We are so happy to see our first computational paper Why does thionating a carbonyl molecule make it a better electron acceptor? (DOI: 10.1039/D2CP05186A) appeared on the welcoming PCCP! We show that the enhanced electron affinity of heavy-atom substituted (‘doped’) organic molecules can be (generally) understood by considering the weaker antibonding interaction between carbon and heavy elements, leading to lower LUMO levels overall. Electronegativity, despite the implication of this term, is not a suitable parameter to gauge the effect of heavy elements on electron affinity.

Being an embarrassed author, I must further point out that our finding is analogous to what was disclosed by Prof. Fonseca Guerra in the context of the hydrogen-bond donor capability of chalcogenoamides. The origin of the trend of selenoamides > thioamides > carboxamides can be traced to the degree of the positively charged N-H group (the H-bond donor), caused by the varying antibonding interactions between carbon and chalcogens.