Effect of Rotational Couplings on Vibrational Spectrum Line Shape of the Bending Mode in Low-Density Supercritical Water: Density and Hydrogen Isotopes Dependencies

The effect of rotations on the line shape of the bending vibrational spectrum for supercritical water was analyzed using classical molecular dynamics simulation for the flexible point-charge SPC/Fw model. The experimental infrared spectrum of the bending mode at the low densities of 0.01–0.04 g·cm^?3 and at 400 °C was essentially reproduced without any other assumptions. The spectrum line shape at low densities consists of two broad rotational bands due to the rotational couplings, as in the case of the O–H stretch mode. This is due to the time-scale separation breakdown but is not due to the presence of any definite clusters. The rotational couplings become more significant at higher temperatures. The separations between the bending band center and the rotational broad side-bands are found to be linearly correlated with the inverse of the total moment of inertia of the water isotopic species, which is clear molecular-level evidence for the rotational couplings.