Magnetically induced current densities in Al4 (2-) and Al4 (4-) species studied at the coupled-cluster level.
Magnetically induced current densities in the four-membered rings of Al4(2-) and Al4(4-) species have been calculated at the coupled-cluster singles and doubles (CCSD) level by applying the recently developed gauge-including magnetically induced current (GIMIC) method. The strength of the ring-current susceptibilities were obtained by numerical integration of the current densities passing through a cross section perpendicular to the Al4 ring. The GIMIC calculations support the earlier notion that Al4 (2-) with formally two pi electrons sustains a net diatropic ring current. The diatropic contribution to the ring-current susceptibility is carried by the electrons in both the sigma (16.7 nAT) and the pi (11.3 nAT) orbitals. The induced ring current in the Al4 (4-) compounds, with four pi electrons, consists of about equally strong diatropic sigma and paratropic pi currents of about 14 and -17 nAT, respectively. The net current susceptibilities obtained for Al4Li-, Al4Li2, Al4Li3(-), and Al4Li4 at the CCSD level using a triple-zeta basis set augmented with polarization functions are 28.1, 28.1, -5.9, and -3.1 nAT, respectively. The corresponding diatropic (paratropic) contributions to the ring-current susceptibilities are 32.4 (0.0), 36.7 (0.0), 18.9 (-19.9), and 18.6 (-16.8) nAT, respectively. For the Al4(2-) and Al4(4-) species, the net currents circling each Li+ cation is estimated to 4.3 and 2.4 nAT, respectively.
Department of Chemistry, University of Helsinki, P.O. Box 55 (A.I. Virtanens plats 1), FIN-00014 Helsinki, Finland.
Ying-Chan
YC
Lin
Jonas
J
Jusélius
Dage
D
Sundholm
Jürgen
J
Gauss