TY - JOUR

T1 - Scalar and spin-orbit relativistic corrections to the NICS and the induced magnetic field

T2 - The case of the E12
2- spherenes (E = Ge, Sn, Pb)

AU - Castro, Abril Carolina

AU - Osorio, Edison

AU - Jiménez-Halla, J. Oscar C

AU - Matito, Eduard

AU - Tiznado, William

AU - Merino, Gabriel

PY - 2010/9/14

Y1 - 2010/9/14

N2 - Can relativistic effects modify the NICS and the Bind values? In this manuscript we evaluate the relativistic corrections incorporated via the zeroth-order regular approximation to the calculations of nucleus-independent chemical shifts and the induced magnetic field (Bind) in the E 12
2- spherenes (E = Ge, Sn, Pb). We found that both electron delocalization descriptors are strongly affected by the relativistic corrections. For instance, for plumbaspherene, the difference in values from the nonrelativistic to the relativity-included calculation is almost 40 ppm! Our results show that the changes observed in the NICS and Bind values in the title cages are a consequence of the treatment of the relativistic effects. If these effects are included as scalar or spin-orbit calculations, then we can establish the next trend: Ge12
2- is a nonaromatic species, Sn12
2- is a low aromatic species, and Pb 12
2- is strongly aromatic, according to calculated NICS and Bind values. Thus, any prediction of electron delocalization in molecules containing heavy elements without considering an adequate treatment for relativistic effects may lead to an erroneous chemical interpretation.

AB - Can relativistic effects modify the NICS and the Bind values? In this manuscript we evaluate the relativistic corrections incorporated via the zeroth-order regular approximation to the calculations of nucleus-independent chemical shifts and the induced magnetic field (Bind) in the E 12
2- spherenes (E = Ge, Sn, Pb). We found that both electron delocalization descriptors are strongly affected by the relativistic corrections. For instance, for plumbaspherene, the difference in values from the nonrelativistic to the relativity-included calculation is almost 40 ppm! Our results show that the changes observed in the NICS and Bind values in the title cages are a consequence of the treatment of the relativistic effects. If these effects are included as scalar or spin-orbit calculations, then we can establish the next trend: Ge12
2- is a nonaromatic species, Sn12
2- is a low aromatic species, and Pb 12
2- is strongly aromatic, according to calculated NICS and Bind values. Thus, any prediction of electron delocalization in molecules containing heavy elements without considering an adequate treatment for relativistic effects may lead to an erroneous chemical interpretation.

UR - http://www.scopus.com/inward/record.url?scp=77956566212&partnerID=8YFLogxK

U2 - 10.1021/ct100304c

DO - 10.1021/ct100304c

M3 - Artículo

AN - SCOPUS:77956566212

VL - 6

SP - 2701

EP - 2705

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 9

ER -