Communication: A concerted mechanism between proton transfer of Zundel anion and displacement of counter cation.
Ab initio path integral molecular dynamics simulation of M(+)(H(3)O(2)(-)) (M = Li, Na, and K) has been carried out to analyze how the structure and dynamics of a low-barrier hydrogen-bonded Zundel anion, H(3)O(2)(-), can be affected by the counter alkali metal cation, M(+). Our simulation predicts that the quantum proton transfer in Zundel anion can be strongly coupled to the motion of counter cation located nearby. A smaller cation can induce larger structural distortion of the Zundel anion fragment making the proton transfer barrier higher, and hence, lower the vibrational excitation energy. It is also argued that a large H∕D isotope effect is present.
Quantum Chemical Physics Division, Graduate School of Science, Yokohama-City University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027, Japan.
Akihito
A
Koizumi
Kimichi
K
Suzuki
Motoyuki
M
Shiga
Masanori
M
Tachikawa