Theoretical Chemistry, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
J Phys Chem A. 2012 Jul 5;116(26):7219-27. doi: 10.1021/jp303967s. Epub 2012 Jun 25.
The geometry of ethylenedioxy-tetrathiafulvalene, EDO-TTF, plays an important role in the metal-insulator transition in the charge transfer salt (EDO-TTF)(2)PF(6). The planar and off-planar geometrical conformations of the EDO-TTF molecules are explained using an extended Debye polarizability model for the bond angle. The geometrical structure of EDO-TTF is dictated by its four sulfur bond angles and these are, in turn, determined by the polarizability of the sulfur atoms. With Hartree-Fock and second-order Møller-Plesset perturbation theory calculations on EDO-TTF, TTF, H(2)S, and their oxygen and selenium substituted counterparts we confirm this hypothesis. The Debye polarizability model for bond angles relates directly the optimum bond angle with the polarizability of the center atom. Considering the (EDO-TTF)(2)PF(6) material in this light proves to be very fruitful.
乙撑二氧四硫代富瓦烯（EDO-TTF）的几何形状在电荷转移盐（EDO-TTF）（2）PF（6）中的金属-绝缘体转变中起着重要作用。使用扩展的键角德拜极化率模型解释了 EDO-TTF 分子的平面和非平面几何构象。EDO-TTF 的几何结构由其四个硫键角决定，而这些角又由硫原子的极化率决定。通过对 EDO-TTF、TTF、H（2）S 及其氧和硒取代物的 Hartree-Fock 和二级 Møller-Plesset 微扰理论计算，我们证实了这一假设。键角的德拜极化率模型直接将最佳键角与中心原子的极化率联系起来。从这个角度考虑（EDO-TTF）（2）PF（6）材料非常有成效。
