In the present study, the differential scattering cross-sections, depolarization ratios and Raman shifts of small molecular systems are obtained from configuration iteration wave functions of vibrational self-consistent field (VSCF) states. The transition polarizabilities were modeled using the Placzek approximation, neglecting those contributions not arising from the electric dipole mechanism. This theoretical approach is considered a good approximation for samples that absorb in the UV range if the excitation radiation falls in the visible region, as is the case of the molecules selected for the present study, namely: water, methane, and acetylene. Potential energy and electronic polarizability surfaces are calculated by the CCSD(T) and CC3 methods with aug-cc-p(C)V(T,Q,5)Z basis sets. The vibrational Hamiltonian includes the vibrational angular momentum contribution of the Watson kinetic energy operator. As expected, due to the variational nature of the VSCF and vibrational configuration interaction (VCI) methods, the Raman transition wavenumbers are substantially improved over the harmonic predictions. Surprisingly, the scattering cross-sections obtained using the harmonic approximation or the VSCF method better agrees with the experimental values than those cross-sections predicted using VCI wave functions. The more significant deviations of the VCI results from the experimental reference may be related to the significant uncertainties of the measured cross-sections. Still, it may also indicate that the VCI Raman transition moments may require a more accurate description of the electronic polarizability surface. Finally, the depolarization ratios calculated for H 2 O and C 2 D 2 using harmonic and VCI wave functions have similar accuracy, whereas, for C 2 H 2 and C 2 HD, the VCI results are more accurate.
We herein present an experiment where the concentrations of tartrazine, sunset yellow and amaranth in samples containing these three food dyes are determined by system of equations (SE) and classical least squares (CLS) multivariate calibration methods using light absorption data. Firstly, concentrations are obtained by means of the well-known SE method, that is, by solving a set of three linear equations in which the Beer-Lambert’s proportionality coefficients are obtained from analytical curves. Then, it is shown that the CLS method is a natural extension to SE, with an arbitrarily large number of equations. Nevertheless, within the CLS method, the unknown coefficients are found using mixtures with known concentrations of each dye. In order to introduce the students to the basics of algorithms and numerical computations, data treatment is performed in a command-line fashion using a freely available software. Advantages of multivariate calibration models over univariate ones are made clear, and the performance of the CLS and SE methods is compared based on the root-mean-square error.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.