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A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions

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A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions. / Kulig, Waldemar; Agmon, Noam.

In: Nature Chemistry, Vol. 5, No. 1, 01.2013, p. 29-35.

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Kulig, Waldemar ; Agmon, Noam. / A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions. In: Nature Chemistry. 2013 ; Vol. 5, No. 1. pp. 29-35.

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@article{9aa6d5b9d4ac40049ce32043922158c6,
title = "A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions",
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.",
author = "Waldemar Kulig and Noam Agmon",
year = "2013",
month = "1",
doi = "10.1038/nchem.1503",
language = "English",
volume = "5",
pages = "29--35",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Nature Publishing Group",
number = "1",

}

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TY - JOUR

T1 - A 'clusters-in-liquid' method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions

AU - Kulig, Waldemar

AU - Agmon, Noam

PY - 2013/1

Y1 - 2013/1

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84871565081&partnerID=8YFLogxK

U2 - 10.1038/nchem.1503

DO - 10.1038/nchem.1503

M3 - Article

VL - 5

SP - 29

EP - 35

JO - Nature Chemistry

JF - Nature Chemistry

SN - 1755-4330

IS - 1

ER -