Boughlala Zakaria, Fonseca Guerra Célia, Bickelhaupt F Matthias
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, NL.
Leiden Institute of Chemistry, Leiden University, PO Box 9502, 2300 RA, Leiden, NL.
Chem Asian J. 2017 Oct 5;12(19):2604-2611. doi: 10.1002/asia.201700956. Epub 2017 Sep 13.
We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).
我们使用相对论密度泛函理论，在ZORA-BP86/QZ4P//ZORA-BP86/TZ2P水平下，对整个周期系中典型阴离子碱的气相碱金属阳离子亲和能（AMCA）进行了广泛探索。计算了所有碱与锂、钠、钾、铷和铯阳离子的AMCA值，并与相应的质子亲和能（PA）进行了比较。这项工作的一个目的是提供一组本质上一致的298K时，由第14 - 17族主族元素氢化物在第2 - 6周期构成的所有阴离子（XH⁻）的AMCA值。特别地，我们希望确定当阳离子从质子变化到碱金属阳离子并沿着碱金属阳离子系列变化时，对阳离子的亲和能趋势。我们的主要目的是利用Kohn-Sham分子轨道理论以及定量键能分解分析（EDA），从潜在的成键机制角度理解这些趋势。
