## 摘要

We study magnetic properties of carbon clusters C_{n} by combining the spin-polarized parametrized density functional tight-binding (SDFTB) theory with an unbiased modified basin hopping (MBH) optimization algorithm. With an intent to develop a physically self-consistent technique, we deliberately treat valence electronic charges, spin charges and ionic charges on equal footing. Within the density functional tight-binding (DFTB) theory, we examine the effect of using the orbital angular-momentum unresolved and resolved schemes in calculating the on-site Coulombic energy which, we judge, will have subtle but significant influence on the C_{n}’s magnetism, their topologies and the change with size n their conformational structures. As a concrete means to substantiate our conjecture, we apply the SDFTB/MBH method to C_{n}s and determine their stable magnetic structures within the angular-momentum resolved scheme. Our calculations show that the lowest energy C_{n} changes from a linear-chain shape for n = 3–9, turns over to a singlet monocyclic ring for n = 10–18, becomes a polycyclic ring for n = 19–25 and finally assumes a cage-like geometry at n = 26. Except for n = 4, 6 and 8, all other C_{n}s are found unmagnetized. Accordingly, the newly discovered n that marks the first occurrence of a bi- to tridimensional transition occurs at n = 26, and this size is in contrast to n = 24 which was predicted by similar calculations using the unresolved scheme. Our calculations reveal furthermore two different features. The first one is that the predicted optimized geometries for all of the C_{n}s, except for C_{24}, are structurally the same as the size n = 3–23 of C_{n} calculated by the DFTB/MBH employing the unresolved orbital angular-momentum scheme. As a result, the present calculations which employ the resolved angular-momentum scheme thus showed that the latter affects only the larger size C_{n} starting at C_{24}; this finding redefines therefore the turnover transition point of C_{n} from a bidimensional planar at n = 25 to a tridimensional cage-like at n = 26. The second feature is that the SDFTB/MBH method yields only triplet C_{4}, C_{6} and C_{8}, whereas in our previous work employing DFTB/MBH, not only C_{4} and C_{6}, all of C_{13}, C_{15}, C_{17}, C_{19}, C_{22} and C_{23} were predicted to carry a magnetic moment of 2 μ_{B}. These differences in the magnetism obtained are attributed to the combined use of both the SDFTB/MBH procedure and the orbital angular-momentum resolved scheme.

原文 | ???core.languages.en_GB??? |
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文章編號 | 134 |

期刊 | Theoretical Chemistry Accounts |

卷 | 137 |

發行號 | 10 |

DOIs | |

出版狀態 | 已出版 - 1 10月 2018 |