Interactions between grain size and composition of sediments: two examples

Two contrasting case studies of sediment and detrital mineral composition are investigated in order to outline interactions between chemical composition and grain size. Modern glacial sediments exhibit a strong dependence of the two parameters due to the preferential enrichment of mafic minerals, especially biotite, in the fine-grained fractions. On the other hand, the composition of detrital heavy minerals (here: rutile) appears to be not systematically related to grain-size, but is strongly controlled by location, i.e. the petrology of the source rocks of detrital grains. This supports the use of rutile as a well-suited tracer mineral for provenance studies. The results further suggest that (i) interpretations derived from whole-rock sediment geochemistry should be flanked by grain-size observations, and (ii) a more sound statistical evaluation of these interactions require the development of new tailor-made statistical tools to deal with such so-called two-way compositions

Systematic study of the static electrical properties of the CO molecule: influence of the basis set size and correlation energy

The influence of the basis set size and the correlation energy in the static electrical properties of the CO molecule is assessed. In particular, we have studied both the nuclear relaxation and the vibrational contributions to the static molecular electrical properties, the vibrational Stark effect (VSE) and the vibrational intensity effect (VIE). From a mathematical point of view, when a static and uniform electric field is applied to a molecule, the energy of this system can be expressed in terms of a double power series with respect to the bond length and to the field strength. From the power series expansion of the potential energy, field-dependent expressions for the equilibrium geometry, for the potential energy and for the force constant are obtained. The nuclear relaxation and vibrational contributions to the molecular electrical properties are analyzed in terms of the derivatives of the electronic molecular properties. In general, the results presented show that accurate inclusion of the correlation energy and large basis sets are needed to calculate the molecular electrical properties and their derivatives with respect to either nuclear displacements or/and field strength. With respect to experimental data, the calculated power series coefficients are overestimated by the SCF, CISD, and QCISD methods. On the contrary, perturbation methods (MP2 and MP4) tend to underestimate them. In average and using the 6-311 + G(3df) basis set and for the CO molecule, the nuclear relaxation and the vibrational contributions to the molecular electrical properties amount to 11.7%, 3.3%, and 69.7% of the purely electronic μ, α, and β values, respectively