科研之友
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摘要
The atomic and electronic structures, mechanical properties and potential barriers of formation of a set of meso-meso beta-beta fused porphyrin/metalloporphyrin nanopages, nanotapes, nanotubes and 2D nanofabrics were studied by GGA LC-DFT technique using cluster and PBC models. The porphyrin pages of the nanoclusters are connected with each other by graphene fragments formed by meso-meso beta-beta links. Fusion of all the edges of six porphyrin/metalloporphyrin units produces a novel similar to 1 nm sized molecule of cubic symmetry with a hollow cage inside. It was found that all studied nanoclusters are metastable with formation energies 0.36-7.57 kcal/mol per atom. Under applied mechanical stress, the nanoclusters exhibit superelastic and ultrastrong properties with binding graphene fragments being the weakest links for mechanical rupture. Depending on the spin-dependent reaction pathways, the hollow caged nanoclusters exhibit almost zero or low potential energy barriers (1-10 kcal/ mol) during the initial stages of self-assembly. All nanoclusters exibit the main features of the electronic structures of the parent porphyrins, in particular the nature of HOMO/LUMO states and the relative energetic positions of the metal d states. The induced curvature of the hollow cage nanoclusters leads to admixture of more than 2% of the d(pi perpendicular to) states to the d(sigma) energy region and formation of vacant superatomic molecular orbitals of d character in cubic ligand field. The Fe-derived hollow-caged nanoclusters reveal extremely high spin states with small energy differences between ferromagnetic and antiferromagnetic configurations, which can be utilized for quantum holonomic computations.
- 出版日期2014-7
