TY - JOUR

T1 - Structure and bonding in WCn (n = 2–5) clusters

AU - Flórez, Elizabeth

AU - Merino, Gabriel

AU - Cabellos, José Luis

AU - Ferraro, Franklin

AU - Restrepo, Albeiro

AU - Hadad, C. Z.

PY - 2016/9/1

Y1 - 2016/9/1

N2 - © 2016, Springer-Verlag Berlin Heidelberg. Stochastic explorations of the configurational spaces for WCn(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.

AB - © 2016, Springer-Verlag Berlin Heidelberg. Stochastic explorations of the configurational spaces for WCn(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.

U2 - 10.1007/s00214-016-1979-5

DO - 10.1007/s00214-016-1979-5

M3 - Article

SN - 1432-881X

VL - 135

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

IS - 9

ER -