Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Florian N. Brünig - , Free University of Berlin (Author)
  • Manuel Rammler - , Free University of Berlin (Author)
  • Ellen M. Adams - , Ruhr University Bochum (Author)
  • Martina Havenith - , Ruhr University Bochum (Author)
  • Roland R. Netz - , Free University of Berlin (Author)

Abstract

The theoretical basis for linking spectral signatures of hydrated excess protons with microscopic proton-transfer mechanisms has so far relied on normal-mode analysis. We introduce trajectory-decomposition techniques to analyze the excess-proton dynamics in ab initio molecular-dynamics simulations of aqueous hydrochloric-acid solutions beyond the normal-mode scenario. We show that the actual proton transfer between two water molecules involves for relatively large water-water separations crossing of a free-energy barrier and thus is not a normal mode, rather it is characterized by two non-vibrational time scales: Firstly, the broadly distributed waiting time for transfer to occur with a mean value of 200–300 fs, which leads to a broad and weak shoulder in the absorption spectrum around 100 cm−1, consistent with our experimental THz spectra. Secondly, the mean duration of a transfer event of about 14 fs, which produces a rather well-defined spectral contribution around 1200 cm−1 and agrees in location and width with previous experimental mid-infrared spectra.

Details

Original languageEnglish
Article number4210
JournalNature communications
Volume13
Issue number1
Publication statusPublished - 21 Jul 2022
Peer-reviewedYes
Externally publishedYes

External IDs

PubMed 35864099
ORCID /0000-0002-8120-8553/work/161409567