Molecular Mechanism of Conformational Crossover of Mefenamic Acid Molecules in scCO₂

In this work, we studied conformational equilibria of molecules of mefenamic acid in its diluted solution in scCO2 under isochoric heating conditions in the temperature range of 140–210 °C along the isochore corresponding to the scCO2 density of 1.1 of its critical value. This phase diagram range totally covers the region of conformational transitions of molecules of mefenamic acid in its saturated solution in scCO2. We found that in the considered phase diagram region, the equilibrium of two conformers is realized in this solution. In the temperature range of 140–180 °C, conformer I related to the first, most stable polymorph of mefenamic acid prevails. In the temperature range of 200–210 °C, conformer II, which is related to the second metastable polymorph becomes dominant. Based on the results of quantum chemical calculations and experimental IR spectroscopy data on the mefenamic acid conformer populations, we classified this temperature-induced conformational crossover as an entropy-driven phenomenon

Cosmic rays in molecular clouds probed by H

Context. Low-energy cosmic rays (<1 TeV) play a fundamental role in the chemical and dynamical evolution of molecular clouds, as they control the ionisation, dissociation, and excitation of H2. Their characterisation is therefore important both for the interpretation of observations and for the development of theoretical models. However, the methods used so far for estimating the cosmic-ray ionisation rate in molecular clouds have several limitations due to uncertainties in the adopted chemical networks. Aims. We refine and extend a previously proposed method to estimate the cosmic-ray ionisation rate in molecular clouds by observing rovibrational transitions of H2 at near-infrared wavelengths, which are mainly excited by secondary cosmic-ray electrons. Methods. Combining models of interstellar cosmic-ray propagation and attenuation in molecular clouds with the rigorous calculation of the expected secondary electron spectrum and updated electron-H2 excitation cross sections, we derive the intensity of the four H2 rovibrational transitions observable in cold dense gas: (1−0)O(2), (1−0)Q(2), (1−0)S(0), and (1−0)O(4). Results. The proposed method allows the estimation of the cosmic-ray ionisation rate for a given observed line intensity and H2 column density. We are also able to deduce the shape of the low-energy cosmic-ray proton spectrum impinging upon the molecular cloud. In addition, we present a look-up plot and a web-based application that can be used to constrain the low-energy spectral slope of the interstellar cosmic-ray proton spectrum. We finally comment on the capability of the James Webb Space Telescope to detect these near-infrared H2 lines, which will make it possible to derive, for the first time, spatial variation in the cosmic-ray ionisation rate in dense gas. Besides the implications for the interpretation of the chemical-dynamic evolution of a molecular cloud, it will finally be possible to test competing models of cosmic-ray propagation and attenuation in the interstellar medium, as well as compare cosmic-ray spectra in different Galactic regions