Oliveira Vytor, Kraka Elfi
Computational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University , 3215 Daniel Ave, Dallas, Texas 75275-0314, United States.
J Phys Chem A. 2017 Dec 14;121(49):9544-9556. doi: 10.1021/acs.jpca.7b10196. Epub 2017 Dec 4.
The noncovalent interactions of 32 complexes involving pnicogens, chalcogens, and halogens atoms were investigated at the CCSD(T)/aug-cc-pVTZ level of theory. Two different types of complexes could be distinguished on the basis of geometric parameters, electron difference densities, and the charge transfer mechanisms associated with each type. In the type I conformation, the monomers adopt a skewed orientation allowing charge to be transfer between both monomers, whereas in the type II conformation the monomers adopt a linear arrangement, maximizing charge transfer in only one direction. Type I complexes involving the interaction between pnicogens and chalcogens cannot be unambiguously defined as chalcogen or pnicogen bonds, they are an admixture of both. The charge transfer dependence on the conformation adopted by the complexes described in this work can serve as a novel conformationally driven design concept for materials.
在CCSD(T)/aug-cc-pVTZ理论水平下，研究了32种涉及氮族元素、氧族元素和卤族元素原子的配合物的非共价相互作用。根据几何参数、电子密度差以及与每种类型相关的电荷转移机制，可以区分出两种不同类型的配合物。在I型构象中，单体采取倾斜取向，使得电荷能够在两个单体之间转移；而在II型构象中，单体采取线性排列，仅在一个方向上使电荷转移最大化。涉及氮族元素与氧族元素相互作用的I型配合物不能明确地定义为氧族元素键或氮族元素键，它们是两者的混合。本文所述配合物所采用的构象对电荷转移的依赖性可作为一种新型的构象驱动材料设计概念。
