The 2D-to-3D geometry hopping in small boron clusters: The charge effect

Infrared-Driven Charge Transfer in Transition Metal B12F12 Clusters

“…Product channels of m/z = 359 amu and lighter exhibit an intense broad peak in the 1200 -1250 cm ─1 region owing to the fact that each isotopologue has several associated isotopomers (i.e., isotopic isomers) contributing to the observed spectrum. For example, the m/z = 359 amu product, which corresponds to production of 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 10 spectrum owing to the vibrational isotope effect. In comparing the spectra recorded for the m/z = 356 -360 amu product channels, which correspond to formation of 10 rationalized if we draw analogy with the textbook example of NaCl, which exists as Na δ+ •Cl δ─ in its ground electronic state, but which dissociates to form neutral products via its lowest thermodynamic threshold in the gas-phase.…”

“…For example, the m/z = 359 amu product, which corresponds to production of 10 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 10 spectrum owing to the vibrational isotope effect. In comparing the spectra recorded for the m/z = 356 -360 amu product channels, which correspond to formation of 10 rationalized if we draw analogy with the textbook example of NaCl, which exists as Na δ+ •Cl δ─ in its ground electronic state, but which dissociates to form neutral products via its lowest thermodynamic threshold in the gas-phase. This, of course, is due to the imbalance between the electron affinity of Cl (3.51 eV) and the ionization energy of Na (5.14 eV).…”

Double aromaticity in transition metal centered double-ring boron clusters M@B2n (M = Ti, Cr, Fe, Ni, Zn; n = 6, 7, 8)

“…The 2D-3D structural transition of neutral boron cluster occurs at B 20 , of which the double-ring tubular structure is proved to be the most stable. 51,55,56 The charge effect has also affected the geometrical transition, 57 and anionic boron cluster remains planar or quasi-planar up to B 24 − . 58 But there are still exceptions, recent studies report a flat cage B 14 cluster 59 and a) Author to whom the correspondence should be addressed.…”

A semi-empirical Hamiltonian for boron, phosphorus and compounds containing boron, phosphorus and silicon.

“…Numerous boron studies have indicated that when precision is required, DFT may be inferior to post Hartree-Fock methods 52 . It is always possible that the clusters or the bulk phases are poorly calculated with DFT, or they are inconsistently calculated.…”

“…The robust check includes structures that are not included in the fitting database, are generally larger structures, and have been previously been studied using DFT 34,39,40,52,[67][68][69][70][71][72] . The energy ordering is checked and the spatial structure is checked.…”