Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions
Research output: Contribution to journal › Research article › Contributed › peer-review
Contributors
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 language | English |
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Article number | 4210 |
Journal | Nature communications |
Volume | 13 |
Issue number | 1 |
Publication status | Published - 21 Jul 2022 |
Peer-reviewed | Yes |
Externally published | Yes |
External IDs
PubMed | 35864099 |
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ORCID | /0000-0002-8120-8553/work/161409567 |