Dioxygen Binding to all 3d, 4d, and 5d Transition Metals from Coupled‐Cluster Theory

Abstract

Understanding how transition metals bind and activate dioxygen (O 2) is limited by experimental and theoretical uncertainties, making accurate quantum mechanical descriptors of interest. Here we report coupled-cluster CCSD(T) energies with large basis sets and vibrational and relativistic corrections for 160 3d, 4d, and 5d metal-O 2 systems. We define four reaction energies (120 in total for the 30 metals) that quantify OÀ O activation and reveal linear relationships between metal-oxygen and OÀ O binding energies. The CCSD(T) data can be combined with thermochemical cycles to estimate chemisorption and physisorption energies for each metal from metal oxide embedding energies, in good correlation with atomization enthalpies (R 2 = 0.75). Spin-geometry variations can break the linearities, of interest to circumventing the Sabatier principle. Pt, Pd, Co, and Fe form a distinct group with the weakest O 2 binding. R 2 up to 0.84 between surface adsorption energies and our energies for MO 2 systems indicate relevance also to real catalytic systems.

Heterogeneous molecular Co–N–C catalysts for efficient electrochemical H2O2 synthesis

“…In the preferential edge-on adsorption model, the Co–O interaction will be governed by the σ-type bond formed by the non-bonding Co-d z 2 orbital and the oxygen π* anti-bonding orbital. 21,22 We performed a qualitative comparison using the Co-d z 2 orbital center () determined from their spin-polarized pDOS (Fig. S4, ESI†).…”

“…In the preferential edge-on adsorption model, the Co-O interaction will be governed by the s-type bond formed by the non-bonding Co-d z 2 orbital and the oxygen p* anti-bonding orbital. 21,22 We performed a qualitative 23 We further compared the theoretical ORR potentials in Fig. 2(d) from the calculated Gibbs free energy (G) schemes along the 2e À -ORR and the 4e À -associative and 4e À -dissociative ORR pathways (the elementary steps are provided in the…”