Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM) , Vrije Universiteit Amsterdam , De Boelelaan 1083 , NL-1081 HV Amsterdam , The Netherlands.
Leiden Institute of Chemistry , Leiden University , PO Box 9502, NL-2300 RA Leiden , The Netherlands.
J Phys Chem A. 2019 Oct 24;123(42):9137-9148. doi: 10.1021/acs.jpca.9b03814. Epub 2019 Jul 24.
We have carried out an extensive quantum chemical exploration of gas-phase alkali metal cation affinities (AMCAs) of archetypal neutral bases across the periodic system using relativistic density functional theory. One objective of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all neutral maingroup-element hydrides XH of groups 15-18 along the periods 1-6. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a canonical energy decomposition analysis (EDA). We compare the trends in XH AMCAs with the trends in XH proton affinities (PAs). We also examine the differences between the trends in AMCAs of the neutral XH bases with those in the corresponding anionic XH bases. Furthermore, we analyze how the cation affinity of our neutral Lewis bases changes along the group-1 cations H, Li, Na, K, Rb, and Cs.
我们使用相对论密度泛函理论对整个周期系统中典型中性碱基的气相碱金属阳离子亲和力 (AMCA) 进行了广泛的量子化学探索。这项工作的一个目标是提供一组内在一致的 298 K AMCA 值，涵盖了周期表 1-6 中的第 15-18 族所有中性主族元素氢化物 XH。我们的主要目的是使用 Kohn-Sham 分子轨道理论和规范能量分解分析 (EDA) 来理解这些趋势的基础键合机制。我们将 XH 的 AMCA 趋势与 XH 质子亲和力 (PA) 的趋势进行比较。我们还检查了中性 XH 碱基的 AMCA 趋势与相应的阴离子 XH 碱基的 AMCA 趋势之间的差异。此外，我们分析了我们的中性路易斯碱基的阳离子亲和力如何沿第 1 族阳离子 H、Li、Na、K、Rb 和 Cs 变化。
