Rotational Motion and Nuclear Spin Interconversion of H₂O Encapsulated in C₆₀ Appearing in the Low-Temperature Heat Capacity

Abstract

The heat capacity of H₂O encapsulated in fullerene C₆₀ is determined for the first time at temperatures between 0.6 and 200 K. The water molecule in H₂O@C₆₀ undergoes quantum rotation at low temperature, and the ortho-H₂O and para-H₂O isomers are identified by labeling the rotational energy levels with the nuclear spin states. A rounded heat capacity maximum is observed at ∼2 K after rapid cooling due to splitting of the rotational J _KaKc = 1₀₁ ground state of ortho-H₂O. This anomalous feature decreases in magnitude over time, reflecting the conversion of ortho-H₂O to para-H₂O. Time-dependent heat capacity measurements at constant temperature reveal three nuclear spin conversion processes: a thermally activated transition with E_a ≈ 3.2 meV and two temperature-independent tunneling processes with time constants of τ₁ ≈ 1.5 h and τ₂ ≈ 11 h.