Multiple scattered wave study of the relativistic and nonrelativistic electronic structure and bonding for cis-diamminedichloroplatinum(II)

Fernando Zuloaga, Ramiro Arratia-Pérez

Resultado de la investigación: Article

6 Citas (Scopus)

Resumen

A detailed analysis of the valence molecular orbitals of cis-[Pt(NH3)2Cl2] is presented. Ground-state results for the relativistic Dirac scattered wave (DSW) calculations and its nonrelativistic limit (DNR (c = ∞)) together with the nonrelativistic Schrödinger multiple scattered wave (MSW) results show the importance of relativistic effects in this molecule. The analysis yield interesting features; e.g., relativistic effects increase the relative splitting between levels containing significant 5d metal character. The Pauli decomposition for the orbitals showing large contributions from metal atoms suggests that spin contaminations are significant. Furthermore, the established MOs reveal that L → 5d(Pt) donation is low in comparison to L → 6p(Pt) donation so that metal p orbitals play a fundamental role in the bonding scheme for this molecule. Contour maps for the relativistic HOMO level show the existence of a Cl-Cl bonding region and suggest that an almost neutral ligand Cl2 molecule exists in the complex, its free molecular electronegativity value is drastically reduced, and the Pt atom is responsible for this result.

Idioma originalEnglish
Páginas (desde-hasta)4491-4498
Número de páginas8
PublicaciónJournal of Physical Chemistry
Volumen90
N.º19
EstadoPublished - 1986

Huella dactilar

Cisplatin
Electronic structure
Metals
relativistic effects
electronic structure
Molecules
metals
molecules
orbitals
Atoms
Electronegativity
Molecular orbitals
Ground state
atoms
molecular orbitals
contamination
Contamination
Ligands
Decomposition
valence

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Citar esto

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title = "Multiple scattered wave study of the relativistic and nonrelativistic electronic structure and bonding for cis-diamminedichloroplatinum(II)",
abstract = "A detailed analysis of the valence molecular orbitals of cis-[Pt(NH3)2Cl2] is presented. Ground-state results for the relativistic Dirac scattered wave (DSW) calculations and its nonrelativistic limit (DNR (c = ∞)) together with the nonrelativistic Schr{\"o}dinger multiple scattered wave (MSW) results show the importance of relativistic effects in this molecule. The analysis yield interesting features; e.g., relativistic effects increase the relative splitting between levels containing significant 5d metal character. The Pauli decomposition for the orbitals showing large contributions from metal atoms suggests that spin contaminations are significant. Furthermore, the established MOs reveal that L → 5d(Pt) donation is low in comparison to L → 6p(Pt) donation so that metal p orbitals play a fundamental role in the bonding scheme for this molecule. Contour maps for the relativistic HOMO level show the existence of a Cl-Cl bonding region and suggest that an almost neutral ligand Cl2 molecule exists in the complex, its free molecular electronegativity value is drastically reduced, and the Pt atom is responsible for this result.",
author = "Fernando Zuloaga and Ramiro Arratia-P{\'e}rez",
year = "1986",
language = "English",
volume = "90",
pages = "4491--4498",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Multiple scattered wave study of the relativistic and nonrelativistic electronic structure and bonding for cis-diamminedichloroplatinum(II)

AU - Zuloaga, Fernando

AU - Arratia-Pérez, Ramiro

PY - 1986

Y1 - 1986

N2 - A detailed analysis of the valence molecular orbitals of cis-[Pt(NH3)2Cl2] is presented. Ground-state results for the relativistic Dirac scattered wave (DSW) calculations and its nonrelativistic limit (DNR (c = ∞)) together with the nonrelativistic Schrödinger multiple scattered wave (MSW) results show the importance of relativistic effects in this molecule. The analysis yield interesting features; e.g., relativistic effects increase the relative splitting between levels containing significant 5d metal character. The Pauli decomposition for the orbitals showing large contributions from metal atoms suggests that spin contaminations are significant. Furthermore, the established MOs reveal that L → 5d(Pt) donation is low in comparison to L → 6p(Pt) donation so that metal p orbitals play a fundamental role in the bonding scheme for this molecule. Contour maps for the relativistic HOMO level show the existence of a Cl-Cl bonding region and suggest that an almost neutral ligand Cl2 molecule exists in the complex, its free molecular electronegativity value is drastically reduced, and the Pt atom is responsible for this result.

AB - A detailed analysis of the valence molecular orbitals of cis-[Pt(NH3)2Cl2] is presented. Ground-state results for the relativistic Dirac scattered wave (DSW) calculations and its nonrelativistic limit (DNR (c = ∞)) together with the nonrelativistic Schrödinger multiple scattered wave (MSW) results show the importance of relativistic effects in this molecule. The analysis yield interesting features; e.g., relativistic effects increase the relative splitting between levels containing significant 5d metal character. The Pauli decomposition for the orbitals showing large contributions from metal atoms suggests that spin contaminations are significant. Furthermore, the established MOs reveal that L → 5d(Pt) donation is low in comparison to L → 6p(Pt) donation so that metal p orbitals play a fundamental role in the bonding scheme for this molecule. Contour maps for the relativistic HOMO level show the existence of a Cl-Cl bonding region and suggest that an almost neutral ligand Cl2 molecule exists in the complex, its free molecular electronegativity value is drastically reduced, and the Pt atom is responsible for this result.

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M3 - Article

VL - 90

SP - 4491

EP - 4498

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 19

ER -