Effect of ion vibration for proton-transfer reaction of ammonia cation

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Abstract
Ion vibration gives rise to a new pulsing dipole moment which affects the long‐range interaction with the target molecule. This pulsing long‐range interaction mechanism has been applied to the proton‐transfer reaction NH+ 3(ν)+NH3→NH2+NH+ 4 in which the vibrational mode‐specific depression of the reaction rate is observed. Significance of the vibrationally induced dipole moment of NH+ 3(ν) has been clarified in such a way that the origin of the depression is ascribed to the interaction of this pulsing dipole moment with the permanent dipole moment of NH3. The results of calculation agree qualitatively well with the experimental result [Chupka and Russell, J. Chem. Phys. 4 8, 1527 (1968)].