Ab-initio structure, energy and stable Cr isotopes equilibrium fractionation of some geochemically relevant H-O-Cr-Cl complexes

Twelve Cr(III) molecules and six Cr(VI) molecules of geochemical interest in the system Cr-H-O-Cl were investigated by ab initio Density Functional Theory in the aim of determining stationary state geometries, electronic energies and vibrational properties. The vibrational analysis conducted on the 50Cr, 52Cr, 53Cr and 54Cr isotopomers indicates important separative effects which result in mass spectrometric measurable fractionation factors in a wide thermal range. The effect of the central cation on the computed vibrational modes is interpreted in terms of Redlich's product rule with the introduction of an isotopic ergodicity factor related to the effect of bulk molecular masses and momenta of inertia about the principal rotational axes. After the initial gas phase optimization, some relevant molecules were subjected to the effects of reaction field through Onsager's Model, Tomasi's continuum Model and Conductor-like Screening Model procedures. Structures and vibrational properties prove in all cases not to be severely affected by solvation, although the effect of the reaction field is to reduce somewhat the isotopic fractionation in Cr(III)-Cr(VI) aqueous redox equilibria, with respect to the gaseous state. Some of the computed separative effects are applicable to geochemical investigations.