Related Experiment Video
Updated: May 15, 2026

Proton Transfer and Protein Conformation Dynamics in Photosensitive Proteins by Time-resolved Step-scan Fourier-transform Infrared Spectroscopy
Published on: June 27, 2014
A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous
1The Fritz Haber Research Center, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Abstract:
In liquid water the transfer of an excess proton between two water molecules occurs through the Zundel cation, H(2)O···H(+)···OH(2). The proton-transfer mode is the asymmetric stretch of the central O···H(+)···O moiety, but there is no consensus on its identification in the infrared spectra of acidic aqueous solutions. Also, in experiments with protonated gas-phase water clusters, its position shifts with cluster size, which makes its relationship with solution spectra unclear. Here we introduce a 'clusters-in-liquid' approach for calculating the infrared spectrum from any set of charges, even single protons. We apply this procedure to multistate empirical valence-bond trajectories of protonated liquid water and to ab initio molecular dynamics of the protonated water dimer and hexamer in the gas phase. The calculated proton-transfer mode is manifested in both systems as a peak near 1,740 cm(-1), in quantitative agreement with a band of similar frequency in the experimental infrared spectrum of protonated water clusters.
Related Concept Videos
Infrared (IR) Spectroscopy: Overview
Different compounds display unique properties due to their...
NMR and Mass Spectroscopy of Carboxylic Acids
While α protons of carboxylic acids absorb at 2–2.5 ppm, β protons absorb further upfield.
Carboxylic acids are easily identified by dissolving them in deuterium oxide, which results in a rapid exchange of the acidic protons with deuterium. This leads to the disappearance of the acidic...
Spectroscopy of Carboxylic Acid Derivatives
In the...
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
IR Frequency Region: Fingerprint Region
The...
IR and UV–Vis Spectroscopy of Carboxylic Acids
However, the stretching absorptions for the C=O bond vary depending on the structure of carboxylic acids. The C=O bond of the free carboxylic acids shows a higher stretching frequency, 1760 cm−1, while H-bonded carboxylic acids (dimers) exhibit stretching absorptions at a lower frequency, 1710 cm−1. The C=O bond of the...

