The behavior of a paramagnetic system in electric and magnetic fields as exemplified by revisiting Li@B10H14

Abstract

The electric and magnetic properties of the Li@B₁₀H₁₄ complex, considered as a novel inorganic electride-type system with potential for second-order non-linear optical (NLO) applications, have already been studied. However, the reported C_2v structure is not the global energy minimum and therefore its electronic and magnetic properties need to be revisited. Moreover, by applying more accurate computational protocols (ROHF-CCSD/CCSD(T) and larger basis sets) we show that the model chemistry used earlier (UMP2/6-31+G(d)) is not sufficient for reliable description of the NLO responses of this open-shell doublet complex. The global minimum based on the C_s symmetry is significantly (by ca. 25 kcal mol⁻¹) more stable than the C_2v structure and it should be viewed as a system with moderate NLO responses. An excess of unpaired electron density is also responsible for the contact and pseudo-contact contributions to the magnetic properties, which was not considered in the earlier work.