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)

Abril Carolina Castro, Edison Osorio, J. Oscar C Jiménez-Halla, Eduard Matito, William Tiznado, Gabriel Merino

Resultado de la investigación: Article

31 Citas (Scopus)

Resumen

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.

Idioma originalEnglish
Páginas (desde-hasta)2701-2705
Número de páginas5
PublicaciónJournal of Chemical Theory and Computation
Volumen6
N.º9
DOI
EstadoPublished - 14 sep 2010

Huella dactilar

relativistic effects
Orbits
Magnetic fields
scalars
orbits
orbit calculation
magnetic fields
Relativity
Electrons
Chemical shift
heavy elements
chemical equilibrium
relativity
electrons
trends
Molecules
nuclei
predictions
approximation
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Citar esto

Castro, Abril Carolina ; Osorio, Edison ; Jiménez-Halla, J. Oscar C ; Matito, Eduard ; Tiznado, William ; Merino, Gabriel. / 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). En: Journal of Chemical Theory and Computation. 2010 ; Vol. 6, N.º 9. pp. 2701-2705.
@article{382a46eafe07471795df4e15f424003e,
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 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.",
author = "Castro, {Abril Carolina} and Edison Osorio and Jim{\'e}nez-Halla, {J. Oscar C} and Eduard Matito and William Tiznado and Gabriel Merino",
year = "2010",
month = "9",
day = "14",
doi = "10.1021/ct100304c",
language = "English",
volume = "6",
pages = "2701--2705",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
publisher = "American Chemical Society",
number = "9",

}

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). / Castro, Abril Carolina; Osorio, Edison; Jiménez-Halla, J. Oscar C; Matito, Eduard; Tiznado, William; Merino, Gabriel.

En: Journal of Chemical Theory and Computation, Vol. 6, N.º 9, 14.09.2010, p. 2701-2705.

Resultado de la investigación: Article

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 - Article

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 -