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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A density functional study of Ce@C-82: Explanation of the Ce preferential bonding site
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A density functional study of Ce@C-82: Explanation of the Ce preferential bonding site

机译：Ce @ C-82的密度泛函研究：Ce优先键位的解释

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摘要

Ce has been found experimentally to be preferentially incorporated into the C-82 isomer of C-2v symmetry as have other lanthanoids in M@C-82 (M = La, Pr, Nd, etc.). We have investigated the underlying reason for this preference by calculating structural and electronic properties of Ce@C-82 using density functional theory. The ground-state structure of Ce@C-82 is found to have the cerium atom attached to the six-membered ring on the C-2 axis of the C-82-C-2v cage, and the encapsulated atom is found to perturb the carbon cage due to chemical bonding. We have found Ce to favor this C-2v chemisorption site in C-82 by 0.62 eV compared to other positions on the inside wall of the cage. The specific preference of the metal atom to this six-membered ring is explained through electronic structure analysis, which reveals strong hybridization between the d orbitals of cerium and the pi orbitals of the cage that is particularly favorable for this chemisorption site. We propose that this symmetry dictated interaction between the cage and the-lanthanide d orbital plays a crucial role when C-82 forms in the presence of Ce to produce Ce@C-82 and is also more generally applicable for the formation of other lanthanoid M@C-82 molecules. Our theoretical computations are the first to explain this well-established fact. Last, the vibrational spectrum of Ce@C-82 has been simulated and analyzed to gain insight into the metal-cage vibrations.
机译：实验发现，铈与C @ 82中的其他镧系元素一样，优先掺入C-2v对称的C-82异构体中（M = La，Pr，Nd等）。我们通过使用密度泛函理论计算Ce @ C-82的结构和电子性质，研究了这种偏爱的根本原因。发现Ce @ C-82的基态结构的铈原子连接到C-82-C-2v笼的C-2轴上的六元环上，并且发现被封装的原子会扰动碳笼由于化学键合。我们发现Ce与笼子内壁上的其他位置相比，对C-82中的C-2v化学吸附位点的偏爱为0.62 eV。通过电子结构分析解释了金属原子对该六元环的特定偏好，该结构揭示了铈的d轨道与笼子的pi轨道之间的强杂交，这对于该化学吸附位点特别有利。我们认为，这种对称性决定了笼子与镧系元素d轨道之间的相互作用在Ce-82在Ce存在下形成并生成Ce @ C-82时起着至关重要的作用，并且更普遍地适用于其他镧系元素M的形成。 @ C-82分子。我们的理论计算是第一个解释这一事实的人。最后，对Ce @ C-82的振动光谱进行了模拟和分析，以了解金属笼式振动。

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