検索対象:     
報告書番号:
※ 半角英数字
 年 ~ 
 年

Quantum chemical study of atomic structure evolution of Co$$_{x}$$/C$$_{60}$$ (x $$leq$$ 2.8) composites

Co$$_{x}$$/C$$_{60}$$(x $$leq$$ 2.8)混合物の原子的構造の進展に関する量子化学的研究

Avramov, P.; 楢本 洋*; 境 誠司; 鳴海 一雅; Lavrentiev, V.*; 前田 佳均

Avramov, P.; Naramoto, Hiroshi*; Sakai, Seiji; Narumi, Kazumasa; Lavrentiev, V.*; Maeda, Yoshihito

CoとC$$_{60}$$からなる新奇化合物Co$$_{x}$$/C$$_{60}$$(x $$leq$$ 2.8)の局所的な原子配置を、Co$$_{n}$$(C$$_{60}$$)$$_{m}$$(n=1, 2, m=2, 3)について、B3LYP/6-31G$$^{*}$$法を用いた第一原理計算によって研究した。n=1の異性体については、スピン状態S=1/2の場合がエネルギー的に安定で、それに対して、n=2の異性体はスピン状態S=1のときにより安定だった。また、n=1, 2のいずれの場合も$$eta$$$$^{2}$$型(C$$_{60}$$の6員環間に2座で配位)のCoの配位がエネルギー的に安定だった。$$eta$$$$^{2'}$$型の配位(6員環-5員環間に2座で配位)、さらに$$eta$$$$^{5}$$型の配位(5員環に5座で配位)は、Co原子がC$$_{60}$$ケージ上をマイグレートする際に中間体になりえ、さらに、Co$$_{x}$$/C$$_{60}$$は、最終的にCoダイマーの形成によって平衡状態の原子配置に近づくことを明らかにした。

The main features of the local atomic structure of novel Co$$_{x}$$/C$$_{60}$$ (x $$leq$$ 2.8) complex mixtures were studied using the ${it ab initio}$ B3LYP/6-31G$$ast$$ method for a set of low and high energy Co$$_{n}$$(C$$_{60}$$)$$_{m}$$ (n = 1, 2, m = 2, 3) clusters in low and intermediate spin states. For the n = 1 isomers the spin state S = 1/2 is energetically preferable whereas the low energy isomers of n = 2 have an intermediate spin state of S = 1. The $$eta$$$$^{2}$$ (6-6 edge of C$$_{60}$$) type of cobalt ion coordination is preferable for both n = 1 and n = 2 cases. The $$eta$$$$^{2'}$$ (coordination with 6-5 edge) and even the $$eta$$$$^{5}$$ (C$$_{5}$$ fragment) types can serve as low and high energy intermediates for the cobalt ion's migration around the C$$_{60}$$ cage. Formation of cobalt dimers can be the final stage of evolution of Co$$_{x}$$/C$$_{60}$$ atomic structure approaching the equilibrium atomic geometry.

Access

:

- Accesses

InCites™

:

パーセンタイル:44.97

分野:Chemistry, Physical

Altmetrics

:

[CLARIVATE ANALYTICS], [WEB OF SCIENCE], [HIGHLY CITED PAPER & CUP LOGO] and [HOT PAPER & FIRE LOGO] are trademarks of Clarivate Analytics, and/or its affiliated company or companies, and used herein by permission and/or license.