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

0475065 - ÚACH 2018 RIV GB eng J - Článek v odborném periodiku
Medved, M. - Demissie, T.B. - McKee, M.L. - Hnyk, Drahomír
The behavior of a paramagnetic system in electric and magnetic fields as exemplified by revisiting Li@B10H14.
Physical Chemistry Chemical Physics. Roč. 19, č. 19 (2017), s. 12229-12236. ISSN 1463-9076. E-ISSN 1463-9084
Grant CEP: GA ČR(CZ) GA16-01618S
Institucionální podpora: RVO:61388980
Klíčová slova: nonlinear-optical properties * coupled-cluster theory * open-shell systems * 3-dimensional aromaticity * polyhedral boranes
Obor OECD: Inorganic and nuclear chemistry
Impakt faktor: 3.906, rok: 2017

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.
Trvalý link: http://hdl.handle.net/11104/0271948