Search for Chirality in Hydrogenated Magnesium Nanosilicates: A DFT and TD-DFT Investigation

The formation of silicate grains in the interstellar medium (ISM), especially those containing chiral surfaces like clinopyroxenes, is poorly understood. Moreover, silicate interactions with various forms of hydrogen – proton (H+), neutral H (HI), and molecular hydrogen (H2) – are of high importance as hydrogen comprises > 90% of the ISM gas budget and these species play important roles in the formation of new molecules in space. Furthermore, silicate surfaces catalyze the formation of H2 in the interstellar medium, formed on dust grain surfaces by H-H association. The technical difficulty of in situ laboratory investigations of nanosilicate nucleation using astrophysically relevant environmental conditions makes computational chemistry a useful tool in studying potential nanosilicate structures. Furthermore, chiral surfaces interacting with chiral organic molecules could serve as the templates that lead to the enantiomeric excess of l-amino acids and d-polyols detected in carbonaceous meteorites. However, in order for this effect to take place, an excess of one chiral form of a mineral is required to break the symmetry. This symmetry breaking event could have been due to asymmetric absorption of circularly polarized light by the nanosilicate as it traverses star-forming regions. We investigate this possibility using a metastable chiral form of an enstatite dimer as an input for density functional theory (DFT) and time dependent (TD-)DFT calculations to obtain various properties and the circular dichroism spectra. All in all, twenty-six magnesium nanosilicate structures were studied using varying degrees of hydrogenation: none, with HI, with H+, and with H2. The HSE06/aug-cc-pVQZ level of theory was used for the DFT calculations. TD-DFT calculations utilized the CAM-B3LYP/cc-pVQZ and ωB97X-D3/cc-pVQZ functional/basis set pairings. Results show that (1) all twenty-six structures have absorption bands that fall within the 0.6–28.3 µm range available with the newly launched James Webb Space Telescope and (2) there is a small enantioselective effect by UV-CPL on the eight chiral enstatite dimers (predicted g-values of up to 0.007). While the observed effect is small, it opens up the possibility that it is the inorganic material that becomes enantiomerically biased by UV-CPL, driving chiral enhancements in meteoritic organic molecules.