A 'clusters-in-liquid' Method for Calculating Infrared Spectra Identifies the Proton-transfer Mode in Acidic Aqueous Solutions

Overview

Journal Nat Chem

Specialty Chemistry

Date 2012 Dec 19

PMID 23247174

Citations 23

Authors

Waldemar Kulig

Noam Agmon

Affiliations

Soon will be listed here.

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.

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