Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Ion-mediated hydrogen-bond rearrangement through tunnelling in the iodide–dihydrate complex


A microscopic picture of hydrogen-bond structure and dynamics in ion hydration shells remains elusive. Small ion–dihydrate molecular complexes are ideal systems with which to investigate the interplay and competition between ion–water and water–water interactions. Here, state-of-the-art quantum dynamics simulations provide evidence for tunnelling in hydrogen-bond rearrangements in the iodide–dihydrate complex and show that it can be controlled through isotopic substitutions. We find that the iodide ion weakens the neighbouring water–water hydrogen bond, leading to faster water reorientation than in the analogous water trimer. These faster dynamics, which are apparently at odds with the slowdown observed in the first hydration shell of iodide in solution, can be traced back to the presence of a free OH bond in the iodide–dihydrate complex, which effectively triggers the overall structural rearrangements within it. Besides providing indirect support for cooperative hydrogen-bond dynamics in iodide solutions, the analysis presented here suggests that iodide ions may accelerate hydrogen-bond rearrangements at aqueous interfaces, where neighbouring water molecules can be undercoordinated.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Ground-state geometry and OH-stretch vibrational frequencies of the iodide–dihydrate complex.
Fig. 2: Ground-state tunnelling pathways and splitting pattern in the iodide–dihydrate complex.
Fig. 3: Tunnelling timescales in the isotopologues of the iodide–dihydrate complex.
Fig. 4: Temperature-dependent free energies along the tunnelling pathways.
Fig. 5: Determining local free energies associated with different hydrogen-bonding environments in the I(HOD)(D2O) isotopologue of the iodide–dihydrate complex.

Code availability

The computer codes used in this study are available from the authors upon request.

Data availability

Any data generated and analysed for this study that are not included in this Article and its Supplementary Information are available from the authors upon request.


  1. Sneen, R. A. Substitution at a saturated carbon atom. XVII. Organic ion pairs as intermediates in nucleophilic substitution and elimination reactions. Acc. Chem. Res. 6, 46–53 (1973).

    Article  CAS  Google Scholar 

  2. Pregel, M., Dunn, E., Nagelkerke, R., Thatcher, G. & Buncel, E. Alkali–metal ion catalysis and inhibition in nucleophilic displacement reaction of phosphorus–sulfur–and carbon–based esters. Chem. Soc. Rev. 24, 449–455 (1995).

    Article  CAS  Google Scholar 

  3. Collins, K. D., Neilson, G. W. & Enderby, J. E. Ions in water: characterizing the forces that control chemical processes and biological structure. Biophys. Chem. 128, 95–104 (2007).

    Article  CAS  Google Scholar 

  4. Kunz, W. Specific ion effects in colloidal and biological systems. Curr. Opin. Colloid Interface Sci. 15, 34–39 (2010).

    Article  CAS  Google Scholar 

  5. Nostro, P. L. & Ninham, B. W. Hofmeister phenomena: an update on ion specificity in biology. Chem. Rev. 112, 2287–2322 (2012).

    Article  Google Scholar 

  6. Tobias, D. J., Stern, A. C., Baer, M. D., Levin, Y. & Mundy, C. J. Simulation and theory of ions at atmospherically relevant aqueous liquid–air interfaces. Annu. Rev. Phys. Chem. 64, 339–359 (2013).

    Article  CAS  Google Scholar 

  7. Lehtipalo, K. et al. The effect of acid–base clustering and ions on the growth of atmospheric nano-particles. Nat. Commun. 7, 11594 (2016).

    Article  CAS  Google Scholar 

  8. Winter, M. & Brodd, R. J. What are batteries, fuel cells, and supercapacitors? Chem. Rev. 104, 4245–4270 (2004).

    Article  CAS  Google Scholar 

  9. Pollard, T. P. & Beck, T. L. Toward a quantitative theory of hofmeister phenomena: from quantum effects to thermodynamics. Curr. Opin. Colloid Interface Sci. 23, 110–118 (2016).

    Article  CAS  Google Scholar 

  10. Bakker, H., Kropman, M. & Omta, A. Effect of ions on the structure and dynamics of liquid water. J. Phys. Condens. Matter 17, S3215 (2005).

    Article  CAS  Google Scholar 

  11. Jungwirth, P. & Tobias, D. J. Specific ion effects at the air/water interface. Chem. Rev. 106, 1259–1281 (2006).

    Article  CAS  Google Scholar 

  12. Robertson, W. H. & Johnson, M. A. Molecular aspects of halide ion hydration: the cluster approach. Annu. Rev. Phys. Chem. 54, 173–213 (2003).

    Article  CAS  Google Scholar 

  13. Ayala, R., Martinez, J. M., Pappalardo, R. R. & Marcos, E. S. Study of the stabilization energies of halide–water clusters: an application of first-principles interaction potentials based on a polarizable and flexible model. J. Chem. Phys. 121, 7269–7275 (2004).

    Article  Google Scholar 

  14. Kamarchik, E. & Bowman, J. M. Quantum vibrational analysis of hydrated ions using an ab initio potential. J. Phys. Chem. A 114, 12945–12951 (2010).

    Article  CAS  Google Scholar 

  15. Wang, X.-G. & Carrington, T. Jr. Rovibrational levels and wavefunctions of ClH2O. J. Chem. Phys. 140, 204306 (2014).

    Article  Google Scholar 

  16. Kamarchik, E., Toffoli, D., Christiansen, O. & Bowman, J. M. Ab initio potential energy and dipole moment surfaces of the F(H2O) complex. Spectrochim. Acta A 119, 59–62 (2014).

    Article  CAS  Google Scholar 

  17. Sarka, J., Lauvergnat, D., Brites, V., Császár, A. G. & Léonard, C. Rovibrational energy levels of the F(H2O) and F(D2O) complexes. Phys. Chem. Chem. Phys. 18, 17678–17690 (2016).

    Article  CAS  Google Scholar 

  18. Bajaj, P., Wang, X.-G., Carrington, T. Jr. & Paesani, F. Vibrational spectra of halide–water dimers: insights on ion hydration from full-dimensional quantum calculations on many-body potential energy surfaces. J. Chem. Phys. 148, 102321 (2018).

    Article  Google Scholar 

  19. Wolke, C. T. et al. Thermodynamics of water dimer dissociation in the primary hydration shell of the iodide ion with temperature-dependent vibrational predissociation spectroscopy. J. Phys. Chem. A 119, 1859–1866 (2015).

    Article  CAS  Google Scholar 

  20. Yang, N., Duong, C. H., Kelleher, P. J., Johnson, M. A. & McCoy, A. B. Isolation of site-specific anharmonicities of individual water molecules in the I(H2O)2 complex using tag-free, isotopomer selective IR-IR double resonance. Chem. Phys. Lett. 690, 159–171 (2017).

    Article  CAS  Google Scholar 

  21. Cheng, X. & Steele, R. P. Efficient anharmonic vibrational spectroscopy for large molecules using local-mode coordinates. J. Chem. Phys. 141, 104105 (2014).

    Article  Google Scholar 

  22. Cheng, X., Talbot, J. J. & Steele, R. P. Tuning vibrational mode localization with frequency windowing. J. Chem. Phys. 145, 124112 (2016).

    Article  Google Scholar 

  23. Wang, Y. & Bowman, J. M. Ab initio potential and dipole moment surfaces for water. II. Local-monomer calculations of the infrared spectra of water clusters. J. Chem. Phys. 134, 154510 (2011).

    Article  Google Scholar 

  24. Bajaj, P., Götz, A. W. & Paesani, F. Toward chemical accuracy in description of ion–water interactions through many-body representations. I. Halide–water dimer potential energy surfaces. J. Chem. Theory Comput. 12, 2698–2705 (2016).

    Article  CAS  Google Scholar 

  25. Brown, S. E. et al. Monitoring water clusters ‘melt’ through vibrational spectroscopy. J. Am. Chem. Soc. 139, 7082–7088 (2017).

    Article  CAS  Google Scholar 

  26. Pugliano, N. & Saykally, R. J. Measurement of quantum tunneling between chiral isomers of the cyclic water trimer. Science 257, 1937–1940 (1992).

    Article  CAS  Google Scholar 

  27. Keutsch, F. N. & Saykally, R. J. Water clusters: untangling the mysteries of the liquid, one molecule at a time. Proc. Natl Acad. Sci. USA 98, 10533–10540 (2001).

    Article  CAS  Google Scholar 

  28. Keutsch, F. N., Cruzan, J. D. & Saykally, R. J. The water trimer. Chem. Rev. 103, 2533–2578 (2003).

    Article  CAS  Google Scholar 

  29. Richardson, J. O., Althorpe, S. C. & Wales, D. J. Instanton calculations of tunneling splittings for water dimer and trimer. J. Chem. Phys. 135, 124109 (2011).

    Article  Google Scholar 

  30. Richardson, J. O. & Althorpe, S. C. Ring-polymer instanton method for calculating tunneling splittings. J. Chem. Phys. 134, 054109 (2011).

    Article  Google Scholar 

  31. Barducci, A., Bussi, G. & Parrinello, M. Well-tempered metadynamics: a smoothly converging and tunable free-energy method. Phys. Rev. Lett. 100, 020603 (2008).

    Article  Google Scholar 

  32. Knipping, E. M. et al. Experiments and simulations of ion-enhanced interfacial chemistry on aqueous NaCl aerosols. Science 288, 301–306 (2000).

    Article  Google Scholar 

  33. Parrinello, M. & Rahman, A. Study of an F center in molten KCl. J. Chem. Phys. 80, 860–867 (1984).

    Article  CAS  Google Scholar 

  34. Feynman, R. P. Statistical Mechanics: A Set of Lectures (Benjamin, New York, 1972).

  35. Richardson, J. O. Perspective: ring-polymer instanton theory. J. Chem. Phys. 148, 200901 (2018).

    Article  Google Scholar 

  36. Richardson, J. O. Ring-polymer instanton theory. Int. Rev. Phys. Chem. 37, 171–216 (2018).

    Article  CAS  Google Scholar 

  37. Laio, A. & Parrinello, M. Escaping free-energy minima. Proc. Natl Acad. Sci. USA 99, 12562–12566 (2002).

    Article  CAS  Google Scholar 

  38. Tribello, G. A., Bonomi, M., Branduardi, D., Camilloni, C. & Bussi, G. PLUMED 2: new feathers for an old bird. Comput. Phys. Commun. 185, 604–613 (2014).

    Article  CAS  Google Scholar 

Download references


The authors thank M.A. Johnson and N. Yang for stimulating discussions about the vibrational spectroscopy and dynamics of the I(H2O)2 complex and its isotopologues. This research was supported by the National Science Foundation Center for Chemical Innovation ‘Center for Aerosol Impacts on Chemistry of the Environment’ (grant no. CHE-1305427) and by the Swiss National Science Foundation (project no. 175696). Calculations were performed using the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation (grant no. ACI-1053575, allocation TG-CHE110009), the High Performance Computing Modernization Program (HPCMP), which is supported by the Air Force Office of Scientific Research (grant no. FA9550-16-1-0327), as well as the Triton Shared Computing Cluster (TSCC) at the San Diego Supercomputer Center.

Author information

Authors and Affiliations



P.B. performed all simulations, contributed to data analysis and co-wrote the paper. J.O.R. guided the RPI calculations, contributed to data analysis and co-wrote the paper. F.P. initiated the project, guided the simulation design and data analysis, and co-wrote the paper.

Corresponding author

Correspondence to Francesco Paesani.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figures 1–3, Supplementary Tables 1–9, Supplementary Methods, Supplementary Data and Analysis.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bajaj, P., Richardson, J.O. & Paesani, F. Ion-mediated hydrogen-bond rearrangement through tunnelling in the iodide–dihydrate complex. Nat. Chem. 11, 367–374 (2019).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing