title: Scalar and Spin-Orbit Relativistic Corrections to the NICS and the Induced Magnetic Field: The case of the E12(2-) Spherenes (E = Ge, Sn, Pb).
abstract: Can relativistic effects modify the NICS and the B(ind) 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 (B(ind)) in the E12(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 B(ind) 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 Pb12(2-) is strongly aromatic, according to calculated NICS and B(ind) 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.
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: Abril Carolina
authors.initials: AC
authors.lastname: Castro
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: Edison
authors.initials: E
authors.lastname: Osorio
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: J Oscar C
authors.initials: JO
authors.lastname: Jiménez-Halla
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: Eduard
authors.initials: E
authors.lastname: Matito
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: William
authors.initials: W
authors.lastname: Tiznado
authors.affiliation: Departamento de Química, División de Ciencias Naturales y Exactas, Universidad de Guanajuato, Col. Noria Alta s/n C.P. 36050, Guanajuato, Gto, México, Departamento de Ciencias Químicas, Facultad de Ecología y Recursos Naturales, Universidad Andres Bello, Av. República 275, Santiago-Chile, and Institute of Physics, University of Szczecin, 70-451 Szczecin, Poland.
authors.forename: Gabriel
authors.initials: G
authors.lastname: Merino