Dirac scattered-wave study of trigonal bipyramidal silver clusters Ag 5q+ (q=0,2-4)

Ramiro Arratia-Perez, Gulzari L. Malli

Resultado de la investigación: Article

22 Citas (Scopus)

Resumen

The electronic structure of the neutral and cationic pentaatomic silver bare clusters is investigated by the Dirac scattered-wave (DSW) method. The results indicate that there is significant 5s1/2-4d5/2 hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag5q+ (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (2E′) orbital degeneracy of Ag5 in D3h geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D3h geometry of Ag5 will not distort due to Jahn-Teller effect. It is found that the hyperfine coupling constants calculated by using a four-component wave function for the Ag52+ and Ag 54+ clusters differ significantly from previously computed hfi using a second-order perturbation to the Schrödinger Hamiltonian. First ionization potentials and excitation energies are predicted for all the species as calculated by the spin-restricted transition state method.

Idioma originalEnglish
Páginas (desde-hasta)6610-6622
Número de páginas13
PublicaciónThe Journal of Chemical Physics
Volumen85
N.º11
EstadoPublished - 1986

Huella dactilar

Hamiltonians
Silver
silver
Jahn-Teller effect
perturbation
Molecular interactions
Geometry
Ionization potential
Excitation energy
Molecular orbitals
relativistic effects
Wave functions
geometry
Potential energy
spin-orbit interactions
ionization potentials
Ground state
Electronic structure
molecular orbitals
Orbits

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

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abstract = "The electronic structure of the neutral and cationic pentaatomic silver bare clusters is investigated by the Dirac scattered-wave (DSW) method. The results indicate that there is significant 5s1/2-4d5/2 hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag5q+ (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (2E′) orbital degeneracy of Ag5 in D3h geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D3h geometry of Ag5 will not distort due to Jahn-Teller effect. It is found that the hyperfine coupling constants calculated by using a four-component wave function for the Ag52+ and Ag 54+ clusters differ significantly from previously computed hfi using a second-order perturbation to the Schr{\"o}dinger Hamiltonian. First ionization potentials and excitation energies are predicted for all the species as calculated by the spin-restricted transition state method.",
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Dirac scattered-wave study of trigonal bipyramidal silver clusters Ag 5q+ (q=0,2-4). / Arratia-Perez, Ramiro; Malli, Gulzari L.

En: The Journal of Chemical Physics, Vol. 85, N.º 11, 1986, p. 6610-6622.

Resultado de la investigación: Article

TY - JOUR

T1 - Dirac scattered-wave study of trigonal bipyramidal silver clusters Ag 5q+ (q=0,2-4)

AU - Arratia-Perez, Ramiro

AU - Malli, Gulzari L.

PY - 1986

Y1 - 1986

N2 - The electronic structure of the neutral and cationic pentaatomic silver bare clusters is investigated by the Dirac scattered-wave (DSW) method. The results indicate that there is significant 5s1/2-4d5/2 hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag5q+ (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (2E′) orbital degeneracy of Ag5 in D3h geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D3h geometry of Ag5 will not distort due to Jahn-Teller effect. It is found that the hyperfine coupling constants calculated by using a four-component wave function for the Ag52+ and Ag 54+ clusters differ significantly from previously computed hfi using a second-order perturbation to the Schrödinger Hamiltonian. First ionization potentials and excitation energies are predicted for all the species as calculated by the spin-restricted transition state method.

AB - The electronic structure of the neutral and cationic pentaatomic silver bare clusters is investigated by the Dirac scattered-wave (DSW) method. The results indicate that there is significant 5s1/2-4d5/2 hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag5q+ (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (2E′) orbital degeneracy of Ag5 in D3h geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D3h geometry of Ag5 will not distort due to Jahn-Teller effect. It is found that the hyperfine coupling constants calculated by using a four-component wave function for the Ag52+ and Ag 54+ clusters differ significantly from previously computed hfi using a second-order perturbation to the Schrödinger Hamiltonian. First ionization potentials and excitation energies are predicted for all the species as calculated by the spin-restricted transition state method.

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M3 - Article

VL - 85

SP - 6610

EP - 6622

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

ER -