State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, People's Republic of China.
Dalton Trans. 2012 Jun 28;41(24):7272-7. doi: 10.1039/c2dt00009a. Epub 2012 May 9.
To deeply understand the charge-transporting nature of Pt(CN(t)Bu)(2)(CN)(2) nanowires induced by intermolecular Pt···Pt interactions, calculations based on first-principle band structure and Marcus theory have been performed. The calculated bandwidths of the valence band, conducting band, and the effective masses of hole and electron are almost equal. This suggests that this complex has ambipolar transport characteristics, in agreement with experimental results. Density of states analysis revealed that the hole transport resulted mainly from the Pt···Pt interactions, while the electron transport was derived mainly from the CN groups. The character of the frontier molecular orbitals, reorganization energies and transfer integrals in different directions also supports the calculated first-principle band structure. Moreover, an investigation into the intermolecular interaction energy of neighbors revealed that there is a remarkable relationship between the intermolecular interaction energy and the transfer integral.
为了深入理解分子间 Pt···Pt 相互作用诱导的 Pt(CN(t)Bu)(2)(CN)(2)纳米线的电荷输运性质，我们进行了基于第一性原理能带结构和 Marcus 理论的计算。价带、导带和空穴及电子的有效质量的计算带宽几乎相等。这表明该配合物具有双极性输运特性，与实验结果一致。态密度分析表明，空穴输运主要源于 Pt···Pt 相互作用，而电子输运主要源于 CN 基团。不同方向的前线分子轨道、重组能和转移积分的性质也支持计算的第一性原理能带结构。此外，对相邻分子间相互作用能的研究表明，分子间相互作用能与转移积分之间存在显著关系。
