We report the results of the first pseudopotential plane-wave simulations of the static properties of ammonia monohydrate phase I (AMH I) and ammonium hydroxide. Our calculated fourth-order logarithmic equation of state, at zero pressure and temperature, has molar volume, bulk modulus, and the first derivative of the bulk modulus with respect to pressure, Both this and the lattice parameters are in very good agreement with experimental values. The monohydrate transforms, via a solid-state proton transfer reaction, to ammonium hydroxide at 5.0(4) GPa. The equation of state of ammonium hydroxide is, We calculate the reaction enthalpy, at absolute zero, and thus estimate the enthalpy of formation, at 298 K. This result places an upper limit of 84 kJ mol−1 on the barrier to rotation of the ammonium cation, and yields an average hydrogen bond enthalpy of ∼23 kJ mol−1.
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15 October 2001
Research Article|
October 15 2001
Ab initio simulation of ammonia monohydrate and ammonium hydroxide
A. D. Fortes;
A. D. Fortes
Research School of Geological and Geophysical Sciences, Birkbeck College and University College London, Gower Street, London WC1E 6BT, United Kingdom
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J. P. Brodholt;
J. P. Brodholt
Research School of Geological and Geophysical Sciences, Birkbeck College and University College London, Gower Street, London WC1E 6BT, United Kingdom
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I. G. Wood;
I. G. Wood
Research School of Geological and Geophysical Sciences, Birkbeck College and University College London, Gower Street, London WC1E 6BT, United Kingdom
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L. Vočadlo;
L. Vočadlo
Research School of Geological and Geophysical Sciences, Birkbeck College and University College London, Gower Street, London WC1E 6BT, United Kingdom
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H. D. B. Jenkins
H. D. B. Jenkins
Department of Chemistry, University of Warwick, Coventry CV4 7AL, West Midlands, United Kingdom
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J. Chem. Phys. 115, 7006–7014 (2001)
Article history
Received:
June 11 2001
Accepted:
July 10 2001
Citation
A. D. Fortes, J. P. Brodholt, I. G. Wood, L. Vočadlo, H. D. B. Jenkins; Ab initio simulation of ammonia monohydrate and ammonium hydroxide . J. Chem. Phys. 15 October 2001; 115 (15): 7006–7014. https://doi.org/10.1063/1.1398104
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