Structures of liquid and aqueous water isotopologues at ambient temperature from ab initio path integral simulations

The heavy hydrogen isotopes D and T are found in trace amounts in water, and when their concentration increases they can play an intricate role in modulating the physical properties of the liquid. We present an analysis of the microscopic structures of ambient light water (H₂O(l)), heavy water (D₂O(l)), T₂O(l), HDO(aq) and HTO(aq) studied by ab initio path integral molecular dynamics (PIMD). Unlike previous ab initio PIMD investigations of H₂O(l) and D₂O(l) [Chen et al., Phys. Rev. Lett., 2003, 91, 215503] [Machida et al., J. Chem. Phys., 2017, 148, 102324] we find that D₂O(l) is more structured than H₂O(l), as is predicted by the experiment. The agreement between the experiment and our simulation for H₂O(l) and D₂O(l) allows us to accurately predict the intra- and intermolecular structures of T₂O(l) HDO(aq) and HTO(aq). T₂O(l) is found to have a similar intermolecular structure to that of D₂O(l), while the intramolecular structure is more compact, giving rise to a smaller dipole moment than those of H₂O(l) and D₂O(l). For the mixed isotope species, HDO(aq) and HTO(aq), we find smaller dipole moments and fewer hydrogen bonds when compared with the pure species H₂O and D₂O. We can attribute this effect to the relative compactness of the mixed isotope species, which results in a lower dipole moment than that of the pure species.