Ground and excited electronic structures of electride and alkalide units: The cases of Metal‐Tren, ‐Azacryptand, and ‐TriPip222 complexes

Abstract

AbstractA systematic electronic structure analysis was conducted for M(L)n molecular electrides and their corresponding alkalide units M(L)n@M′ (M/M′ = Na, K; L = Tren, Azacryptand, TriPip222; n = 1, 2). All complexes belong to the “superalkali” category due to their low ionization potentials. The saturated molecular electrides display M+(L)n− form with a greatly diffuse quasispherical electron cloud. They were identified as “superatoms” considering the contours of populating atomic‐type molecular orbitals. The observed superatomic Aufbau order of M(Tren)2 is 1S, 1P, 1D, 1F, 2S, 2P, and 1G and it is consistent with those of M(Azacryptand) and M(TriPip222) up to the analyzed 1F level. Their excitation energies decrease gradually moving from M(Tren)2 to M(Azacryptand) and to M(TriPip222). The studied alkalide complexes carry [M(L)n]+@M′− ionic structure and their dissociation energies vary in the sequence of K(L)n@Na > Na(L)n@Na > K(L)n@K > Na(L)n@K. Similar to molecular electrides, the anions of alkalide units occupy electrons in diffuse Rydberg‐like orbitals. In this work, excited states of [M(L)n@M′]0/+/− and their trends are also analyzed.