We apply a newly parameterized central force field to highlight the problem of proton transport in fuel cell membranes and show that central force fields are potential candidates to describe chemical reactions on a classical level. After a short sketch of the parameterization of the force field, we validate the obtained force field for several properties of water. The experimental and simulated radial distribution functions are reproduced very accurately as a consequence of the applied parameterization procedure. Further properties, geometry, coordination, diffusion coefficient and density, are simulated adequately for our purposes. Afterwards we use the new force field for the molecular dynamics simulation of a swollen polyelectrolyte membrane similar to the widespread Nafion 117. We investigate the equilibrated structures, proton transfer, lifetimes of hydronium ions, the diffusion coefficients, and the conductivity in dependence of water content. In a short movie we demonstrate the ability of the obtained force field to describe the bond breaking/formation, and conclude that this force field can be considered as a kind of a reactive force field. The investigations of the lifetimes of hydronium ions give us the information about the kinetics of the proton transfer in a membrane with low water content. We found the evidence for the second order reaction. Finally, we demonstrate that the model is simple enough to handle the large systems sufficient to calculate the conductivity from molecular dynamics simulations. The detailed analysis of the conductivity reveals the importance of the collective moving of hydronium ions in membrane, which might give an interesting encouragement for further development of membranes. Figure: The structure of water in one pore of the highly hydrated Nafion membranes.
This is a preview of subscription content, log in to check access.
Buy single article
Instant unlimited access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Kreuer KD, Paddison SJ, Spohr E, Schuster M (2004) Chem Rev 104:4637–4678
Tuckerman M, Laasonen K, Sprik M, Parrinello MJ (1995) Chem Phys 103:150–161
Schmitt U, Voth G (1999) J Chem Phys 111:9361–9381
Walbran S, Kornyshev A (2001) J Chem Phys 114:10039–10048
Day T, Soudackov A, Cuma M, Schmitt U, Voth G (2002) J Chem Phys 117:5839–5849
Spohr E, Commer P, Kornyshev A (2002) J Phys Chem B106:10560–10569
Petersen M, Wang F, Blake N, Metiu H, Voth G (2005) J Phys Chem B 109:3727–3730
van Duin A, Dasgupta S, Lorant F, Goddard III W (2001) J Phys Chem A 105:9396–9409
Yin K, Xia Q, Xu D, Chen C (2006) Comput Chem Eng 30:1346–1353
Lyubartsev A, Laaksonen A (2000) Chem Phys Lett 325:15–21
Wernet P, Nordlund D, Bergmann U, Cavalleri M, Odelius M, Ogasawara H, Naslund LA, Hirsch TK, Ojamae L, Glatzel P et al. (2004) Science 304:995
Soper AK (2000) Chem Phys 258:121–137
Hofmann D, Apostolakis J (2003) J Mol Struc:Theo Chem 647:17–39
Lemberg H, Stillinger FH (1975) J Chem Phys 62:1677–1690
Arthur J, Haymet ADJ (1998) Fluid Phase Equilibria 150:91–96
Bresme F (2001) J Chem Phys 115:7564–7574
Soper AK (1996) Chem Phys 202:295–306
Lyubartsev A, Laaksonen A (1995) Phys Rev E52:3730–3737
Bernal J, Fowler RH (1933) J Chem Phys 1:515–548
Elliot J, Hanna S, Elliot A, Cooley G (1999) Phys Chem Chem Phys 1:4855–4863
Hofmann D, Kuleshova L, D’Aguano B (2007) Phys Chem Let 448:138–143
Matsuoka O, Clementi E, Yoshimine M (1976) J Chem Phys 64:1351–1361
Bursulaya B, Kim H (1998) J Chem Phys 109:4911–4919
Guillot B (2002) J Mol Liquids 101:219–260
Watanabe K, Klein M (1989) Chem Phys 131:157–167
Berendsen H, Postma J, van Gunsteren W, Hermans J (1981) Interaction models for water in relation to protein hydration. In: Pullmann, Dodrecht (eds) pp 331–342
Wallqvist A, Astrand P-O (1995) J Chem Phys 102:6559–6565
Silvestrelli P, Parrinello M (1999) J Chem Phys 111:3572–3580
Mayo SL, Olafson BD, Goddard III WA (1990) J Phys Chem 94:8897–8909
Gebel G (2000) Polymer 41:5829–5838
Wescott J, Qi Y, Subramanian L, Capehart T (2006) J Chem Phys 124:134702–134716
Boero M, Ikeshoji T, Terakura K (2005) Chem Phys Chem 6: 1775–1779
Wedler G (1982) Lehrbuch der physikalischen Chemie. In Verlag Chemie; Chapter Die Bestimmung der Reaktionsordnung, pp 161–165
Moilanen DE, Piletic IR, Fayer MD (2006) J Phys Chem A110:9084–9088
Lowry TH, Richardson KS (1981) Mechanism and theory in organic chemistry. In: second ed.; Haper & Row, Publishers:; Chapter Kinetics and Mechanism, pp 174–188
Lonegran M, Shriver D, Ratner M (1995) Electrochimica Acta 40:2041–2048
Zawodzinski T, Derouin C, Radzinski S, Sherman R, Smith V, Springer, T, Gottesfeld A (1993) J Electrochem Soc 140:1041–1047
Spaeth M, Kreuer K, Maier J, Cramer C (1999) J Solid State Chem 148:169–177
The authors would like to thank for financial support the Sardinia Region and the Italian Ministry of Research (MIUR), NUME project (http://www.progetto-nume.it/). The authors are also indebted to Lorenzo Pisani for many useful discussions.
Electronic Supplementary Material
Below is the link to the electronic supplementary material.
Supplementary material (the movie of molecular dynamics in hydrated Nafion membrane including one proton transfer) is available (AVI 13.4 mb)
About this article
Cite this article
Hofmann, D.W.M., Kuleshova, L. & D’Aguanno, B. Molecular dynamics simulation of hydrated Nafion with a reactive force field for water. J Mol Model 14, 225–235 (2008) doi:10.1007/s00894-007-0265-9
- Molecular dynamics
- Radial distribution function
- Reactive force field