Bonding, optical, and magnetic properties of paramagnetic Ag41+ and Ag43+ clusters

doi:10.1016/0022-2364(87)90231-9

Journal of Magnetic Resonance (1969)

Volume 73, Issue 1, 1 June 1987, Pages 134-142

Journal of Magnetic ...

https://doi.org/10.1016/0022-2364(87)90231-9 Get rights and content

Abstract

The electronic structure of the paramagnetic Ag₄⁺ and Ag₄³⁺ clusters is investigated by the Dirac scattered-wave method. The results show that relativistic effects are not very large, but they cannot be neglected. Due to relativity, nonnegligible 4d–5s hybridization arises in the bonding molecular orbitals. Spin-orbit interaction splits the occupied valence d band by 0.9 eV. Molecular hyperfine interactions (hfi) are calculated through a first-order perturbation to the Dirac Hamiltonian. The predicted hfi and excitation energies have enabled us to distinguish clearly between Ag₄⁺ and Ag₄³⁺. The hyperfine tensors for Ag₄⁺ are predicted to be anisotropic, whereas those for Ag₄³⁺ are mostly isotropic. The theoretical spectral assignments for Ag₄³⁺ are in good agreement with recent optical and ESR studies.

References (32)

R van Hardeveld et al.
Adv. Catal.
(1972)
A.D Stevens et al.
Chem. Phys. Lett.
(1984)
G Apai et al.
Solid State Commun.
(1981)
W Schulze et al.
Chem. Phys.
(1978)
D.A Case et al.
Chem. Phys. Lett.
(1976)
G.A Ozin
E Moisar
Photogr. Sci. Eng.
(1982)
P Fayet et al.
Phys. Rev. Lett.
(1985)
J Texter et al.
J. Phys. Chem.
(1986)

R.S Eachus et al.

J. Chem. Soc. A

(1970)

C.E Forbes et al.

Mol. Phys.

(1974)

R Arratia-Perez et al.

J. Chem. Phys.

(1983)

J.P Lopez et al.

J. Chem. Phys.

(1984)

D.A Case et al.

J. Chem. Phys.

(1984)

D.A Case

J. Chem. Phys.

(1985)

Cited by (10)

Cationic silver clusters in zeolite rho and sodalite
2002, Studies in Surface Science and Catalysis
The silver agglomeration process in γ-irradiated AgNaCs-rho zeolites and AgNa-sodalites has been investigated by electron paramagnetic resonance spectroscopy. In dehydrated rho zeolites the subsequent formation of Ag⁰, Ag₂⁺, Ag₃²⁺ and Ag₄³⁺ was observed. Ag₄³⁺ cluster, stable at room temperature, after NH₃ adsorption is coordinated by six ammonia ligands, two in a first coordination sphere and four in a second one forming the multicore complex Ag₄³⁺(NH₃′)₂(NH₃″)₄. In dehydrated sodalite the Ag₆⁵⁺ cluster is produced in the course of low temperature radiolysis as the result of electron trapping by the assemble of six Ag⁺ cations located in the same sodalite cage.
Calculated paramagnetic properties of matrix isolated Au<inf>3</inf> cluster
1995, Chemical Physics Letters
Non-relativistic (NR-Xα) and Dirac (DSW-Xα) spin-restricted calculations on the matrix isolated Au₃ cluster are reported. It is shown that the resolved hyperfine interactions arising from the apical gold atom and the anisotropic effects on the spin distribution and on the paramagnetic properties could be adequately interpreted by using Dirac operators and Dirac cluster wave functions. The DSW-Xα calculations are in reasonable agreement with empirical and resolved paramagnetic resonance data of the Au₃ cluster isolated on the C₆D₆ matrix.
Spin-orbit effects on heavy metal octahedral clusters
1993, Journal of Molecular Structure: THEOCHEM
The relativistic electronic structure of octahedral Mo₆, W₆, Ag₆ and Au₆ clusters has been investigated using the self-consistent field Dirac scattered wave (SCF-DSW) method. It is shown that spin—orbit interaction breaks the three-fold nonrelativistic Fermi (E_F) level of each cluster into its four-fold and two-fold relativistic electronic states. The E_F levels of the Mo₆ and W₆ clusters (of symmetry Γ₈⁺) fall in the d-band complex, the 2E+_F level of the Ag₆ cluster falls in the s-band complex, and the E_F level of the Au₆ cluster (Γ₈⁻) is located in the hybridized s—d-band complex. The contour plots of the relativistic highest occupied molecular orbital of the W₆ and Au₆ clusters support this view. We have folded the calculated spinor populations and the relativistic one-electron molecular orbital energies of the valence band of each cluster with gaussians to obtain the convoluted total and partial local density of states (DOS). The partial DOS thus obtained indicates that the d_$32$ and d_$52$ sub-bands of the Mo₆ and W₆ clusters are overlapped, whereas in the Ag₆ cluster these sub-bands are separated by about 1.2 eV. In the Au₆ cluster these sub-bands are almost completely separated (by about 1.9 eV), in good agreement with photoelectron data of high nuclearity gold—phosphine clusters. The calculated spin—orbit splitting of the valence d-band of the Ag₆ and Au₆ clusters are in agreement with the observed d-band splitting of a series of small clusters of gold and silver supported on carbon substrates.
Inside a superatom: The M<inf>7</inf><sup>q</sup> (M=Cu, Ag, q=1+, 0, 1-) case
2010, ChemPhysChem
Paramagnetic silver clusters in molecular sieves: Zeolite rho
2003, Solid State Phenomena
Effective core potential-configuration interaction study of electronic structure and geometry of small neutral and cationic Ag<inf>n</inf> clusters: Predictions and interpretation of measured properties
1993, The Journal of Chemical Physics

View all citing articles on Scopus

View full text

Bonding, optical, and magnetic properties of paramagnetic Ag41+ and Ag43+ clusters

Abstract

Adv. Catal.

Chem. Phys. Lett.

Solid State Commun.

Chem. Phys.

Chem. Phys. Lett.

Photogr. Sci. Eng.

Phys. Rev. Lett.

J. Phys. Chem.

J. Chem. Soc. A

Mol. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

J. Chem. Phys.

Bonding, optical, and magnetic properties of paramagnetic Ag₄¹⁺ and Ag₄³⁺ clusters