilidad” and CODI Project 10170 is gracefully acknowledged. F.F. is grateful to “El Patrimonio Autónomo Fondo Nacional de Financiamiento para la Ciencia, la Tecnología y la Innovación Francisco José de Caldas”, Project No. 211665842965.

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Correspondence to Elizabeth Flórez or C. Z. Hadad.

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The online version of this article (doi:) contains supplementary material (Tables 1SI–3SI; Cartesian coordinates for all structures reported in the paper at PBE0/def2-TZVP level of theory; Cartesian coordinates for the global minima, reoptimized using the B3LYP/def2-TZVP model chemistry; and Cartesian coordinates for the first 2 most stable WC2 structures (quintuplet and triplet) reoptimized at CCSD/def2-TZVP level of theory), which is available to authorized users. (PDF 423 kb)

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Flórez, E., Merino, G., Cabellos, J.L. et al. Structure and bonding in WC n (n = 2–5) clusters. Theor Chem Acc 135, 216 (2016). https://doi.org/10.1007/s00214-016-1979-5

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