### 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 5s_{1/2}-4d_{5/2} hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag_{5}^{q+} (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (^{2}E′) orbital degeneracy of Ag_{5} in D_{3h} geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D_{3h} geometry of Ag_{5} 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 Ag_{5}^{2+} and Ag _{5}^{4+} 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 original | English |
---|---|

Páginas (desde-hasta) | 6610-6622 |

Número de páginas | 13 |

Publicación | The Journal of Chemical Physics |

Volumen | 85 |

N.º | 11 |

Estado | Published - 1986 |

### Huella dactilar

### ASJC Scopus subject areas

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

### Citar esto

_{5}

^{q+}(q=0,2-4).

*The Journal of Chemical Physics*,

*85*(11), 6610-6622.

}

_{5}

^{q+}(q=0,2-4)',

*The Journal of Chemical Physics*, vol. 85, n.º 11, pp. 6610-6622.

**Dirac scattered-wave study of trigonal bipyramidal silver clusters Ag _{5}^{q+} (q=0,2-4).** / Arratia-Perez, Ramiro; Malli, Gulzari L.

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.

UR - http://www.scopus.com/inward/record.url?scp=8644276661&partnerID=8YFLogxK

M3 - Article

VL - 85

SP - 6610

EP - 6622

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

ER -

_{5}

^{q+}(q=0,2-4). The Journal of Chemical Physics. 1986;85(11):6610-6622.