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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 ,
Daniel Tunega ,
Anibal Javier Ramirez-Cuesta ,
Alexander Ivanov  and
Jana Valúchová
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
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Abstract

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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.

Keywords

DFTDMSOHydrogen BondsINSKaoliniteVibrational Spectra
Type
Article
Information
Clays and Clay Minerals , Volume 58 , Issue 1 , February 2010 , pp. 52 - 61
Copyright
Copyright © Clay Minerals Society 2010

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