Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics

Nandy, Aditya; Chu, Daniel K.; Harper, Daniel R.; Duan, Chenru; Arunachalam, Naveen; Cytter, Yael; Kulik, Heather J.

doi:10.1039/D0CP02977G

Title: Large-scale comparison of 3d and 4d transition metal complexes illuminates the reduced effect of exchange on second-row spin-state energetics

Journal Article · Tue Sep 08 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D0CP02977G· OSTI ID:1648590

^[1];

^[2]; Harper, Daniel R. ^[1]; Duan, Chenru ^[1];

^[2]; Cytter, Yael ^[2];

^[2]

Department of Chemical Engineering;Massachusetts Institute of Technology;Cambridge;USA;Department of Chemistry
Department of Chemical Engineering;Massachusetts Institute of Technology;Cambridge;USA

Density functional theory (DFT) is widely used in transition-metal chemistry, yet essential properties such as spin-state energetics in transition-metal complexes (TMCs) are well known to be sensitive to the choice of the exchange–correlation functional. Increasing the amount of exchange in a functional typically shifts the preferred ground state in first-row TMCs from low-spin to high-spin by penalizing delocalization error, but the effect on properties of second-row complexes is less well known. We compare the exchange sensitivity of adiabatic spin-splitting energies in pairs of mononuclear 3d and 4d mid-row octahedral transition-metal complexes. We analyze hundreds of complexes assembled from four metals in two oxidation states with ten small monodentate ligands that span a wide range of field strengths expected to favor a variety of ground states. We observe consistently lower but proportional sensitivity to exchange fraction among 4d TMCs with respect to their isovalent 3d TMC counterparts, leading to the largest difference in sensitivities for the strongest field ligands. The combined effect of reduced exchange sensitivities and the greater low-spin bias of most 4d TMCs means that while over one-third of 3d TMCs change ground states over a modest variation (ca. 0.0–0.3) in exchange fraction, almost no 4d TMCs do. Differences in delocalization, as judged through changes in the metal–ligand bond lengths between spin states, do not explain the distinct behavior of 4d TMCs. Instead, evaluation of potential energy curves in 3d and 4d TMCs reveals that higher exchange sensitivities in 3d TMCs are likely due to the opposing effect of exchange on the low-spin and high-spin states, whereas the effect on both spin states is more comparable in 4d TMCs.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); National Science Foundation (NSF)

Grant/Contract Number:: SC0018096; N00014-17-1-2956; N00014-18-1-2434; CBET-1704266; 1122374; ACI-1548562

OSTI ID:: 1648590

Alternate ID(s):: OSTI ID: 1713198

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Vol. 22 Journal Issue: 34; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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