Abstract
Brute force histogram calculation and a recently developed method to efficiently reconstruct the free energy profile of complex systems (the single-sweep method) are combined with ab initio molecular dynamics to study possible local mechanisms for the diffusion of hydrogen in sodium alanates. These compounds may help to understand key properties of solid state hydrogen storage materials. In this work, the identity of a mobile species observed in experiments characterizing the first dissociation reaction of sodium alanates is investigated. The activation barrier of two suggested processes for hydrogen diffusion in Na3AlH6 is evaluated and, by comparing our results with available experimental information, we are able to discriminate among them and to show that one is compatible with the observed signal while the other is not.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Bogdanovi B., Schwickardi M.: Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials. J. Alloys Compd. 1, 253–254 (1997)
Peles A., Alford J.A., Ma Z., Yang L., Chou M.Y.: First-principles study of NaAlH4 and Na3AlH6 complex hydrides. Phys. Rev. B 70, 165105–165112 (2004)
Li S., Jena P., Ahuja R.: Effect of Ti and metal vacancies on the electronic structure, stability, and dehydrogenation of Na3AlH6: supercell band-structure formalism and gradient-corrected density-functional theory. Phys. Rev. B 73, 214107–214114 (2006)
Kiran B., Kandalam A.K., Jena P.: Hydrogen storage and the 18-electron rule. J. Chem. Phys. 124, 224703–224706 (2006)
Kiran B., Jena P., Li X., Grubisic A., Stokes S.T., Gantefor G.F., Bowen K.H., Burgert R., Schnockel H.: Magic rule for Al n H m magic clusters. Phys. Rev. Lett. 98, 256802–256804 (2007)
Ke X., Tanaka I.: Decomposition reactions for NaAlH4 and Na3AlH6, and NaH: first-principles study. Phys. Rev. B 71, 024117–024133 (2005)
Araujo C.M., Li S., Ahuja R., Jena P.: Vacancy-mediated hydrogen desorption in NaAlH4. Phys. Rev. B 72, 165101–165107 (2005)
Voss J., Shi Q., Jacobsen H.S., Zamponi M., Lefmann K., Vegge T.: Hydrogen dynamics in Na3AlH6: a combined density functional theory and quasielastic neutron scattering study. J. Phys. Chem. B 111, 3886–3892 (2007)
Palumbo O., Cantelli R., Paolone A., Jensen C.M., Srinivasan S.S.: Point defect dynamics and evolution of chemical reactions in alanates by anelastic spectroscopy. J. Phys. Chem. B 109, 1168–1173 (2005)
Palumbo O., Paolone A., Cantelli R., Jensen C.M., Sulic M.: Fast H-vacancy dynamics during alanate decomposition by anelastic spectroscopy. Proposition of a model for Ti-enhanced hydrogen transport. J. Phys. Chem. B 110, 9105–9111 (2006)
Mills G., Jonsson H.: Quantum and thermal effects in H2 dissociative adsorption—evaluation of free-energy barriers in multidimensional quantum-systems. Phys. Rev. Lett. 72, 1124–1127 (1994)
Jonsson H., Mills G., Jacobsen K.W.: Nudged elastic band method for finding minimum energy paths of transitions. In: Berne, B.J., Ciccotti, G., Coker, D.F. (eds) Classical and Quantum Dynamics in the Condensed Phase, pp. 385–404. World Scientific, Singapore (1998)
Henkelman G., Uberuaga B.P., Jonsson H.: A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000)
Maragliano L., Vanden-Eijnden E.: Single-sweep methods for free energy calculations. J. Chem. Phys. 128, 184110 (2008)
Maragliano L., Fischer A., Vanden-Eijnden E., Ciccotti G.: String method in collective variables: minimum free energy paths and isocommittor surfaces. J. Chem. Phys. 125, 024106–024115 (2006)
Vanden Eijnden E.: Transition path theory. In: Ferrario, M., Ciccotti, G., Binder, K. (eds) Computer Simulation in Condensed Matter: From Materials to Chemical Biology, pp. 349–391. Springer, Berlin (2006)
Ronnebro E., Noreus D., Kadir K., Reiser A., Bogdanovic B.: Investigation of the perovskite related structures of NaMgH3, NaMgF, and Na3AlH6. J. Alloys Compd. 299, 101–106 (2000)
Vuilleumier R.: Density functional theory based ab initio MD using the Car-Parrinello approach. In: Ferrario, M., Ciccotti, G., Binder, K. (eds) Computer Simulation in Condensed Matter: From Materials to Chemical Biology, pp. 223–285. Springer, Berlin (2006)
Becke A.D.: Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098–3100 (1988)
Lee C., Yang W., Parr R.G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988)
Troullier N., Martins J.L.: Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991)
Martyna G.J., Klein M.L., Tuckerman M.: Nose-Hoover chains: the canonical ensemble via continuous dynamics. J. Chem. Phys. 97, 2635–2643 (1992)
Vanden-Eijnden E., Ciccotti G.: Second-order integrator for Langevin equations with holonomic constraints. Chem. Phys. Lett. 492, 310–316 (2006)
CPMD, Copyright IBM Corp. 1990–2001, Copyright MPI für Festkorperforschung Stuttgart 1997–2004
Sprik M.: Computation of the pK of liquid water using coordination constraints. Chem. Phys. 258, 139–150 (2000)
Maragliano L., Vanden-Eijnden E.: A temperature accelerated method for sampling free energy and determining reaction pathways in rare events simulations. Chem. Phys. Lett. 426, 168–175 (2006)
Weinan E., Ren W., Vanden-Eijnden E.: String method for the study of rare events. Phys. Rev. B 66, 052301–052305 (2002)
Weinan E., Ren W., Vanden-Eijnden E.: Simplified and improved string method for computing the minimum energy paths in barrier-crossing event. J. Chem. Phys. 126, 164103–164108 (2007)
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2008 Springer Science+Business Media B.V.
About this chapter
Cite this chapter
Monteferrante, M., Bonella, S., Meloni, S., Vanden-Eijnden, E., Ciccotti, G. (2008). Calculations of free energy barriers for local mechanisms of hydrogen diffusion in alanates. In: Yip, S., de la Rubia, T.D. (eds) Scientific Modeling and Simulations. Lecture Notes in Computational Science and Engineering, vol 68. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-9741-6_13
Download citation
DOI: https://doi.org/10.1007/978-1-4020-9741-6_13
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-9740-9
Online ISBN: 978-1-4020-9741-6
eBook Packages: Mathematics and StatisticsMathematics and Statistics (R0)