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

Florian N. Brünig, Manuel Rammler, Ellen M. Adams, Martina Havenith and Roland R. Netz ()
Additional contact information
Florian N. Brünig: Freie Universität Berlin, Department of Physics
Manuel Rammler: Freie Universität Berlin, Department of Physics
Ellen M. Adams: Ruhr-Universität Bochum, Department of Physical Chemistry II
Martina Havenith: Ruhr-Universität Bochum, Department of Physical Chemistry II
Roland R. Netz: Freie Universität Berlin, Department of Physics

Nature Communications, 2022, vol. 13, issue 1, 1-12

Abstract: 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.

Date: 2022
References: View references in EconPapers View complete reference list from CitEc
Citations: View citations in EconPapers (1)

Downloads: (external link)
https://www.nature.com/articles/s41467-022-31700-x Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-31700-x

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-022-31700-x

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().