Geometry, bonding, and optical and magnetic properties of Cu(CO)3. A theoretical study

Ramiro Arratia-Perez, Frank U. Axe, Dennis S. Marynick

Resultado de la investigación: Article

4 Citas (Scopus)

Resumen

A detailed analysis of the geometry, bonding, and optical and magnetic properties of copper tricarbonyl is presented. The molecule is shown to be planar, with D3h symmetry. The calculations show good agreement with optical spectral data and with the observed 63Cu and 13C hyperfine tensors. Spin-orbit and spin-polarization effects contribute to the axial departure of the 13C and 17O hyperfine tensors. Spin-orbit effects are modelled through a four-component relativistic molecular orbital formalism, and core spin-polarization effects are estimated from quasi-relativistic spin-unrestricted calculations. Spin-orbit effects introduce significant ligand orbital mixings, split the metal-based 3d orbitals by ∼0.15 eV, and introduce small but nonnegligible "orbital" contributions to the hyperfine tensors at the Cu, C, and O sites. The calculations predict that the unpaired electron spends most of its time on the CO ligand and has about 25% copper 4pz character.

Idioma originalEnglish
Páginas (desde-hasta)5177-5183
Número de páginas7
PublicaciónJournal of Physical Chemistry
Volumen91
N.º20
EstadoPublished - 1987

Huella dactilar

Carbon Monoxide
Tensors
Magnetic properties
Spin polarization
Orbits
Optical properties
magnetic properties
optical properties
Geometry
Copper
geometry
Ligands
Molecular orbitals
tensors
orbits
orbitals
Metals
copper
ligands
Molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Citar esto

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Geometry, bonding, and optical and magnetic properties of Cu(CO)3. A theoretical study. / Arratia-Perez, Ramiro; Axe, Frank U.; Marynick, Dennis S.

En: Journal of Physical Chemistry, Vol. 91, N.º 20, 1987, p. 5177-5183.

Resultado de la investigación: Article

TY - JOUR

T1 - Geometry, bonding, and optical and magnetic properties of Cu(CO)3. A theoretical study

AU - Arratia-Perez, Ramiro

AU - Axe, Frank U.

AU - Marynick, Dennis S.

PY - 1987

Y1 - 1987

N2 - A detailed analysis of the geometry, bonding, and optical and magnetic properties of copper tricarbonyl is presented. The molecule is shown to be planar, with D3h symmetry. The calculations show good agreement with optical spectral data and with the observed 63Cu and 13C hyperfine tensors. Spin-orbit and spin-polarization effects contribute to the axial departure of the 13C and 17O hyperfine tensors. Spin-orbit effects are modelled through a four-component relativistic molecular orbital formalism, and core spin-polarization effects are estimated from quasi-relativistic spin-unrestricted calculations. Spin-orbit effects introduce significant ligand orbital mixings, split the metal-based 3d orbitals by ∼0.15 eV, and introduce small but nonnegligible "orbital" contributions to the hyperfine tensors at the Cu, C, and O sites. The calculations predict that the unpaired electron spends most of its time on the CO ligand and has about 25% copper 4pz character.

AB - A detailed analysis of the geometry, bonding, and optical and magnetic properties of copper tricarbonyl is presented. The molecule is shown to be planar, with D3h symmetry. The calculations show good agreement with optical spectral data and with the observed 63Cu and 13C hyperfine tensors. Spin-orbit and spin-polarization effects contribute to the axial departure of the 13C and 17O hyperfine tensors. Spin-orbit effects are modelled through a four-component relativistic molecular orbital formalism, and core spin-polarization effects are estimated from quasi-relativistic spin-unrestricted calculations. Spin-orbit effects introduce significant ligand orbital mixings, split the metal-based 3d orbitals by ∼0.15 eV, and introduce small but nonnegligible "orbital" contributions to the hyperfine tensors at the Cu, C, and O sites. The calculations predict that the unpaired electron spends most of its time on the CO ligand and has about 25% copper 4pz character.

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