Abstract
IT has long been known that the substitution of deuterium for hydrogen in hydrogen-bonded materials can lead to a change in the geometry of the hydrogen bonds—the so-called Ubbelohde effect1. There can also be significant accompanying changes in the physical properties of the material. Among the most striking examples is the increase in the transition temperature, Tc, of hydrogen-ordering systems of the KH2PO4 type by >100K on full deuteration. In all of these systems, Tc decreases under pressure, making it possible in principle to compare protonated and deuterated forms at the same Tc by applying pressure to the latter. Here we report the results of a high-pressure neutron diffraction study of the deuterated H(D)-ordering material PbDPO4. We find that much, and possibly all, of the increase in Tc on deuteration is attributable to the accompanying changes in the hydrogen-bond dimensions. This suggests that purely mass-dependent effects on the quantum-mechanical tunnelling between the equivalent H(D) potential minima—an explanation that has been favoured previously—have little or no direct influence on Tc. Substantial revisions to the theory of this type of ordering transition are apparently required.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Robertson, J. M. & Ubbelohde, A. R. Proc. R. Soc. A170, 222–240 (1939).
Blinc, R. J. Phys. Chem. Solids 13, 204–211 (1960).
Tokunaga, M. & Matsubara, T. Ferroelectrics 72, 175–191 (1987).
Tun, Z., Nelmes, R. J., Kuhs, W. F. & Stansfield, R. F. D. J. Phys. C21, 245–258 (1988).
Tibballs, J. E., Nelmes, R. J. & Mclntyre, G. J. J. Phys. C15, 37–58 (1982).
Tibballs, J. E. & Nelmes, R. J. J. Phys. C15, 849–853 (1982).
Samara, G. A. Ferroelectrics 71, 161–182 (1987).
Silsbee, H. B., Uehling, E. A. & Schmidt, V. H. Phys. Rev. A133, 165–170 (1964).
Ichikawa, M., Motida, K. & Yamada, N., Phys. Rev. B36, 874–876 (1987).
Samara, G. A. & Semmingsen, D. J. chem. Phys. 71, 1401–1407 (1979).
Nelmes, R. J. J. Phys. C21, L881–L886 (1988).
Katrusiak, A. & Nelmes, R. J. J. Phys. C19, L765–L772 (1986).
Negran, T. J. et al. Ferroelectrics 6, 179–182 (1974).
Mylov, V. P., Shirokov, A. M., Shuvalov, L. A., Kharitonov, V. N. & Brzhezina, B. Soviet Phys. Crystallogr. 24, 738–739 (1979).
Kuhs, W. F., Ahsbahs, H., Londono, D. & Finney, J. L. Physica B156/157, 684–687 (1989).
Zucker, U. H., Perenthaler, E., Kuhs, W. F., Bachmann, R. & Schulz, H., J. appl. Cryst. 16, 358 (1983).
Piltz, R. O., McMahon, M. I. & Nelmes, R. J. Ferroelectrics 108, 271–276 (1990).
Lawrence, M. C. & Robertson, G. N. J. Phys. C13, 1053–1059 (1980).
Matsubara, T. & Matsushita, E. Prog. theor. Phys. 71, 209–11 (1984).
McMahon, M. I., Piltz, R. O. & Nelmes, R. J. Ferroelectrics 108, 277–282 (1990).
Kojyo, N. & Onodera, Y. J. phys. Soc. Japan 57, 4391–4402 (1988).
Lockwood, D. J., Ohno, N., Nelmes, R. J. & Arend, H., J. Phys. C18, L559–L565 (1985).
Motida, K. & Ichikawa, M. J. phys. Soc. Japan 58, 2810–2816 (1989).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
McMahon, M., Nelmes, R., Kuhst, W. et al. Geometric effects of deuteration on hydrogen-ordering phase transitions. Nature 348, 317–319 (1990). https://doi.org/10.1038/348317a0
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/348317a0
This article is cited by
-
Tuning ferroelectric phase transition temperature by enantiomer fraction
Nature Communications (2024)
-
Microscopic Difference of Hydrogen Double-minimum Potential Well Detected by Hydroxyl Group in Hydrogen-bonded System
Scientific Reports (2020)
-
Geometric isotope effect of deuteration in a hydrogen-bonded host–guest crystal
Nature Communications (2018)
-
Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system
Nature (2016)
-
Isotope effect on the circular dichroism spectrum of methyl α-D-glucopyranoside in aqueous solution
Scientific Reports (2015)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.