$G_0{W}_0$ Ionization Potentials of First-Row Transition Metal Aqua Ions

Abstract

We report computations of the vertical ionization potentials within the $GW$ approximation of the near-complete series of first-row transition metal (V-Cu) aqua ions in their most common oxidation states, i.e. V${}^{3+}$, Cr${}^{3+}$, Cr${}^{2+}$, Mn${}^{2+}$, Fe${}^{3+}$, Fe${}^{2+}$, Co${}^{2+}$, Ni${}^{2+}$, and Cu${}^{2+}$. The $d$-orbital occupancy of these systems spans a broad range from $d^2$ to $d^9$. All the structures were first optimized at the density functional theory level using a large cluster of explicit water molecules that are embedded in a continuum solvation model. Vertical ionization potentials were computed with the one-shot $G_0{W}_0$ approach on a range of transition metal ion clusters (6, 18, 40, and 60 explicit water molecules) wherein the convergence with respect to the basis set size was evaluated using the systems with 40 water molecules. We assess the results using three different density functional approximations as starting points for the vertical ionization potential calculations, namely $G_0{W}_0$@PBE, $G_0{W}_0$@PBE0, and $G_0{W}_0$@r${}^2$SCAN. While the predicted ground-state structures are similar with all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with the experiment when using the $G_0{W}_0$@PBE0 and $G_0{W}_0$@r${}^2$SCAN approaches, with the r2SCAN based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures were compared with available experimental data and are in good agreement.

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