Ro-translational dynamics of confined water. I. The confined asymmetric rotor model.

Abstract

Confinement effects on the ro-translational (RT) dynamics of water, trapped in rare gas matrices or within endofullerenes (i.e., H2O@C60), can be experimentally assessed using rotationally resolved far-infrared, or mid-infrared, spectroscopy [Putaud et al., J. Chem. Phys. 156, 074305 (2022) (Paper II)]. The confined rotor model is used here to reveal how the quantized rotational and frustrated translational energy levels of confined water interact and mix by way of the confinement-induced rotation-translation coupling (RTC). An eccentric but otherwise isotropic 3D harmonic effective potential is used to account for confinement effects, thereby allowing the dependence of the magnitude of the RTC on the topology of the model confinement potential, the resulting intricate mixing schemes, and their impact on the RT energy levels to be examined in detail. The confined rotor model thus provides a convenient framework to investigate the matrix and isotope effects on the RT dynamics of water under extreme confinement probed spectroscopically, thereby potentially providing insight into the mechanisms and rates for ortho-H2O ↔ para-H2O nuclear spin isomer interconversion in confined water.