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 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
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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.
UR - http://www.scopus.com/inward/record.url?scp=8644276661&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:8644276661
VL - 85
SP - 6610
EP - 6622
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 11
ER -