On the photoelectron spectrum of AgO−

Abstract

The 364 nm negative ion photoelectron spectrum of AgO− is reported. Transitions to the A 2Σ+ state and the X 2Π1/2 and X 2Π3/2 spin–orbit states of AgO are observed. The electronic ground state of AgO− is found to have a vibrational frequency of 497 (20) cm−1 and an equilibrium bond length of 1.935 (15) Å. The electron affinity of AgO is found to be 1.654 (2) eV.

Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Atoms and Monoxides

“…The difference between G 0 W 0 results and the experimental spectra is large, with differences up to 0.9 eV for G 0 W 0 @LDA and up to 0.7 eV for G 0 W 0 @GGA. While a small part of this difference may be attributed to our comparison of vertical binding energy predictions (from G 0 W 0 ) to experimental adiabatic binding energies, the bond length changes are smallless than 0.06 Å for CuO − and less 0.07 Å for AgO − from Franck−Condon simulations; 23,24 therefore, we believe that the true adiabatic and vertical energies do not differ significantly. The larger error is attributed to the partial d character of the orbital, and we see from CuO − and AgO − that even orbitals with only some admixture of d can be difficult to accurately simulate from GW calculations.…”

“…where (24) with c, c′ being indices for empty states and v, v′ being indices for occupied states, and ε c and ε v denote the quasiparticle energies. If the ground state is not spin polarized, its neutral excitations can be computed with a basis set two times reduced, with singlet excitations corresponding to a BSE Hamiltonian with…”

Dissociation energies of Ag–RG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies

“…This represents an important number as the dissociation energy of AgO has proven challenging to measure experimentally despite its importance in the determination of other parameters. [39] The currently accepted value is an early mass spectrometric determination The values determined in this study mark a significant revision in the AgO dissociation energy more in line with, but still marginally higher than, high-level calculations.…”

“…This represents an important number as the dissociation energy of AgO has proven challenging to measure experimentally despite its importance in the determination of other parameters. [39] The currently accepted value is an early mass spectrometric determination of 52.7  3.5 kcal mol -1 (= 2.29  0.15 eV  18400  1200 cm -1 ) by Smoes et al using a Knudsen cell. [40] This value has long been considered unreliable, however, representing a significant outlier in comparison with other experimental and calculated values.…”

Correction to Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Monoxides

“…In our benchmarks, the incorrectly located, strongly defined poles result in an especially poor theoretical description of anion binding energies. Furthermore, since experiments do not show evidence of any shakeup processes in the energy range near the monoxide anion quasiparticles being benchmarked, 8,9,11 we can therefore safely infer that the G 0 W 0 @LDA and G 0 W 0 @GGA self-energy pole structure is in general rather unphysical. Finally, this erratum demonstrates that the broadening of self-energy poles located in the vicinity of quasiparticle energies can significantly affect the resulting GW quasiparticle energies.…”