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The Combined Inelastic Neutron Scattering (INS) and Solid-State DFT Study of Hydrogen-Atoms Dynamics in Kaolinite-dimethylsulfoxide Intercalate

Published online by Cambridge University Press:  01 January 2024

L’ubomír Smrčok*
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 36 Bratislava, Slovak Republic
Daniel Tunega
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 36 Bratislava, Slovak Republic Institute of Soil Research, University of Natural Resources and Applied Life Sciences, Peter Jordan Strasse 82, A-1190 Vienna, Austria
Anibal Javier Ramirez-Cuesta
Affiliation:
ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, United Kingdom
Alexander Ivanov
Affiliation:
Institute Laue-Langevin, 6 rue Jules Horowitz, 38042 Grenoble, Cedex 9, France
Jana Valúchová
Affiliation:
Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-845 36 Bratislava, Slovak Republic
*
* E-mail address of corresponding author: lubomir.smrcok@savba.sk

Abstract

Vibrational spectra of two kaolinite-dimethylsulfoxide intercalates, obtained using inelastic neutron scattering (INS), were analyzed with a view to understanding the dynamics of the hydrogen atoms in the structure. The main focus was on the spectral region 0–1700 cm−1, which is difficult to analyze using optical spectroscopy. The experimental vibrational spectra of kaolinite:dimethylsulfoxide and kaolinite:d6-dimethylsulfoxide collected using two different spectrometers were interpreted by means of the solid-state DFT calculations. Calculated spectra were obtained by both normal-mode analysis and molecular dynamics going beyond the harmonic approximation. The Al-O-H bending modes were found to be spread over the large interval 100−1200 cm−1, with the dominant contributions located between 800 and 1200 cm−1. The shape of the individual hydrogen spectrum depends on whether or not the respective hydrogen atom is involved in an O-H⋯O hydrogen bond and on its strength. The modes corresponding to the in-plane movements of the inner-surface hydrogen atoms are well defined and always appear at the top of the intervals of energy transfer. In contrast, the modes generated by the out-of-plane movements of the hydrogen atoms are spread over large energy intervals extending down to the region of external (lattice) modes. The C-H modes are concentrated mainly in the three regions 1200–1450 cm−1, 800–1100 cm−1, and 0–400 cm−1. While the first two regions are typical of the various deformational modes of methyl groups, the low-energy region is populated by the modes corresponding to the movements of the whole dimethylsulfoxide molecule.

Type
Article
Copyright
Copyright © Clay Minerals Society 2010

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References

Brandenburg, K., 2006 Inelastic neutron scattering and lattice dynamics of minerals Diamond 14 291329.Google Scholar
Durig, J.R. Player, C.M. Jr. and Bragin, J., 1970 Low-frequency vibrations of molecular crystals VII. DMSO and DMSO-d6. The Journal of Chemical Physics 52 42244233.Google Scholar
Fan, Y.B. Solin, S.A. Kim, H. Pinnavaia, T.J. and Neumann, D.A., 1992 Elastic and inelastic neutron-scattering study of hydrogenated and deuterated trimethylammonium pillared vermiculite clays Journal of Chemical Physics 96 70647071 10.1063/1.462538.CrossRefGoogle Scholar
Ferrario, M. and Ryckaert, J.P. (1985) Constant pressureconstant temperature molecular dynamics for rigid and partially rigid molecular systems. Molecular Physics, 54, 587603.CrossRefGoogle Scholar
Frost, R.L. and Kloprogge, J.T. (1999) Raman spectroscopy of the low frequency region of kaolinite at 298 and 77 K. Applied Spectroscopy, 53, 16101616.CrossRefGoogle Scholar
Horrocks, W.D. Jr. and Cotton, F.A., 1961 Infrared and Raman spectra and normal co-ordinate analysis of dimethyl sulfoxide and dimethyl sulfoxide-d6 Spectrochimica Acta 17 134147 10.1016/0371-1951(61)80059-3.CrossRefGoogle Scholar
Johnston, C.T. Helsen, J. Schoonheydt, R.A. Bish, D.L. and Agnew, S.F., 1998 Single-crystal Raman spectroscopic study of dickite American Mineralogist 83 7584 10.2138/am-1998-1-208.CrossRefGoogle Scholar
Johnston, C.T. Bish, D.L. Eckert, J. and Brown, L.A., 2000 Infrared and inelastic neutron scattering study of the 1.03- and 0.95-nm kaolinite-hydrazine intercalation complexes Journal of Physical Chemistry B 104 80808088 10.1021/jp001075s.CrossRefGoogle Scholar
Kresse, G. and Hafner, J., 1993 Ab initio molecular dynamics for open-shell transition metals Physical Review B 48 1311513118 10.1103/PhysRevB.48.13115.CrossRefGoogle ScholarPubMed
Kresse, G. and Hafner, J., 1994 Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements Journal of Physics: Condensed Matter 6 82458527.Google Scholar
Kresse, G. and Furthműller, J., 1996 Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Computational Materials Science 6 1550 10.1016/0927-0256(96)00008-0.CrossRefGoogle Scholar
Kirkpatrick, R.J. Kalinchev, A.G. Wang, J. Hou, X. Amonette, J. and Theo Kloprogge, editor, J., 2005 Molecular modeling of the vibrational spectra of interlayer and surface species of layered double hydroxides The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Aurora, CO, USA The Clay Minerals Society 239285.Google Scholar
Mitchell, P.C.H. Parker, S.F. Ramirez-Cuesta, A.J. and Tomkinson, J., 2005 Vibrational Spectroscopy with Neutrons Singapore World Scientific 10.1142/5628.CrossRefGoogle Scholar
Martens, W.N. Frost, R.L. Kristof, J. and Horvath, E., 2002 Modification of kaolinite surfaces through intercalation with deuterated dimethylsulfoxide Journal of Physical Chemistry B 106 41624171 10.1021/jp0130113.CrossRefGoogle Scholar
Nosê, S.J., 1984 A unified formulation of the constant temperature molecular dynamics methods Journal of Chemical Physics 81 511519 10.1063/1.447334.CrossRefGoogle Scholar
Olejnik, S. Aylmore, L.A.G. Posner, A.M. and Quirk, J.P., 1968 Infrared spectra of kaolin mineral-dimethylsulfoxide complexes The Journal of Physical Chemistry 72 241249 10.1021/j100847a045.CrossRefGoogle Scholar
Ramirez-Cuesta, A.J., 2004 aCLIMAX 4.0.1. The new version of the software for analyzing and interpreting INS spectra Computer Physics Communications 157 226238 10.1016/S0010-4655(03)00520-4.CrossRefGoogle Scholar
Safford, S.J. Schaffer, P.C. Leung, P.S. Doebbler, G.F. Brady, G.W. and Lyden, E.F.X., 1969 Neutron inelastic scattering and X-ray studies of aqueous solutions of dimethylsulfoxide and dimethylsulphone The Journal of Chemical Physics 50 21402159 10.1063/1.1671344.CrossRefGoogle Scholar
Scholtzová, E. and Smrčok, L., 2009 Hydrogen bonding and vibrational spectra in kaolinite-dimethylsulfoxide and — dimethylselenoxide intarcalates — a solid state computational study Clays and Clay Minerals 57 5471 10.1346/CCMN.2009.0570106.CrossRefGoogle Scholar
Sládkovičcová, M. Smrčok, L. Mach, P. Tunega, D. and Ramirez-Cuesta, A.J., 2008 Inelastic neutron scattering and DFT study of 1,6-anhydro-β-D-glucopyranose Journal of Molecular Structure 874 108120 10.1016/j.molstruc.2007.03.042.CrossRefGoogle Scholar
Steiner, T., 2002 The hydrogen bond in the solid state Angewandte Chemie, International Edition 41 4876 10.1002/1521-3773(20020104)41:1<48::AID-ANIE48>3.0.CO;2-U.3.0.CO;2-U>CrossRefGoogle ScholarPubMed
Wada, N. and Kamitakahara, W.A., 1991 Inelastic neutronscattering and Raman-scattering studies of muscovite and vermiculite layered silicates Physical Review B 43 23912397 10.1103/PhysRevB.43.2391.CrossRefGoogle Scholar