Morphologies and Cryo Activities of Transition Metal Clusters: Every Atom counts!

Cations and anions of size selected transition metal (TM) clusters attach N2 molecules under single collision cryo conditions, and they may or may not subsequently activate the adsorbates. Cryo kinetics, infrared photon dissociation (IR-PD) spectra and DFT modelling reveal insights on the cluster morphologies and on likely or unlikely activation pathways. The analysis of spin states [1a, b] and molecular orbitals unveils the fluxional electronics of adsorbate cluster complexes. Our studies have so far covered clusters of Cobalt [2], Nickel [3,4,5], Rhodium [6,7], Iron [8,9], bimetallic Rhodium-Iron alloys [10,11], Tantalum [12,13,14], and Ruthenium [15]. This presentation shall cover selected examples and outline routes to future work.

[1b] Phys. Rev. Lett. 107, 233401 (2011) DOI: 10.1103/PhysRevLett.107.233401

[1a] J. Chem. Phys. 143, 104302 (2015) DOI: 10.1063/1.4929482

[2] Phys. Chem. Chem. Phys. 17, 10358 (2015) DOI: 10.1039/c5cp00047e

[3] J. Phys. Chem. C 121, 10907–10918 (2017) DOI: 10.1021/acs.jpcc.6b12167

[4] J. Chem. Phys. 147, 184304 (2017) DOI: 10.1063/1.4997403

[5] J. Chem. Phys. 147, 184305 (2017) DOI: 10.1063/1.4997407

[6] Top. Catal. 61, 106 (2018) DOI: 10.1007/s11244-017-0865-2

[7] Mol. Phys. 119, e1953172 (2021) DOI: 10.1080/00268976.2021.1953172

[8] J. Chem. Phys. 155(24), 244306 (2021) DOI: 10.1063/5.0064965

[9] J. Chem. Phys. 155(24), 244305 (2021) DOI: 10.1063/5.0064966

[10] J. Chem. Phys. 156(1), 014302 (2022) DOI: 10.1063/5.0075289

[11] J. Chem. Phys. 156(5), 054308 (2022) DOI: 10.1063/5.0075286

[12] Phys. Chem. Chem. Phys. 23, 11345 (2021) DOI: 10.1039/D0CP06208A

[13] J. Chem. Phys. 159, 164306 (2023) DOI: 10.1063/5.0157218

[14] J. Chem. Phys. 159, 164303 (2023) DOI: 10.1063/5.0157217

[15] to be published