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A benchmark study of dioxygen complexes based on coupled cluster and density functional theory
by Marcel Swart, Marc Reimann
This Submission thread is now published as
Submission summary
| Authors (as registered SciPost users): | Marcel Swart |
| Submission information | |
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| Preprint Link: | https://doi.org/10.26434/chemrxiv-2023-56kdv-v3 (pdf) |
| Date accepted: | 2024-07-23 |
| Date submitted: | 2024-07-17 15:32 |
| Submitted by: | Swart, Marcel |
| Submitted to: | SciPost Chemistry |
| Ontological classification | |
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| Academic field: | Chemistry |
| Specialties: |
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| Approach: | Computational |
Abstract
A set of five compounds containing peroxo, superoxo or bis-mu-oxo moieties has been studied in the gas phase using CCSD(T)/aug-cc-pVQZ, also in combination with Goodson’s continued fraction approach. The corresponding analytical frequencies corroborate assignments of bands from experiments, and thus provide a consistent set of reference data that can be used for benchmarking a range of density functional approximations. A total of 100 density functionals have been checked for the general bond lengths, the specific peroxo/superoxo bond lengths, angles, and vibrational frequencies. There is not one density functional that performs equally well for all of these properties, not even within one class of density functionals.
Author comments upon resubmission
The first reviewer is absolutely correct that the exact energy of a given system depends on many variables, such as the basis set, inclusion (or not) of relativistic corrections (scalar vs. 2-component spin-orbit vs. 4-component spin-orbit, and which type: X2C, Pauli, Douglas-Kroll, Zora), solvent effects, finite nucleus effects, etc. etc. And indeed it does not make sense to compare results obtained by 6-31G* with ones obtained by aug-cc-pVQZ, or those obtained including scalar relativistic corrections with those obtained with 4-component spin-orbit relativistic corrections. This argument, however, does not apply to our manuscript, as all energies are obtained with a constant set of choices!
Nevertheless, we have decided to remove the absolute energies from the manuscript, focusing now on our important findings regarding structures and vibrational frequencies. With this change we think that the manuscript is now ready for acceptance.
List of changes
All reference to a comparison of electronic energies has been removed, Table S5 has been removed, Table S6 has been remade based only on data from Tables S1-S4, figures have been redrawn for Table S5 (previously S6), and text in main text discussing the overall performance has been updated.
Published as SciPost Chem. 3, 001 (2024)