Proton dynamics in solids

François Fillaux, DR-CNRS

Protons in solids can be involved in a variety of chemical bonds: covalent, ionic and hydrogen bonds. Owing to the light mass, protons undergo displacements with very large amplitude compared to other atoms. Proton dynamics are of great impact in many properties of the solid state: proton transfer, phase transitions, proton conduction... Such anharmonic dynamics only can be rationalized with advanced tools of quantum mechanics.
Vibrational spectroscopy is best to observing proton dynamics in solids. Neutron scattering provide information complementary to the more common infrared and Raman techniques.

Lecture of 13 december 2004 Contact

Some key results :

Quantum correlations of protons in crystals

Where are protons and deuterons in KHpD1-pCO3? A neutron diffraction study,
F. Fillaux and A. Cousson, Z. Phys. Chem. 222 (2008) 1279-1290.(pdf)
Oldenbourg Wissenschaftsverlag, München

Nonlocal protons and deuterons opposed to disorder: a single-crystal neutron diffraction study of KH0_.76D_0.24CO₃ and a theoretical framework,
F. Fillaux and A. Cousson, J. Phys.:Condens. Matter 20 (2008) 252202.(pdf)

A neutron diffraction study of macroscopically entangled proton states in the high temperature phase of the KHCO₃ crystal at 340 K,
F. Fillaux, A. Cousson and M. J Gutmann, J. Phys.:Condensed Matter, 20 (2008) 015225. (pdf)

Proton tranfer in the KHCO₃ and benzoin acid crystals : a quantum view,
F. Fillaux, J. Mol. Struct. 38, (2007), 308-318.(pdf)

Proton transfer across hydrogen bonds: From reaction path to Schrödinger's Cat,
F. Fillaux, A. Cousson and M. J. Gutmann, Pure Applied Chemistry 79, (2007), 1023-1039.(pdf)

Macroscopic quantum tunnelling of protons in the KHCO₃ crystal,
F. Fillaux, A. Cousson, M. J. Gutmann, J. Mol. Struct. 790 (2006) 122-126.(pdf)

Macroscopic quantum entanglement and 'super-rigidity' of protons in the KHCO₃ crystal from 30 to 300 K
F. Fillaux, A. Cousson and M. J. Gutmann, J. Phys.: Cond. Matter, 18 (2006) 3229-3249.(pdf)

Comment on: "Quantum correlation between protons in potassium bicarbonate"
by D. A. Keen and S. W. Lovesey, J. Phys.: Cond. Matter, 15 (2003) 4937-4946.
F. Fillaux and A. Cousson, J. Phys.: Cond. Matter, 16 (2004) 1007-1010.(pdf)

Observation of the Dynamical Structure Arising from Spatially Extended Quantum Entanglement and Long-Lived Quantum Coherence in the KHCO₃ Crystal.
F. Fillaux, A. Cousson and D. Keen, Phys. Rev. B, 67 (2003) 054301.(pdf)

Incoherent elastic neutron scattering study of the vibrational dynamics and spin-related symmetry of protons in the KHCO3 crystal.
S. Ikeda and F. Fillaux, Phys. Rev. B, 59 (1999) 4134.(pdf)

The Pauli principle and the vibrational dynamics of protons in solids : a new spin related symmetry.
F. Fillaux, Physica D, 113 (1998) 172.(pdf)

Hydrogen bond dynamics

A neutron scattering study of strong-symmetric hydrogen bonds in potassium and cesium hydrogen bistrifluoroacetates: Determination of the crystal structures and of the single-well potentials for protons.
F. Fillaux, A. Cousson, J. F. R. Archilla and J. Tomkinson, J. Chem. Phys. 128 (2008), 204502.(pdf)

Vibrational Spectroscopy and Quantum Localization, F. Fillaux in Energy Localization and Transfer. Editors T. Dauxois, A. Litvak-Hinenzon, R. MacKay and A. Spanoudaki. Advanced series in nonlinear dynamics, Vol 22 (World Scientific Publishing Co. Pte Ltd., 2004) p.73-148.(pdf)

Inelastic neutron scattering study of the localized dynamics of protons in KHCO3 single crystals.
S. Ikeda, S. Kashida, H. Sugimoto, Y. Yamada, S. M. Bennington and F. Fillaux, Phys. Rev. B, 66 (2002) 184302.(pdf)

New proton dynamics in solids revealed by vibrational spectroscopy with neutrons.
F. Fillaux, J. Mol. Struct., 511-512 (1999) 35.(pdf)

Proton transfer across hydrogen bonds

Extended tunnelling states in the benzoic acid crystal : Infrared and Raman spectra of the OH and OD stretching modes, F. Fillaux, F. Romain, M-H Limage and N. Leygue, Phys. Chem. Chem. Phys., 2006, 4327-4336.(pdf)

Proton transfer in maloaldehyde : From reaction path to Schrödinger's Cat
F. Fillaux and B. Nicolaï, Chem. Phys. Letters 415 (2005) 357-361.(pdf)

Quantum entanglement and nonlocal proton transfer dynamics in dimers of formic acid and analogues.
F. Fillaux, Chem. Phys. Letters, 408 (2005) 302-306. (pdf)

Comment on: 'A symmetric hydrogen bond revisited: potassium hydrogen maleate by variable temperature, variable pressure neutron diffraction and plane-wave DFT methods' [Chem. Phys. Lett. 381 (2003) 102],
F. Fillaux, A. Cousson and J. Tomkinson, Chem. Phys. Lett., 399 (2004) 2891. (pdf)

Quantum proton transfer and orientational disorder in the benzoic acid crystal: vibrational spectra, mechanism and theory.
F. Fillaux, M. -H. Limage and F. Romain, Chem. Phys., 276 (2002) 181-210.(pdf)

The impact of vibrational spectroscopy with neutrons on our view of quantum dynamics in hydrogen bonds and proton transfer.
F. Fillaux, J. Mol. Struct., 615 (2002) 45-59.(pdf)

Hydrogen bonding and quantum dynamics in the solid state.
F. Fillaux, International Review in Physical Chemistry, 19 (2000) 553.(pdf)

Hydrogen bonding. A historical perspective.
F. Fillaux and J. P. Perchard, J. Chim. Phys., Hors série (2000) 91.

Structure and dynamics of the hydrogen bond in potassium hydrogen maleate: a neutron scattering study.
F. Fillaux, N. Leygue, J. Tomkinson, A. Cousson and W. Paulus, Chem.Phys., 244 (1999) 387.(pdf)

Rotational tunnelling of methyle group

Collective rotational tunnelling of methyl groups and quantum solitons in 4-methylpyridine: Neutron scattering studies of single crystals
F. Fillaux, B. Nicolaï, W. Paulus, E. Kaiser-Morris and A. Cousson, Phys. Rev. B, 68 (2003) 224301.(pdf)

The effect of methyl deuteration on the crystalline structure in Lithium acetate dihydrate
B. Nicolaï, A. Cousson and F. Fillaux, Chem. Phys., 290 (2003) 101-120.(pdf)

Experimental Studies and Theory of Nonlinear Rotational Dynamics in the Quantum Regime: the Interplay of Structure, Dynamics and Localization in Crystals.
F. Fillaux, B. Nicolaï and A. Cousson (World Scientific, Publishing Co., Inc, 2003).(pdf)

Collective Rotational Tunnelling and Quantum sine-Gordon Solitons.
F. Fillaux, (World Scientific, Publishing Co., Inc, 2003).(pdf)

Structure of manganese diacetate tetrahydrate and low-temperature methyl-group dynamics.
B. Nicolaï, G. J. Kearley, A. Cousson, W. Paulus, F. Fillaux, F. Gentner, L. Schröder, and D. Watkin, Acta Cryst. B57 (2001) 36.

Crystal structure and low-temperature methyl-group dynamics of cobalt and nickel acetates.
B. Nicolaï, G. J. Kearley, M. R. Johnson, F. Fillaux and E. Suard, J.Chem.Phys., 109 (1998) 9062.(pdf)

Inelastic neutron-scattering study of the sine-Gordon breather interactions in isotopic mixtures of 4-methyle-pyridine.
F. Fillaux, C. J. Carlile and G. J. Kearley, Phys.Rev.B, 58 (1998) 11416.(pdf)

Inelastic neutron scattering study of methyl tunnelling in an oriented single-crystal of 2,6-dimethylpyrazine at low temperature and rotational potential calculations.
B. Nicolaï, E. Kaiser, F. Fillaux, G. J. Kearley, A. Cousson and W. Paulus, Chem.Phys., 226 (1998) 1.(pdf)

Free protons and proton conduction

Inelastic neutron scattering studies of polypyrroles and partially deuterated analogues.
F. Fillaux, S. F. Parker and L. T. Yu, Solid State Ionics, 14 (2001) 451-57.(pdf)

Inelastic neutron scattering study of the proton dynamics in Bi-dopped manganese oxides.
F. Fillaux, C. Cachet, S. F. Parker, J. Tomkinson, A. Quivy, and L. T. Yu, J. Electrochem. Soc., 147 (2000) 4184.

New proton dynamics in solids revealed by vibrational spectroscopy with neutrons.
F. Fillaux, Solid State Ionics, 125 (1999) 69.(pdf)

Inelastic neutron scattering study of the proton dynamics in HNO3 graphite intercalation compounds.
F. Fillaux, S. Menu, J. Conard, H. Fuzellier, S. F. Parker, A. C. Hanon and J. Tomkinson, Chem.Phys., 242 (1999) 273.(pdf)

Inelastic neutron scattering studies of polyanilines and partially deuterated analogues.
F. Fillaux, N. Leygue, R. Baddour-Hadjean, S. F. Parker, Ph. Colomban, A. Gruger, A. Régis and L.T.Yu, Chem.Phys., 216 (1997) 281.(pdf)

Inelastic neutron-scattering study of free proton dynamics in γ-MnO2.
F. Fillaux, S. M. Bennington, J. Tomkinson and L. T. Yu, Chem.Phys., 209 (1996) 111. (pdf)

Bibliography