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Dioxygen Binding to all 3d, 4d, and 5d Transition Metals from Coupled‐Cluster Theory
Author(s) -
Moltved Klaus A.,
Kepp Kasper P.
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000529
Subject(s) - chemisorption , chemistry , physisorption , binding energy , transition metal , cluster (spacecraft) , metal , coupled cluster , catalysis , chemical physics , computational chemistry , adsorption , atomic physics , molecule , physics , computer science , programming language , biochemistry , organic chemistry
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 O−O activation and reveal linear relationships between metal‐oxygen and O−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.