Impact of the Condensed-Phase Environment on the Translation-Rotation Eigenstates and Spectra of a Hydrogen Molecule in Clathrate Hydrates

We systematically investigate the manifestations of the condensed-phase environment of the structure II clathrate hydrate in the translation-rotation (TR) dynamics and the inelastic neutron scattering (INS) spectra of an H₂ molecule confined in the small dodecahedral cage of the hydrate. The aim is to elucidate the extent to which these properties are affected by the clathrate water molecules beyond the confining cage and the proton disorder of the water framework. For this purpose, quantum calculations of the TR eigenstates and INS spectra are performed for H₂ inside spherical clathrate domains of gradually increasing radius and the number of water molecules ranging from 20 for the isolated small cage to more than 1800. For each domain size, several hundred distinct hydrogen-bonding topologies are constructed in order to simulate the effects of the proton disorder. Our study reveals that the clathrate-induced splittings of the j = 1 rotational level and the translational fundamental of the guest H₂ are influenced by the condensed-phase environment to a dramatically different degree, the former very strongly and the latter only weakly.