skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H 2PO 4 -(H 2O) 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 H 2PO 4 -(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H 2PO 4 -, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretationmore » of IRMPD spectra of microhydrated ions.« less

Authors:
 [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)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1214438
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Sun, Shou -Tian, Jiang, Ling, Liu, J. W., Heine, Nadja, Yacovitch, Tara I., Wende, Torsten, Asmis, Knut R., Neumark, Daniel M., and Liu, Zhi -Feng. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations. United States: N. p., 2015. Web. doi:10.1039/C5CP02253C.
Sun, Shou -Tian, Jiang, Ling, Liu, J. W., Heine, Nadja, Yacovitch, Tara I., Wende, Torsten, Asmis, Knut R., Neumark, Daniel M., & Liu, Zhi -Feng. Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations. United States. doi:10.1039/C5CP02253C.
Sun, Shou -Tian, Jiang, Ling, Liu, J. W., Heine, Nadja, Yacovitch, Tara I., Wende, Torsten, Asmis, Knut R., Neumark, Daniel M., and Liu, Zhi -Feng. Fri . "Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations". United States. doi:10.1039/C5CP02253C. https://www.osti.gov/servlets/purl/1214438.
@article{osti_1214438,
title = {Microhydrated dihydrogen phosphate clusters probed by gas phase vibrational spectroscopy and first principles calculations},
author = {Sun, Shou -Tian and Jiang, Ling and Liu, J. W. and Heine, Nadja and Yacovitch, Tara I. and Wende, Torsten and Asmis, Knut R. and Neumark, Daniel M. and Liu, Zhi -Feng},
abstractNote = {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.},
doi = {10.1039/C5CP02253C},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = ,
volume = ,
place = {United States},
year = {2015},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

IR Spectra of Phosphate Ions in Aqueous Solution:  Predictions of a DFT/MM Approach Compared with Observations
journal, July 2004

  • Klähn, Marco; Mathias, Gerald; Kötting, Carsten
  • The Journal of Physical Chemistry A, Vol. 108, Issue 29
  • DOI: 10.1021/jp048617g

Why nature chose phosphates
journal, March 1987


The regulation and function of phosphate in the human body
journal, January 2004


The Guanine Nucleotide-Binding Switch in Three Dimensions
journal, November 2001


Interaction of adenosine 5'-triphosphate with Mg2+: vibrational study of coordination sites by use of 18O-labeled triphosphates
journal, January 1988

  • Takeuchi, Hideo.; Murata, Hiroshi.; Harada, Issei.
  • Journal of the American Chemical Society, Vol. 110, Issue 2
  • DOI: 10.1021/ja00210a013

The GAP arginine finger movement into the catalytic site of Ras increases the activation entropy
journal, April 2008

  • Kotting, C.; Kallenbach, A.; Suveyzdis, Y.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 17
  • DOI: 10.1073/pnas.0712095105

A phosphoryl transfer intermediate in the GTPase reaction of Ras in complex with its GTPase-activating protein
journal, September 2006

  • Kotting, C.; Blessenohl, M.; Suveyzdis, Y.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 38
  • DOI: 10.1073/pnas.0604128103

Toward a General Method to Observe the Phosphate Groups of Phosphoenzymes with Infrared Spectroscopy
journal, September 2006


Structure and dynamics of phosphate ion in aqueous solution: An ab initio QMCF MD study
journal, November 2008

  • Pribil, Andreas B.; Hofer, Thomas S.; Randolf, Bernhard R.
  • Journal of Computational Chemistry, Vol. 29, Issue 14
  • DOI: 10.1002/jcc.20968

Hydrogen transfer and hydration properties of HnPO43−n (n=0–3) in water studied by first principles molecular dynamics simulations
journal, June 2009

  • Tang, Emilia; Di Tommaso, Devis; de Leeuw, Nora H.
  • The Journal of Chemical Physics, Vol. 130, Issue 23
  • DOI: 10.1063/1.3143952

Accuracy of the microsolvation–continuum approach in computing the pKa and the free energies of formation of phosphate species in aqueous solution
journal, January 2010

  • Tang, Emilia; Di Tommaso, Devis; de Leeuw, Nora H.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 41
  • DOI: 10.1039/c0cp00175a

Dependence of pKa on solute cavity for diprotic and triprotic acids
journal, January 2011

  • Lee, Tae Bum; McKee, Michael L.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 21
  • DOI: 10.1039/c1cp20161a

Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water
journal, October 2012

  • Pluhařová, Eva; Ončák, Milan; Seidel, Robert
  • The Journal of Physical Chemistry B, Vol. 116, Issue 44
  • DOI: 10.1021/jp306348b

Vibrational Spectra of Phosphate Ions in Aqueous Solution Probed by First-Principles Molecular Dynamics
journal, March 2012

  • VandeVondele, Joost; Tröster, Philipp; Tavan, Paul
  • The Journal of Physical Chemistry A, Vol. 116, Issue 10
  • DOI: 10.1021/jp211783z

Micro-Raman observation on the H 2 PO 4 association structures in a supersaturated droplet of potassium dihydrogen phosphate (KH 2 PO 4 )
journal, January 2013

  • Syed, Kamran Ajmal; Pang, Shu-Feng; Zhang, Yun
  • The Journal of Chemical Physics, Vol. 138, Issue 2
  • DOI: 10.1063/1.4773585

Micro-Raman Observation on the HPO 4 2– Association Structures in an Individual Dipotassium Hydrogen Phosphate (K 2 HPO 4 ) Droplet
journal, February 2012

  • Syed, Kamran Ajmal; Pang, Shu-Feng; Zhang, Yun
  • The Journal of Physical Chemistry A, Vol. 116, Issue 6
  • DOI: 10.1021/jp2110743

An ab Initio, Infrared, and Raman Investigation of Phosphate Ion Hydration
journal, October 2003

  • Pye, Cory C.; Rudolph, Wolfram W.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 41
  • DOI: 10.1021/jp035594h

Neutron scattering studies on the hydration of phosphate ions in aqueous solutions of K3PO4, K2HPO4 and KH2PO4
journal, January 2003

  • Mason, P. E.; Cruickshank, J. M.; Neilson, G. W.
  • Physical Chemistry Chemical Physics, Vol. 5, Issue 20
  • DOI: 10.1039/b306344e

Hydrogen-Bonded Structure in Concentrated Aqueous Phosphoric Acid Solutions
journal, May 2000

  • Kameda, Yasuo; Sugawara, Kentaro; Hosaka, Takayoshi
  • Bulletin of the Chemical Society of Japan, Vol. 73, Issue 5
  • DOI: 10.1246/bcsj.73.1105

Systematic Study of Hydration Patterns of Phosphoric(V) Acid and Its Mono-, Di-, and Tripotassium Salts in Aqueous Solution
journal, May 2009

  • Śmiechowski, Maciej; Gojło, Emilia; Stangret, Janusz
  • The Journal of Physical Chemistry B, Vol. 113, Issue 21
  • DOI: 10.1021/jp810195h

Photoelectron emission spectroscopy of inorganic anions in aqueous solution
journal, March 1981


Free Energies of Hydration in the Gas Phase of the Anions of Some Oxo Acids of C, N, S, P, Cl, and I
journal, October 1995

  • Blades, Arthur T.; Klassen, John S.; Kebarle, Paul
  • Journal of the American Chemical Society, Vol. 117, Issue 42
  • DOI: 10.1021/ja00147a019

Electrospray: From ions in solution to ions in the gas phase, what we know now
journal, November 2009

  • Kebarle, Paul; Verkerk, Udo H.
  • Mass Spectrometry Reviews, Vol. 28, Issue 6
  • DOI: 10.1002/mas.20247

Photoelectron spectroscopy of Cl , Br , and I solvated in water clusters
journal, December 1994

  • Markovich, Gil; Pollack, Stuart; Giniger, Rina
  • The Journal of Chemical Physics, Vol. 101, Issue 11
  • DOI: 10.1063/1.467965

Microscopic hydration of the fluoride anion
journal, January 1999

  • Cabarcos, Orlando M.; Weinheimer, Corey J.; Lisy, James M.
  • The Journal of Chemical Physics, Vol. 110, Issue 1
  • DOI: 10.1063/1.478075

Probing solution-phase species and chemistry in the gas phase
journal, July 2002

  • Wang, Xue-Bin; Yang, Xin; Wang, Lai-Sheng
  • International Reviews in Physical Chemistry, Vol. 21, Issue 3
  • DOI: 10.1080/01442350210157348

M OLECULAR A SPECTS OF H ALIDE I ON H YDRATION : The Cluster Approach
journal, October 2003


Spectroscopy and dynamics of excess electrons in clusters
journal, August 2008


Vibrational Spectroscopy of Microhydrated Conjugate Base Anions
journal, June 2011

  • Asmis, Knut R.; Neumark, Daniel M.
  • Accounts of Chemical Research, Vol. 45, Issue 1
  • DOI: 10.1021/ar2000748

Infrared spectroscopy of hydrated sulfate dianions
journal, September 2006

  • Zhou, Jia; Santambrogio, Gabriele; Brümmer, Mathias
  • The Journal of Chemical Physics, Vol. 125, Issue 11
  • DOI: 10.1063/1.2351675

Cryogenic ion trap vibrational spectroscopy of hydrogen-bonded clusters relevant to atmospheric chemistry
journal, December 2014


Hydration of monomeric metaphosphate anion in the gas phase
journal, December 1989

  • Keesee, R. G.; Castleman, A. W.
  • Journal of the American Chemical Society, Vol. 111, Issue 25
  • DOI: 10.1021/ja00207a004

Hydration in the Gas Phase of the Orthophosphate Anion, (HO) 2 PO 2 - , and the Conversion of the Orthophosphate to the Metaphosphate, PO 3 - , Ion
journal, January 1996

  • Blades, Arthur T.; Ho, Yeunghaw; Kebarle, Paul
  • Journal of the American Chemical Society, Vol. 118, Issue 1
  • DOI: 10.1021/ja952169w

Determination of Ion−Solvent Equilibria in the Gas Phase. Hydration of Diprotonated Diamines and Bis(trimethylammonium) Alkanes
journal, January 1996

  • Blades, Arthur T.; Klassen, John S.; Kebarle, Paul
  • Journal of the American Chemical Society, Vol. 118, Issue 49
  • DOI: 10.1021/ja962641t

Experimental and Theoretical Investigations of the Stability, Energetics, and Structures of H 2 PO 4 - , H 2 P 2 O 7 2- , and H 3 P 3 O 10 2- in the Gas Phase
journal, November 2001

  • Wang, Xue-Bin; Vorpagel, Erich R.; Yang, Xin
  • The Journal of Physical Chemistry A, Vol. 105, Issue 45
  • DOI: 10.1021/jp013244u

Isomer-Selective Detection of Hydrogen-Bond Vibrations in the Protonated Water Hexamer
journal, May 2013

  • Heine, Nadja; Fagiani, Matias R.; Rossi, Mariana
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja401359t

Gas-Phase Peptide Structures Unraveled by Far-IR Spectroscopy: Combining IR-UV Ion-Dip Experiments with Born-Oppenheimer Molecular Dynamics Simulations
journal, February 2014

  • Jaeqx, Sander; Oomens, Jos; Cimas, Alvaro
  • Angewandte Chemie International Edition, Vol. 53, Issue 14
  • DOI: 10.1002/anie.201311189

Infrared Predissociation Vibrational Spectroscopy of Li + (H 2 O) 3–4 Ar 0,1 Reanalyzed Using Density Functional Theory Molecular Dynamics
journal, November 2014

  • Brites, V.; Lisy, J. M.; Gaigeot, M. -P.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 11
  • DOI: 10.1021/jp508699m

Infrared Spectroscopy of Hydrated Bicarbonate Anion Clusters: HCO 3 (H 2 O) 1−10
journal, January 2010

  • Garand, Etienne; Wende, Torsten; Goebbert, Daniel J.
  • Journal of the American Chemical Society, Vol. 132, Issue 2
  • DOI: 10.1021/ja9093132

Infrared Spectroscopy of the Microhydrated Nitrate Ions NO 3 (H 2 O) 1−6
journal, July 2009

  • Goebbert, Daniel J.; Garand, Etienne; Wende, Torsten
  • The Journal of Physical Chemistry A, Vol. 113, Issue 26
  • DOI: 10.1021/jp9017103

Messenger-Tagging Electrosprayed Ions: Vibrational Spectroscopy of Suberate Dianions
journal, May 2009

  • Goebbert, Daniel J.; Wende, Torsten; Bergmann, Risshu
  • The Journal of Physical Chemistry A, Vol. 113, Issue 20
  • DOI: 10.1021/jp809390x

Gas-Phase Vibrational Spectroscopy of Microhydrated Magnesium Nitrate Ions [MgNO 3 (H 2 O) 1−4 ] +
journal, June 2010

  • Jiang, Ling; Wende, Torsten; Bergmann, Risshu
  • Journal of the American Chemical Society, Vol. 132, Issue 21
  • DOI: 10.1021/ja1011806

Vibrational spectroscopy of (SO42−)∙(H2O)n clusters, n=1–5: Harmonic and anharmonic calculations and experiment
journal, September 2007

  • Miller, Yifat; Chaban, Galina M.; Zhou, Jia
  • The Journal of Chemical Physics, Vol. 127, Issue 9
  • DOI: 10.1063/1.2764074

Infrared Spectroscopy of Hydrated Bisulfate Anion Clusters: HSO 4 ¯(H 2 O) 1–16
journal, August 2011

  • Yacovitch, Tara I.; Wende, Torsten; Jiang, Ling
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 17
  • DOI: 10.1021/jz200917f

The Free-Electron-Laser user facility FELIX
journal, January 1995

  • Oepts, D.; van der Meer, A. F. G.; van Amersfoort, P. W.
  • Infrared Physics & Technology, Vol. 36, Issue 1
  • DOI: 10.1016/1350-4495(94)00074-U

An Evaluation of Harmonic Vibrational Frequency Scale Factors
journal, November 2007

  • Merrick, Jeffrey P.; Moran, Damian; Radom, Leo
  • The Journal of Physical Chemistry A, Vol. 111, Issue 45
  • DOI: 10.1021/jp073974n

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

  • VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
  • Computer Physics Communications, Vol. 167, Issue 2
  • DOI: 10.1016/j.cpc.2004.12.014

The Gaussian and augmented-plane-wave density functional method for ab initio molecular dynamics simulations
journal, December 1999

  • Lippert, Gerald; Hutter, Jürg; Parrinello, Michele
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 103, Issue 2
  • DOI: 10.1007/s002140050523

Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals
journal, May 2005


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

A reciprocal space based method for treating long range interactions in ab initio and force-field-based calculations in clusters
journal, February 1999

  • Martyna, Glenn J.; Tuckerman, Mark E.
  • The Journal of Chemical Physics, Vol. 110, Issue 6
  • DOI: 10.1063/1.477923

A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334