Ab initio study of the low-lying electronic states of Ag3−, Ag3, and Ag3+: A coupled-cluster approach

Abstract

The low-lying electronic states of Ag3−(1Σg+,3B2), Ag3(2B2,2A1,2B1,4B2,2Σu+,1 2Σg+,2 2Σg+,2Πu,4Σu+), and Ag3+(1A1,1Σg+,3Σu+,3A1) are studied by ab initio calculations with the Stuttgart effective core potentials and corresponding (8s7p6d)/[6s5p3d] and (8s7p5d3f )/[6s5p3d3f] basis sets. The geometries, vibrational frequencies, and energetic splittings are obtained by the coupled-cluster method including singles and doubles (CCSD) and those including up to the noniterative triples [CCSD(T)] correlation methods with additional frozen core molecular orbitals corresponding to 4s and 4p orbitals. The results for well-studied states (Ag3− 1Σg+;Ag3 2B2,2A1,2Σu+;Ag3+ 1A1) are in good agreement with previous experimental results, and therefore our results for other newly studied states are expected to be reliable. The vertical detachment energies of Ag3− are obtained by the electron excitation equation-of-motion coupled-cluster (EE-EOM-CCSD) method and the average deviation from the experimental results is small without any scaling correction of the obtained values. The effect of the f-functions in the basis sets and the noniterative triples in the CCSD(T) method is discussed; the bond lengths are reduced significantly and the vertical detachment energies and ionization potentials are in much better agreement with experiment.

Strongly enhanced field-dependent single-molecule electroluminescence

“…While finding utility within electronic devices (17,18) and even as electrically excited single-photon sources at cryogenic temperatures (19), the useful properties of individual molecules have not, to date, been used to create novel optical or electroluminescent materials with behavior different from that in bulk. Recently, we reported photoactivated fluorescence from individual Ag n nanoclusters (n ϭ 2ϳ8 atoms) (20), which have been observed and calculated to absorb and emit strongly throughout the visible spectrum (21)(22)(23)(24). Here we report that these same Ag n molecules can be electrically created, thus demonstrating that it is possible to prepare room-temperature electroluminescent single molecules.…”

“…The similarity to photoactivated single silver nanocluster fluorescence (20,28) indicates that both fluorescence and electroluminescence occur from individual Ag n molecules. Since each Ag n molecule has discrete electronic energy levels defined by its size and geometry (21)(22)(23)(24), radiative electron-hole pair recombination occurs only at the Ag nanoclusters within the discolored AgO regions of the films. This narrow recombination zone leads to extremely low film dielectricity, except at the individual electroluminescent molecules.…”

Interactions of Neutral and Cationic Transition Metals with the Redox System of Hydroquinone and Quinone: Theoretical Characterization of the Binding Topologies, and Implications for the Formation of Nanomaterials

“…The resulting cohesive energy per metal atom generally increases from an isolated dimer via a 1D wire and a 2D layer to the three-dimensional (3D) bulk ( Figure 4, Table 5). [42][43][44][45][46] Therefore, an initially weak bimetallic interaction may be overcome in a final 1D or 2D metallic array, but encompasses a barrier en route to the metallic product.…”

Validation of Methods for Computational Catalyst Design: Geometries, Structures, and Energies of Neutral and Charged Silver Clusters

“…16,18 On the basis of available validation tests, 20,22,23 we chose coupled cluster theory with single and double excitations and quasiperturbative connected triple excitations (CCSD(T)) 40 to optimize the structures of isomers of Ag 2−4 , Ag 2−4 + , and Ag 2−3…”