Counterintuitive effects of isotopic doping on the phase diagram of H2-HD-D2 molecular alloy

Molecular hydrogen forms the archetypical quantum solid. Its quantum nature is revealed by behavior which is classically impossible, and by very strong isotope effects(1). Isotope effects between H2, D2 and HD molecules come from mass difference, and the different quantum exchange effects: fermionic H2 molecules have antisymmetric wavefunctions, whilst bosonic D2 molecules have symmetric wavefunctions and HD molecules have no exchange symmetry. To investigate how the phase diagram depends on quantum-nuclear effects, we use high pressure and low temperature in-situ Raman spectroscopy to map out the phase diagrams of H2-HD-D2 with various isotope concentrations over a wide P-T range. We find that mixtures of H2, HD and D2 behave as an isotopic molecular alloy (ideal solution), and exhibit symmetry-breaking phase transitions between
phases I-II and III. Surprisingly, all transitions occur at higher pressures for the alloys than either pure H2 or D2 (2). This runs counter to any quantum effects based on isotope mass, but can be explained by quantum trapping of high kinetic energy states by the exchange interaction.