Probing the structural and electronic properties of AgnH− (n = 1–3) using photoelectron imaging and theoretical calculations

Abstract

Structural and electronic properties of silver hydride cluster anions (Ag n H − ; n = 1-3) have been explored by combining the negative ion photoelectron imaging spectroscopy and theoretical calculations. The photoelectron spectrum of AgH − exhibits transitions from AgH − 2 + to AgH 1 + and AgH 3 + , with the electron affinity (EA) 0.57(3) eV. For Ag 2 H − , the only observed transition is from Ag 2 H − (C ∞v ) 1 + to Ag 2 H (C 2v ) 2 A and the electron affinity is 2.56(5) eV. Two obvious electron bands are observed in photoelectron imaging of Ag 3 H − , which are assigned to the transitions from Ag 3 H − (C 2v -T, which means C 2v geometry with top site hydrogen) 2 B 2 to Ag 3 H (C 2v -T) 1 A 1 and Ag 3 H (C 2v -T) 3 B 2 . The electron affinity is determined to be 1.61(9) eV. The Ag-H stretching modes in the ground states of AgH and Ag 2 H are experimentally resolved and their frequencies are measured to be 1710(80) and 1650(100) cm −1 , respectively. Aside from the above EAs and the vibrational frequencies, the vertical detachment energies to all ground states and some excited states of Ag n H (n = 1-3) are also obtained. Theoretical calculations reproduce the experimental energies quite well, and the results are used to assign the geometries and electronic states for all related species.

Photoelectron imaging and theoretical calculations of gold–silver hydrides: comparing the characteristics of Au, Ag and H in small clusters

“…Structural characteristics of gold-silver hydrides 42 These common linear or ''T'' planar structures of the above species imply the similar bonding behaviors of Au, Ag and H, which can be attributed to their similar valence shell.…”

“…6, the determined structures and the experimental VDEs of the low-lying metal hydride anions reported in this research are listed. In order to make comparisons with previous results, the experimental VDEs of similar linear and ''T'' planar structures of gold hydride clusters, 17,27 silver hydride clusters, 42 homonuclear gold or silver clusters 8,41 and heteronuclear gold-silver cluster 38 are also included in Fig. 6.…”

Apparent activation of H2O and elimination of H2 from gas‐phase mixed‐metal complexes containing silver, calcium and deprotonated glycine

“…[1][2][3][4][5][6][7][8] For example, many studies have involved the use of photoelectron spectroscopy (PES) and density functional theory (DFT) calculations to investigate the structure of gold-and silver-containing clusters. [9][10][11][12][13][14][15][16][17][18][19][20] Using these methods, Zhao et al found that Au-H interactions are stronger than Ag-H interactions in metal-hydride species, [18] and Wang and co-workers [17,19] were able to show that relativistic effects [7,21] cause Au to form covalent rather than ionic bonds with certain ligands.…”

Photoelectron imaging and theoretical study on the structure and chemical binding of the mixed-ligand M(I) complexes, [HMSH]− (M = Cu, Ag, and Au)

“…ing the adsorption of hydrogen onto metal surfaces and the catalytic mechanism of the metal hydride-catalyzed reactions. A variety of spectroscopic tools, such as matrix infrared spectroscopy, 13 photoelectron spectroscopy, [14][15][16] and emission spectra, 17 have been used to determine the electronic or vibronic energies of transition metal hydrides or dihydrides. Previous photoelectron spectra study of gold dihydride showed a very strong Au-H bonding interaction (due to similar electronegativity), providing a typical model system to understand the covalent capabilities of Au.…”