Probing the Relationship Between Large-Amplitude Motions in H5(+) and Proton Exchange Between H3(+) and H2

Understanding the spectroscopy and dynamics of H5(+) is central in gaining insights into the H3(+) + H2 → H5(+) → H2 + H3(+) proton transfer reaction. This molecular ion exhibits large-amplitude vibrations, which allow for the transfer of a proton between H3(+) and H2 even in its ground vibrational state. With vibrational excitation, the number of open channels for permutations of protons increase. In this work, the minimized energy path variant of diffusion Monte Carlo is used to investigate how the energetically accessible proton permutations evolve as H5(+) is dissociated into H3(+) + H2. Two mechanisms for proton permutation are investigated. The first is the proton hop, which correlates to large-amplitude vibrations of the central proton in H5(+). The second is the exchange of a pair of hydrogen atoms between H3(+) and H2. This mechanism requires several proton hops along with a 120° rotation of H3(+) within the H5(+) molecular ion. This analysis shows that while there is a narrow region of configuration space over which both isomerization processes are energetically accessible, full permutation of the five protons in H5(+) more likely occurs through a stepwise mechanism. Such full permutation of the protons becomes accessible when the shared proton stretch is excited to the vpt = 2 or 3 excited state. The effects of deuteration and rotational excitation of the H2 and H3(+) products are also investigated. Deuteration inhibits permutation of protons, while rotational excitation has only a small impact on these processes.