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Title: Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C5CP02253C· OSTI ID:1214438
 [1];  [2];  [3];  [4];  [5];  [4];  [6];  [7];  [8]
  1. Chinese Univ. of Hong Kong, Shatin (China)
  2. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany); Chinese Academy of Sciences, Dalian (China)
  3. National Supercomputing Center in Shenzhen, Shenzhen (China)
  4. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin (Germany)
  5. Univ. of California, Berkeley, CA (United States)
  6. Universitat Leipzig, Leipzig (Germany)
  7. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  8. Chinese Univ. of Hong Kong, Shatin and Shenzhen (China)
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We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogen bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1214438
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (5)

Infrared Multiphoton Dissociation Spectroscopy with Free-Electron Lasers: On the Road from Small Molecules to Biomolecules journal February 2018
Solvation effects on the vibrational modes in hydrated bicarbonate clusters journal January 2018
Coordination-induced CO 2 fixation into carbonate by metal oxides journal January 2018
Infrared photodissociation spectroscopy of ion-radical networks in cationic dimethylamine complexes journal January 2018
Solvation effects on the N–O and O–H stretching modes in hydrated NO 3 − (H 2 O) n clusters journal January 2018

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