Bartashevich Ekaterina V, Mukhitdinova Svetlana E, Klyuev Iliya V, Tsirelson Vladimir G
Chemistry Department, South Ural State University (National Research University), 76, Lenin Av., 454080 Chelyabinsk, Russia.
Quantum Chemistry Department, D.I. Mendeleev University of Chemical Technology, 125047 Moscow, Russia.
Molecules. 2022 Aug 24;27(17):5411. doi: 10.3390/molecules27175411.
Using the orbital-free quantum crystallography approach, we have disclosed the quantitative trends in electronic features for bonds of different strengths formed by tetrel (Tt) atoms in stable molecular complexes consisting of electrically neutral tetrahedral molecules and halide anions. We have revealed the role of the electrostatic and exchange-correlation components of the total one-electron static potential that are determined by the equilibrium atomic structure and by kinetic Pauli potential, which reflects the spin-dependent electron motion features of the weak and strong bonds. The gap between the extreme positions in the electrostatic and total static potentials along the line linking the Tt atom and halide anion is wide for weak bonds and narrow for strong ones. It is in very good agreement with the number of minima in the Pauli potential between the bounded atoms. This gap exponentially correlates with the exchange-correlation potential in various series with a fixed nucleophilic fragment. A criterion for categorizing the noncovalent tetrel bonds (TtB) based on the potential features is suggested.
使用无轨道量子晶体学方法，我们揭示了在由电中性四面体分子和卤化物阴离子组成的稳定分子复合物中，四价元素（Tt）原子形成的不同强度键的电子特征的定量趋势。我们揭示了总单电子静电势的静电和交换相关分量的作用，这些分量由平衡原子结构和动力学泡利势决定，动力学泡利势反映了弱键和强键的自旋相关电子运动特征。沿着连接Tt原子和卤化物阴离子的线，弱键在静电势和总静电势中的极端位置之间的差距很大，而强键的差距很小。这与键合原子之间泡利势中的极小值数量非常吻合。在具有固定亲核片段的各种系列中，这个差距与交换相关势呈指数相关。提出了一种基于势特征对非共价四价元素键（TtB）进行分类的标准。
