Abstract
Single-crystal polarized Raman spectra (3,000–4,000 cm−1 at 3 ≤ T ≤ 300 K) were measured for synthetic alkali-free and natural beryl, Be2Al3Si6O18·xH2O, to determine the behavior of H2O molecules of both Type I and Type II in the cavities. At low temperature, the H2O molecules of Type I displace from the center of cavity and give rise to very weak hydrogen bonding with the host lattice. The H2O Type I translational motion is characterized by substantial anharmonicity and looks like a motion of “a particle in the box” with a frequency of 6.3 cm−1. Water Type II is characterized by a free rotation with respect to the C 2 molecule axis, and it makes possible the water nuclear isomers (i.e. ortho- and para-) to be observed at low temperature.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Notes
The fitting of the observed spectra by Gauss functions results from technical reasons but not Gauss distribution of the oscillators: at low-temperature the bandwidth of the observed modes is less than dimension of a pixel of the CCD-matrix; this circumstance and charge spreading between the neighbor pixels produce “incorrect” contour of the spectral line.
In theory, band width of any vibrational band is defined by a lifetime of the excited state. The latter is governed by dissipation of energy of the excited state (i.e. Born and Huang 1954) or delay of the given phonon into other phonons of lower frequency (i.e. Balkanski et al. 1983). In both cases, a temperature decreasing should result in exponential narrowing of vibrational bands due to freezing-out of low-frequency vibrations.
References
Aines RD, Rossman GR (1984) The high temperature behavior of water and carbon dioxide in cordierite and beryl. Am Mineral 69:319–327
Balkanski M, Wallis RF, Haro E (1983) Anharmonic effects in light scattering due to optical phonons in silicon. Phys Rev B 28:1928–1934
Born M, Huang K (1954) Dynamical theory of crystal lattices. Clarendon Press, Oxford
Charoy B, de Donato P, Barres O, Pinto-Coelho C. (1996) Cannel occupancy in alkali-poor beryl from Serra Branca (Goias, Brazil): spectroscopic characterization. Am Mineral 81:395–403
Gatta GD, Nestola F, Bromiley GD, Mattauch S (2006) The real topological configuration of the extra-framework content in alkali-poor beryl: a multi-methodological study. Am Mineral 91:29–34
Gibbs GV, Breck DW, Meagher EP (1968) Structural refinement of hydrous and anhydrous synthetic beryl, Al2(Be3Si6)O18 and emerald, Al1.9Cr0.1(Be3Si6)O18. Lithos 1:275–285
Hagemann H, Lucken A, Bill H, Gyster-Sanz J, Stalder HA (1990) Polarized Raman spectra of beryl and bazzite. Phys Chem Miner 17:395–401
Kolesov BA, Geiger CA (2000) The orientation and vibrational states of H2O in synthetic alkali-free beryl. Phys Chem Miner 27:557–564
Kolesov BA (2006) Raman spectra of single H2O molecules isolated in cavities of crystals. J Struct Chem 47:21–34
Limbach H-H, Buntkowsky G, Matthes J, Gründemann S, Pery T, Walaszek B, Chaudret B (2006) Novel insights into the mechanism of the ortho/para spin conversion of hydrogen pairs: implications for catalysis and interstellar water. ChemPhysChem 7:551–554
Landau LD, Lifshitz EM (1980) Quantum mechanics, vol 3: course of theoretical physics, 3rd edn. Pergamon Press, Oxford
Mashkovtsev RI, Solntsev VP (2002) Channel constituents in synthetic beryl: ammonium. Phys Chem Miner 29:65–71
Miani A, Tennyson J (2004) Can ortho-para transitions be observed? J Chem Phys 120:2732–2739
Poulet H, Mathieu J-P (1970) Spectres de vibration et symétrie des cristaux. Paris
Prencipe M (2002) Ab initio Hartree–Fock study and charge density analysis of beryl (Al4Be6Si12O36). Phys Chem Miner 29:552–561
Schmetzer K (1989) Types of water in natural and synthetic emerald. Nenes Jahrb Miner Monatsh 1:15–26
Trost J, Eltschka C, Friedrich H (1998) Quantization in molecular potentials. J Phys B 31:361–374
Veber SL, Bagryanskaya EG, Chapovsky PL (2006) On the possibility of enrichment of H2O nuclear spin isomers by adsorption. JETF (Russian) 129:86–95
Wickercheim KA, Buchanan RA (1959) The near-infrared spectrum of beryl. Am Mineral 44:440–445
Wickercheim KA, Buchanan RA (1965) Some remarks concerning the spectra of water and hydroxyl groups in beryl. J Chem Phys 42:1468–1469
Wood DL, Nassau K (1967) Infrared spectra of foreign molecules in beryl. J Chem Phys 47:2220–2228
Wood DL, Nassau K (1968) The characterization of beryl and emerald by visible and infrared absorption spectroscopy. Am Mineral 53:777–800
Acknowledgments
The author thanks V. Thomas, S. Demin, and Dr. Yu.V. Seryotkin of the United Institute of Geology, Geophysics and Mineralogy, Novosibirsk, Russia, for providing the beryl and analcime crystals. P. L. Chapovsky (Institute of Automation and Electrometry, Russian Academy of Sciences, Novosibirsk) is thanked for helpful discussion. The author thanks Prof. Mauro Prencipe and an anonymous referee for helpful comments that improved the manuscript.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Kolesov, B. Vibrational states of H2O in beryl: physical aspects. Phys Chem Minerals 35, 271–278 (2008). https://doi.org/10.1007/s00269-008-0220-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00269-008-0220-z