Chemphyschem. 2021 Mar 23. doi: 10.1002/cphc.202100150. Online ahead of print.
ABSTRACT
The computed fluoride ion affinity (FIA) is a widely applied descriptor to gauge Lewis acidity. Like every other single-parameter Lewis acidity scale, the FIA metric suffers from the one-dimensionality, that prohibits addressing Lewis acidity by the multidimensionality it inherently requires (i.e., reference Lewis base dependency). However, a systematic screening of computed affinities other than the FIA is much less developed. Herein, we extended our CCSD(T)/CBS benchmark of different density functionals and the DLPNO-CCSD(T) method for chloride (CIA), methide (MIA), hydride (HIA), water (WA), and ammonia (AA) affinities. The best performing methods are subsequently applied to yield nearly 800 affinities for 183 p-block element compounds of group 13 – 16 with an estimated accuracy of <10 kJ mol -1 . The study’s output serves as a consistent library for qualitative analyses and a training set for future statistical approaches. A first holistic correlation analysis underscores the need for a multidimensional description of Lewis acidity.
PMID:33755288 | DOI:10.1002/cphc.202100150
