Park Heejune, Meloni Giovanni
Department of Chemistry, University of San Francisco, San Francisco, California 94117, USA.
Dalton Trans. 2017 Sep 12;46(35):11942-11949. doi: 10.1039/c7dt02331f.
The ability of the superalkali LiF to reduce (electron transfer) carbon dioxide (CO) is presented. The CBS-QB3 composite method is employed to obtain reliable information on the geometries and energetics of the investigated species. Transition states and minima were located by scanning the potential energy surface for CO addition to the LiF superalkali. The stability of LiF/CO is explained by high binding energy, charge flows, and the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap. The selectivity of LiF towards CO has also been computed by performing the same calculations for the most abundant atmospheric gas molecule N. These results show a very small chemical affinity of LiF for N.
本文介绍了超碱LiF还原（电子转移）二氧化碳（CO）的能力。采用CBS-QB3复合方法获取有关所研究物种的几何结构和能量学的可靠信息。通过扫描CO加成到LiF超碱的势能面来确定过渡态和极小值。LiF/CO的稳定性通过高结合能、电荷流动以及最高占据分子轨道-最低未占据分子轨道（HOMO-LUMO）能隙来解释。还通过对大气中最丰富的气体分子N进行相同计算，计算了LiF对CO的选择性。这些结果表明LiF对N的化学亲和力非常小。
