An ab initio investigation of bismuth hydration

Abstract

A series of geometry, frequency, and energy calculations of aquabismuth(III) complexes were carried out at up to the MP2/CEP-121G* level. A thorough examination of all species up to and including enneacoordinate species was carried out. The structures of the complexes are compared with experimental data where available. Deviations from the most highly symmetric structures are consistent with the inert-pair effect. In addition, protonated bismuth–oxo clusters of the stoichiometry Bi6O8–n(OH)n(2+n)+, n = 0–4 are examined. The Raman spectrum of bismuth perchlorate with added perchloric and hydrochloric acid is measured.Key words: bismuth, aqua complexes, ab initio, Raman spectra.

An ab initio study of beryllium(II) hydration

“…To support the experimental assignments, ab initio calculations were carried out at the HF, MP2, and B3LYP levels, using the 6-31G * and 6-31+G * basis sets. The agreement between theory and experiment, although good, was not as good as we have typically found [2][3][4][5][6][7]. It was hypothesized that this system had more stringent basis set requirements than those involving other metal ions, so it was felt that further investigation was warranted.…”

Simple soluble Bi(iii) salts as efficient catalysts for the oxidation of alkanes with H2O2

“…Both octahydrates were found to be slightly more stable than the corresponding enneahydrates with the same number of H 2 O molecules (by 1.4-2.0 kcal mol −1 in terms of ΔG s , Table 3), which is in qualitative agreement with previous ab initio theoretical data. 34 Scheme 2 Radical mechanism of the Bi-catalysed alkane oxidation with H 2 O 2 (the rate limiting step of the whole process is boxed).…”

Hydration of beryllium(ii) in aqueous solutions of common inorganic salts. A combined vibrational spectroscopic and ab initio molecular orbital study

“…In order to obtain realistic frequencies of the metal oxygen cluster, an explicit second hydration sphere has to be considered. [79][80][81][82][83][84] Therefore, we constructed clusters with four water molecules in the inner sphere and different numbers of water molecules in the second hydration sphere, namely Be[4 + m] with m = 1, 2, 4 and 8. A cluster denoted Be [6 + 12], [Be(H 2 O) 18 ] 2+ , with 6 waters in the inner-sphere of Be 2+ and 12 waters in the second sphere has also been calculated.…”