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Title: G0W0 Ionization Potentials of First-Row Transition Metal Aqua Ions

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
  2. Zapata Computing, Inc., Boston, MA (United States)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  4. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
+ Show Author Affiliations

Here, 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., V3+, Cr3+, Cr2+, Mn2+, Fe3+, Fe2+, Co2+, Ni2+, and Cu2+. The d-orbital occupancy of these systems spans a broad range from d2 to d9. All of 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 G0W0 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, G0W0@PBE, G0W0@PBE0, and G0W0@r2SCAN. While the predicted ground-state structures are similar to all three exchange-correlation functionals, the vertical ionization potentials were in closer agreement with experiment when using the G0W0@PBE0 and G0W0@r2SCAN approaches, with the r2SCAN-based calculations being significantly less expensive. Computed bond distances and vertical ionization potentials for all structures are in good agreement with available experimental data.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC05-76RL01830; AC02-05CH11231
OSTI ID:
2337907
Report Number(s):
PNNL-SA--182129
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 46 Vol. 127; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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