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We study by computer simulations the coupled rotational and translationaldynamics of three important linear diatomic molecules, namely, carbon monoxide(CO), nitric oxide (NO) and cyanide ion (CN-) in water. Translational diffusionof these molecules is found to be strongly coupled to their own rotationaldynamics which in turn are coupled to similar motions of surrounding water. Weexamined the validity of hydrodynamic predictions and found them to be largelyinsufficient, particularly for rotational diffusion. A mode coupling theoryapproach is developed and applied to understand the complexity oftranslation-rotation coupling.

Translation-Rotation Coupling in the Dynamics of Linear Molecules in Water