Charge polarization with large amplitude hydrogen motion of pyrazinyl radical: implication for the diffusion dynamics

In this Letter we discuss in the case of pyrazinyl radical the effect of the large amplitude motion on the charge polarization. The extra hydrogen of pyrazinyl radical is nonplanar at the equilibrium geometry, whereas it is delocalized in the vibrational ground state along the wagging direction. The large amplitude motion of the hydrogen triply enhances the effective out-of-plane polarizability of the ground state. This augmented charge polarization could play a considerable role in the diffusion dynamics in solutions.