Abstract
The behaviour of the ammonium ion in synthetic buddingtonite, N(D,H)4AlSi3O8, has been studied by infrared (IR) spectroscopy from 20 K to 298 K and by 2H NMR spectroscopy from 120 K to 298 K. IR spectra were collected from 500 to 3500 cm−1. Static 2H NMR spectra collected at 298 K and 120 K are very similar, consisting of a single sharp isotropic resonance, indicating complete averaging of quadrupolar interactions and implying that at these temperatures the ammonium ion is in rapid (<1 μs) randomised motion within the M-site cavity of the feldspar framework. NMR spectroscopy indicates that the splitting of the internal modes of the ammonium ion observed by IR spectroscopy is not due to “freezing in” of the ammonium ion. This observation rules out the formation of a preferred N–H...O hydrogen bond, with precession of the ion about it, as proposed by Kimball and Megaw (1978), because any N–H...O hydrogen bond must be very weak and transient in nature. Contraction of the cavity site upon cooling imposes a distortion upon the ammonium ion that affects vibrational modes. This distortion does not affect the motion of the ammonium ion as observed on the NMR time-scale.
Similar content being viewed by others
References
Beran A, Armstrong J, Rossman GR (1992) Infrared and electron microprobe analysis of ammonium ions in hyalophane feldspar. Eur J Mineral 4:847–850
Duer MJ (2000) Solid-state NMR studies of molecular motion. Annu Rep NMR Spectrosc 43:1–58
Harlov DE, Andrut M, Poter B (2001a) Characterization of tobelite (NH4)Al2[AlSi3O10](OH)2 and ND4-tobelite (ND4)Al2[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra. Phys Chem Minerals 28:268–276
Harlov DE, Andrut M, Poter B (2001b) Characterization of buddingtonite (NH4)[AlSi3O8] and ND4-buddingtonite (ND4)[AlSi3O8] using IR spectroscopy and Rietveld refinement of XRD spectra. Phys Chem Minerals 28:188–198
Harlov DE, Andrut M, Poter B (2001c) Characterization of NH4-phlogopite (NH4)Mg3[AlSi3O10](OH)2 and ND4-phlogopite (ND4)Mg3[AlSi3O10](OD)2 using IR spectroscopy and Rietveld refinement of XRD spectra. Phys Chem Minerals 28:77-86-276
Harris RK (1983) Nuclear magnetic resonance spectroscopy. Longman Scientific and Technical
Kimball MD, Megaw HD (1974) Interim report on the crystal structure of buddingtonite. In: Mackenzie WS and Zussman J (eds) The feldspars, proceedings of the NATO ASI on feldspars, chap I(6). Manchester University Press, Manchester, pp 81–86
Kristensen JH, Farnan I (2001) Computational aspects of motional symmetry in nuclear resonance spectroscopy. Chem Phys 270:109–128
Kristensen JH, Hoatson GL, Vold RL (1999) Effects of restricted rotational diffusion on 2H magic angle spinning nuclear magnetic resonance spectra. J Chem Phys 110:4533–4553
Libowitzky E (1999) Correlation of O-H stretching frequencies and O-H...O hydrogen bond lengths in minerals. Monatshefte für Chemie 120:1047–1059
Likhacheva AY, Paukshtis EA, Seryotkin YV Shulgenko SG (2002) IR spectroscopic characterization of NH4-analcime. Phys Chem Minerals 29:617–623
Mookherjee M, Redfern SAT, Zhang M, Harlov DE (2002a) Orientational order–disorder in synthetic ND4/NH4-phlogopite: a low-temperature infrared study. Eur J Mineral 14:1033–1039
Mookherjee M, Redfern SAT, Zhang M, Harlov DE (2002b) Orientational order–disorder of N(D,H) +4 in tobelite. Am Mineralogist 87:1686–1691
Nakamoto K, Margoshes M, Rundle RE (1955) Stretching frequencies as a function of distances in hydrogen bonds. J Am Chem Soc 77:6480–6486
Oxton IA, Knop O, Falk M (1975) Infrared spectra of the ammonium ion in crystal. I. Ammonium hexachloroplatinate (IV) and hexachlorotellurate (IV). Can J Chem 53:2675–2682
Oxton IA, Knop O, Falk M (1976) Determination of the symmetry of ammonium ions in crystals from the infrared spectra of the isotopically dilute NH3D+ species. J Phys Chem 80:1212–1217
Portsmouth RL, Duer MJ, Gladden LF (1995) 2H NMR studies of single-component adsorption in silicalite: a comparative strudy of benzene and p-xylene. J Chem Soc (Faraday Transact) 91:559–0567
Stebbins JF (1988) NMR spectroscopy and dynamic processes in mineralogy and geochemistry. Mineral Soc Am Rev Mineral 18:405–430
Voncken JHL, Konings RJM, Jansen JBH, Woensdregt CF (1988) Hydrothermally grown buddingtonite, an anhydrous ammonium feldspar (NH4AlSi3O8). Phys Chem Minerals 15:323–328
Wagner EL, Hornig DF (1950) The vibrational spectra of molecules and complex ions in crystals III. Ammonium chloride and deutero-ammonium chloride. J Chem Phys 18:296–304
Yund RA (1983) Diffusion in feldspars. Mineral Soc Am Rev Mineral 2:203–222
Acknowledgements
DH thanks the German Science Foundation for support through grant He 2015-5 to Wilhelm Heinrich. MM gratefully acknowledges financial support from the Natural History Museum (London) and the Cambridge Commonwealth Trust. Sharon Ashbrook (University of Cambridge) is thanked for helpful discussions concerning the interpretation of 2H lineshapes.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Mookherjee, M., Welch, M.D., Pollès, L.L. et al. Ammonium ion behaviour in feldspar: variable-temperature infrared and 2H NMR studies of synthetic buddingtonite, N(D,H)4AlSi3O8. Phys Chem Minerals 32, 126–131 (2005). https://doi.org/10.1007/s00269-005-0455-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00269-005-0455-x