Large Angular Jump Mechanism Observed for Hydrogen Bond Exchange in Aqueous Perchlorate Solution

Journal Article · Fri Jun 11 00:00:00 EDT 2010 · Submitted to Science

DOI:https://doi.org/10.1126/science.1187707· OSTI ID:981665

Ji, Minbiao; Odelius3, Michael; Gaffney1, K J

The mechanism for hydrogen bond (H-bond) switching in solution has remained subject to debate despite extensive experimental and theoretical studies. We have applied polarization-selective multidimensional vibrational spectroscopy to investigate the H-bond exchange mechanism in aqueous NaClO{sub 4} solution. The results show that a water molecule shifts its donated H-bonds between water and perchlorate acceptors by means of large, prompt angular rotation. Using a jump-exchange kinetic model, we extract an average jump angle of 49 {+-} 4{sup o}, in qualitative agreement with the jump angle observed in molecular dynamics simulations of the same aqueous NaClO{sub 4} solution.

• Research Organization: SLAC National Accelerator Lab., Menlo Park, CA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC02-76SF00515
• OSTI ID: 981665
• Report Number(s): SLAC-PUB-14119; TRN: US201012%%973
• Journal Information: Submitted to Science, Journal Name: Submitted to Science
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
HYDROGEN
KINETICS
PERCHLORATES
ROTATION
SPECTROSCOPY
WATER
Other