title: Observation of a Zundel-like transition state during proton transfer in aqueous hydroxide solutions.
abstract: It is generally accepted that the anomalous diffusion of the aqueous hydroxide ion results from its ability to accept a proton from a neighboring water molecule; yet, many questions exist concerning the mechanism for this process. What is the solvation structure of the hydroxide ion? In what way do water hydrogen bond dynamics influence the transfer of a proton to the ion? We present the results of femtosecond pump-probe and 2D infrared experiments that probe the O-H stretching vibration of a solution of dilute HOD dissolved in NaOD/D(2)O. Upon the addition of NaOD, measured pump-probe transients and 2D IR spectra show a new feature that decays with a 110-fs time scale. The calculation of 2D IR spectra from an empirical valence bond molecular dynamics simulation of a single NaOH molecule in a bath of H(2)O indicates that this fast feature is due to an overtone transition of Zundel-like H(3)O(2)(-) states, wherein a proton is significantly shared between a water molecule and the hydroxide ion. Given the frequency of vibration of shared protons, the observations indicate the shared proton state persists for 2-3 vibrational periods before the proton localizes on a hydroxide. Calculations based on the EVB-MD model argue that the collective electric field in the proton transfer direction is the appropriate coordinate to describe the creation and relaxation of these Zundel-like transition states.
authors: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
authors: Sean T
authors: ST
authors: Roberts
authors: Poul B
authors: PB
authors: Petersen
authors: Krupa
authors: K
authors: Ramasesha
authors: Andrei
authors: A
authors: Tokmakoff
authors: Ivan S
authors: IS
authors: Ufimtsev
authors: Todd J
authors: TJ
authors: Martinez
mesh_terms: D003198:Computer Simulation; D006860:Hydrogen Bonding; D006878:Hydroxides / Q000737:chemistry*; D008956:Models, Chemical; D011522:Protons; D013055:Spectrophotometry, Infrared; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D011522:Protons; D014867:Water; C031356:hydroxide ion