Large amplitude motion in cold monohydrated dihydrogen phosphate anions H2PO4−(H2O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations

Ling Jiang; Shou-Tian Sun; Nadja Heine; Jian-Wen Liu; Tara I. Yacovitch; Torsten Wende; Zhi-Feng Liu; Daniel M. Neumark; Knut R. Asmis

doi:10.1039/C3CP54250E

Large amplitude motion in cold monohydrated dihydrogen phosphate anions H₂PO₄⁻(H₂O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations†

Ling Jiang,‡^a Shou-Tian Sun,^b Nadja Heine,^a Jian-Wen Liu,^c Tara I. Yacovitch,§^d Torsten Wende,¶^a Zhi-Feng Liu,*^b Daniel M. Neumark*^de and Knut R. Asmis*^af

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* Corresponding authors

^a Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4–6, D-14195 Berlin, Germany
E-mail: asmis@fhi-berlin.mpg.de

^b Department of Chemistry and Centre for Scientific Modeling and Computation, Chinese University of Hong Kong, Shatin, Hong Kong, China
E-mail: zfliu@cuhk.edu.hk

^c National Supercomputing Center in Shenzhen, Shenzhen, China

^d Department of Chemistry, University of California, Berkeley, California 94720, USA
E-mail: dneumark@berkeley.edu

^e Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

^f Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Linnéstrasse 2, D-04103 Leipzig, Germany

Abstract

The vibrational spectroscopy of monohydrated dihydrogen phosphate anions, H₂PO₄⁻(H₂O), is studied in the O–H stretching (2700–3900 cm⁻¹) and the fingerprint regions (600–1800 cm⁻¹). Assignment of the experimental infrared multiple photon photodissociation spectra based on the predicted harmonic spectra of energetically low-lying 0 K structures is not conclusive. Ab initio molecular dynamics simulations reveal that the water molecule undergoes large amplitude motion, even at low internal temperatures, and that the dipole time correlation function qualitatively captures the anharmonic effects of the low-barrier isomerization reaction on the infrared intensities.

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DOI: https://doi.org/10.1039/C3CP54250E
Article type: Communication
Submitted: 09 Oct 2013
Accepted: 13 Nov 2013
First published: 15 Nov 2013
This article is Open Access

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Phys. Chem. Chem. Phys., 2014,16, 1314-1318

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Large amplitude motion in cold monohydrated dihydrogen phosphate anions H₂PO₄⁻(H₂O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations

L. Jiang, S. Sun, N. Heine, J. Liu, T. I. Yacovitch, T. Wende, Z. Liu, D. M. Neumark and K. R. Asmis, Phys. Chem. Chem. Phys., 2014, 16, 1314 DOI: 10.1039/C3CP54250E

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Physical Chemistry Chemical Physics

Large amplitude motion in cold monohydrated dihydrogen phosphate anions H₂PO₄⁻(H₂O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations†

Abstract

Supplementary files

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Large amplitude motion in cold monohydrated dihydrogen phosphate anions H₂PO₄⁻(H₂O): infrared photodissociation spectroscopy combined with ab initio molecular dynamics simulations

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Physical Chemistry Chemical Physics