The structural landscape in 14-vertex clusters of silicon, M@Si14: when two bonding paradigms collide.

摘要: The structural chemistry of the title clusters has been source controversy in computational literature because identity most stable structure appears to be pathologically dependent on chosen theoretical model. candidate structures include a D3h-symmetric ‘fullerene-like’ isomer with 3-connected vertices (A), an ‘arachno’ architecture (B) and octahedral high vertex connectivities typical ‘closo’ electron-deficient (C). key understanding these apparently very different is fact that they make use limited electron density available from endohedral metal ways. Early transition series favoured one maximises transfer electropositive cage whereas for later metals it minimises repulsions increasingly core-like d electrons. varying role electrons across leads directly strong functional dependency, hence literature.