Magic Numbers for the Photoelectron Anisotropy in Li-Doped Dimethyl Ether Clusters

Abstract

Photoelectron velocity map imaging of Li(CH 3 OCH 3 ) n clusters (1 ≤ n ≤ 175) is used to search for magic numbers related to the photoelectron anisotropy. Comparison with density functional calculations reveals magic numbers at n = 4, 5, and 6, resulting from the symmetric charge distribution with high s-character of the highest occupied molecular orbital. Since each of these three cluster sizes correspond to the completion of a first coordination shell, they can be considered as “isomeric motifs of the first coordination shell”. Differences in the photoelectron anisotropy, the vertical ionization energies and the enthalpies of vaporization between Li(CH 3 OCH 3 ) n and Na(CH 3 OCH 3 ) n can be rationalized in terms of differences in their solvation shells, atomic ionization energies, polarizabilities, metal–oxygen bonds, ligand–ligand interactions and by cooperative effects.

Magnetic deflection of neutral sodium-doped ammonia clusters

“…[2][3][4][5] In bulk solutions the paramagnetic species have been investigated via electron spin resonance (ESR) 6 and nuclear magnetic resonance (NMR) spectroscopy 7 (and references therein). Neutral sodium doped ammonia clusters Na(NH 3 ) n have previously served as model systems to study the electronic properties of the 'ammoniated' electron via photoion spectroscopy, photoelectron spectroscopy and ab initio methods [8][9][10][11][12][13][14][15][16][17][18][19][20] (and references therein). Photoion spectroscopy has revealed that the ion appearance energy of Na(NH 3 ) n decreases systematically with increasing number of solvent molecules 15 (and references therein).…”

Introducing Novel Materials with Diffuse Electrons for Applications in Redox Catalysis and Quantum Computing via Theoretical Calculations

“…Along the metal identity axis, thorium makes the most exotic species forming a Th­(NH 3 ) 10 complex with four diffuse peripheral electrons (article in preparation). Moving along the second axis of the chemical space (ligand identity), water, − dimethyl ether, , crown ethers, − methanol, , cyclams, cryptands, methylated ammonia, ,− and diamines have been shown to create similar systems with various coordination numbers, stabilities, and reactivity.…”

A fresh perspective on metal ammonia molecular complexes and expanded metals: opportunities in catalysis and quantum information

“…These are commonly composed of alkali, alkaline earth, aluminum, oxygen and nitrogen atoms, 6 or even metallic clusters. 14 Expanded metals are similar to organic electrides 15 but the ligands are solvent molecules known to solvate electrons, such as ammonia, 5 water, [16][17][18][19][20] dimethyl ether, 21,22 methanol, 23,24 methylamine, [25][26][27][28][29][30][31] acetonitrile, 32 hexamethylphosphoric triamide (HMPA) 33,34 and tetra-hydrofuran. 35 Electrides and expanded metals can be unified under the general category of solvent separated electrons from metals ions.…”