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Yann DANTEN

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shant shahbazian

Shahid Beheshti University

Pooria Farahani

KTH Royal Institute of Technology

University of California, Riverside

Ludovic Bellot-Gurlet

Sorbonne Université

Universidad Simón Bolívar

Boston University

Fadhil I. Sharrad

Kerbalauniversity

Ana Lilian Montero-Alejo

Universidad de la Habana

Bergische Universität Wuppertal

Tu Darmstadt

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Papers by Yann DANTEN

Correction to “Carbonyl-Based Redox-Active Compounds as Organic Electrodes for Batteries: Escape from Middle–High Redox Potentials and Further Improvement?”

The Journal of Physical Chemistry A

Carbonyl-Based Redox-Active Compounds as Organic Electrodes for Batteries: Escape from MiddleHigh Redox Potentials and Further Improvement?

L'eau supercritique: ordre local et dynamique moléculaire

Atomic Group Decomposition of Charge Transfer Excitation Global Indexes

The Journal of Physical Chemistry A

into molecular subdomains contributions is presented and a software, DOCTRINE (atomic group Decom... more into molecular subdomains contributions is presented and a software, DOCTRINE (atomic group Decomposition Of the Charge TRansfer INdExes) for the implementation of this novel model has been coded. Although our method applies to any fuzzy or to any disjoint exhaustive partitioning of the real space, it is here applied using a definition of chemically relevant molecular subdomains based on the Atoms in Molecules Bader basins. This choice has the relevant advantage of associating intra or inter subdomain contributions to rigorously defined quantum objects, yet bearing a clear chemical meaning. Our method allows for a quantitative evaluation of the subdomain contributions to the charge transfer, the charge transfer excitation length and the dipole moment change upon excitation. All these global indexes may be obtained either from the electron density increment or the electron density depletion upon excitation. However, the subdomain contributions obtained from the two distributions generally differ, therefore allowing to distinguish whether the contribution to a given property of a given subdomain is dominated by one of the two distributions or if both are playing a significant role. As a toy system for the first application of our model, a typical [D−π−A, π = conjugated bridge] compound belonging to the merocyanine dyes family is selected, and the first four excited states of this compound in a strongly polar protic solvent and in a weakly polar solvent are thoroughly investigated.

Seeking for Optimal Excited States in Photoinduced Electron-Transfer ProcessesThe Case Study of Brookers Merocyanine

rational and rotational relaxation of hexafluorobenzene studied by Raman scattering in the supercritical domain

HAL (Le Centre pour la Communication Scientifique Directe), 2006

Assessing the non-ideality of the CO2-CS2system at molecular level: A Raman scattering study

The Journal of Chemical Physics, 2013

The dense phase of CO 2-CS 2 mixtures has been analysed by Raman spectroscopy as a function of th... more The dense phase of CO 2-CS 2 mixtures has been analysed by Raman spectroscopy as a function of the CO 2 concentration (0.02-0.95 mole fractions) by varying the pressure (0.5 MPa up to 7.7 MPa) at constant temperature (313 K). The polarised and depolarised spectra of the induced (ν 2 , ν 3) modes of CS 2 and of the ν 1-2ν 2 Fermi resonance dyad of both CO 2 and CS 2 have been measured. Upon dilution with CO 2 , the evolution of the spectroscopic observables of all these modes displays a "plateau-like" region in the CO 2 mole fraction 0.3-0.7 never previously observed in CO 2organic liquids mixtures. The bandshape and intensity of the induced modes of CS 2 are similar to those of pure CS 2 up to equimolar concentration, after which variations occur. The preservation of the local ordering from pure CS 2 to equimolar concentration together with the non-linear evolution of the spectroscopic observables allows inferring that two solvation regimes exist with a transition occurring in the plateau domain. In the first regime, corresponding to CS 2 concentrated mixtures, the liquid phase is segregated with dominant CS 2 clusters, whereas, in the second one, CO 2 monomers and dimers and CO 2-CS 2 hetero-dimers coexist dynamically on a picosecond timescale. It is demonstrated that the subtle interplay between attractive and repulsive interactions which provides a molecular interpretation of the non-ideality of the CO 2-CS 2 mixture allows rationalizing the volume expansion and the existence of the plateau-like region observed in the pressure-composition diagram previously ascribed to the proximity of an upper critical solution temperature at lower temperatures.

Breaking the Structure of Liquid Hydrogenated Alcohols Using Perfluorinated tert-Butanol: A Multitechnique Approach (Infrared, Raman, and Xray Scattering) Analyzed by DFT and Molecular Dynamics Calculations

The state of aggregation at room temperature of tert-butanol (TBH) and perfluoro tert-butanol (TB... more The state of aggregation at room temperature of tert-butanol (TBH) and perfluoro tert-butanol (TBF) liquid mixtures is assessed by vibrational spectroscopy (Raman and infrared) and X-ray diffraction and analyzed using density functional theory (DFT) and molecular dynamics (MD) simulations. It is shown that larger clusters (mostly tetramers) of TBH are destroyed upon dilution with TBF. Small oligomers, monomers, and mainly heterodimers are present at the equimolar concentration. At variance with slightly interacting solvents, the signature of hetero-oligomers is shown by the appearance of a new broad band detected in the infrared region. The same spectral observation is detected for mixtures of other hydrogenated alcohols (methanol and 1-butanol). The new infrared feature is unaffected by dilution in a polar solvent (CDCl3) in a high-concentration domain, allowing us to assign it to the signature of small hetero-oligomers. MD simulations are used to assess the nature of the species present in the mixture (monomers and small hetero-oligomers) and to follow the evolution of their population upon the dilution. Combining MD simulations with DFT calculations, the infrared spectral profile is successfully analyzed in equimolecular mixtures. This study shows that TBF is a structure breaker of hydrogen-bonded alcohol networks and that the TBF (donor)-TBH (acceptor) heterodimer is the dominant species in an extended range of concentration, centered in the vicinity of the equimolar fraction.

The structure of liquid perfluoro Tert-Butanol using Infrared, Raman and X-Ray scattering analyzed by quantum DFT calculations and molecular Dynamics

Chemical Physics Letters, 2021

Abstract The state of aggregation of room temperature liquid perfluoro tert-butanol (TBF) has bee... more Abstract The state of aggregation of room temperature liquid perfluoro tert-butanol (TBF) has been assessed in comparison with that of its hydrogenated homologue (TBH). This study has been performed using vibrational spectroscopy (Raman scattering and infrared absorption) and X-ray diffraction, analyzed by quantum DFT calculations and Molecular Dynamics simulations. In contrast with TBH, in which large oligomers (aggregates of 4 to 6 molecules) predominate, TBF was found to mainly consist of monomers and dimers. The strongly acidic properties of this molecule, due to the electron-withdrawing effect of its CF3 groups, plays a relevant role in making it a poorly associated alcohol.

Etude par simulation des solutions de complexes de transfert de charge de types i#2-bz (complexe faible) et i#2-py (complexe fort)

On developpe un potentiel realiste entre l'halogene et la molecule aromatique capable de decr... more On developpe un potentiel realiste entre l'halogene et la molecule aromatique capable de decrire les forces intermoleculaires classiques en phase liquide de repulsion, de dispersion et electrostatiques et de prendre en compte les processus de polarisation et de transfert de charge dans les cas des systemes i#2-bz et i#2-py. L'accent est mis egalement sur les proprietes physiques des complexes a l'etat electronique fondamental en phase gazeuse. Les proprietes structurales et thermodynamiques sont calculees par dynamique moleculaire pour les solutions d'iode diluee dans le benzene et dans la pyridine. On s'interesse plus precisement aux effets engendres par la dissolution de l'iode dans ces solvants, mais aussi aux proprietes specifiques comme la presence eventuelle de complexes en solution. Dans l'affirmative, leur structure et leur concentration sont determinees. On analyse les profils de bande (i. R. L. ) des solutions i#2/bz et i#2/py simulee et on s&#3...

Experimental and theoretical studies of tetraethoxysilane gelation doped with Mn (II)

Materials Chemistry and Physics, 1992

Tetraethoysilane (TEOS) gelation at pH 9, in a solution of MnSO,.H,O is studied. Mn (II) species ... more Tetraethoysilane (TEOS) gelation at pH 9, in a solution of MnSO,.H,O is studied. Mn (II) species in the reactive medium cause an important acceleration in the gelation rate. Gels are thermally treated at 200, 400, 600 and 800 "C for 72 hours. The solids are studied by IR spectroscopy, UV-Vis (diffuse reflectance) and XRD techniques. The structure of the solids are optimized by using the Extended Hiickel theoretical method. The results show the formation of the octahedral manganese species in the silica network, which favors the formation of internal hydrogen bonds and explains the observed hydroxylation which remains even at high temperatures.

Infrared spectroscopic study of hydrogen bonding: Hydrogen bond association of phenols with dioxan

Australian Journal of Chemistry, 1966

A tool for deciphering the redox potential ranking of organic compounds: the case study of biomass extracted quinones for sustainable energy

Physical Chemistry Chemical Physics

Carbonyl compounds have emerged as promising organic electrodes for sustainable energy storage. A... more

Interaction of Water Highly Diluted in 1-Alkyl-3-methyl Imidazolium Ionic Liquids with the PF6− and BF4− Anions

The Journal of Physical …, 2009

We have investigated water highly diluted in 1-alkyl-3-methyl imidazolium ionic liquids (ILs) wit... more We have investigated water highly diluted in 1-alkyl-3-methyl imidazolium ionic liquids (ILs) with hexafluorophosphate {PF(6)(-)} and tetrafluoroborate {BF(4)(-)} anions using vibrational spectroscopic measurements in the nu(OH) spectral domain of water (3600-3800 cm(-1)) and DFT calculations. The measured profiles exhibit two well-defined bands at coinciding vibrational transitions assigned with the nu(1) symmetric and nu(3) antisymmetric OH stretching modes of monodispersed water. The local organization and the vibrational spectra of water diluted in ILs have been assessed by DFT calculations (using the B3LYP functional and 6-31+G** basis set). We show that the predicted structures of water interacting (minimally) with two anions in nearly &amp;amp;quot;symmetric&amp;amp;quot; structures of type (A...H-O-H...A) lead to spectral features consistent with the previous spectroscopic observations as well as with those reported here. We emphasize the role of the non additive interaction forces (especially the 3-bodies electrostatic interactions) in the structural organization taking place between the cation-anion couples and for determining preferentially (A...H-O-H...A) associations of water with the anions as well as their consequences on the vibrational spectra of water. We show that the doubly hydrogen-bonded character of water in such associations leads to well-defined spectral features, which are the shifts of the nu(1) and nu(3) stretching modes of water, the separation Delta nu(13) between them (about 80 cm(-1)), and the intensity ratio estimates R = I nu(3)/I nu(1) (IR absorption and Raman). Finally, we evoke the fact that the H-bond interactions of water diluted in these ILs involve a more noticeable electrostatic character than for H-bond interactions of water in usual molecular solvents. In this context, we emphasize that the appearance of the Raman band of the nu(3) mode of water originates from a significant polarization of water due to the local electrostatic fields induced by surrounding ions.

Gaseous hetero dimers of perfluoro tert-butyl alcohol with hydrogenated alcohols by infrared spectroscopy and quantum DFT calculations

Infrared spectroscopy shows that perfluoro tert-butyl alcohol (TBF) forms hydrogen bonded hetero ... more Infrared spectroscopy shows that perfluoro tert-butyl alcohol (TBF) forms hydrogen bonded hetero dimers with hydrogenated alcohols (Methanol, 1-butanol and Tert-butanol) in the gas phase at room temperature. DFT calculations confirm these findings providing structures, stabilization energies and allow a first analysis of the νOH spectra by considering only the diagonal term of the anharmonicity of the vibration. The broad band-shapes of νOH vibration of the TBF molecule engaged in the heterodimer are discussed, considering vibrational phase relaxation.

Far Infrared Spectroscopic Investigations of Liquid Mixtures

Collision- and Interaction-Induced Spectroscopy, 1995

Investigations of induced far infrared profiles of non polar neat liquids and solutions (Van der ... more Investigations of induced far infrared profiles of non polar neat liquids and solutions (Van der Waals and electron donor acceptor binary mixtures) are reported and critically analysed by a multitechnique approach in order to better assess the concept of complex. For neat liquids (benzene and its fluorinated derivatives), the rotational and translational collective diffusive processes affect the spectral density while the ‘packing’ of the molecules governs the short-time dynamic reflected in the α(ω) profiles. In Van der Waals mixtures (C6H6-C6F6), the departures of induced bandshapes (excess intensity) from those of the pure components, might be ascribed to the spectral ‘signature’ of complexes. Finally, in solutions of weak charge transfer complexes (I2-Bz), both electrostatic and charge transfer interactions are found to coexist playing a major role respectively in the long-time and short-time dynamical behaviour of the intermolecular interactions. We emphasise that the studies of the previous solutions are relevant in the context of vibrational spectroscopic investigations of reactive fluids.

Simple method of preparation of novel hydrophobic ionic liquid with a per-fluoro-tert-butoxide anion

New J. Chem., 2016

A simple and atom-economic method for preparation of a novel hydrophobic ionic liquid based on th... more

Solute–solvent interactions governing preferential solvation phenomena of acetaminophen in CO 2-expanded organic solutions

J Supercrit Fluid, 2006

The present work aims to characterize the nature and intensity of the specific and non-specific s... more The present work aims to characterize the nature and intensity of the specific and non-specific solute-solvent interactions responsible for the different solvating behaviour of "CO 2-expanded ethanol" and "CO 2-expanded acetone" towards acetaminophen, an analgesic drug commercially known as paracetamol. The intermolecular interactions between acetaminophen and solvent molecules involved in these expanded media and its sensitivity to solvent composition changes, have been analyzed by high-pressure IR spectroscopy, LSER analysis, and theoretical ab initio calculations performed with acetaminophen-(ethanol) n and acetaminophen-(acetone) n complexes. It comes out that the distinct perturbation experienced by the cybotactic region of acetaminophen in "CO 2-expanded ethanol" and "CO 2-expanded acetone" when CO 2 content increases is basically a consequence of the higher sensitivity to solvent composition changes of the dipole-dipole interactions, established between the acetaminophen carbonyl group and acetone solvent molecules, in relation to that of the hydrogen bond interactions existing between this group and ethanol solvent molecules.

Solute–solvent interactions governing preferential solvation phenomena of acetaminophen in CO2-expanded organic solutionsA spectroscopic and theoretical study

J Supercrit Fluid, 2006

The present work aims to characterize the nature and intensity of the specific and non-specific s... more The present work aims to characterize the nature and intensity of the specific and non-specific solute-solvent interactions responsible for the different solvating behaviour of "CO 2-expanded ethanol" and "CO 2-expanded acetone" towards acetaminophen, an analgesic drug commercially known as paracetamol. The intermolecular interactions between acetaminophen and solvent molecules involved in these expanded media and its sensitivity to solvent composition changes, have been analyzed by high-pressure IR spectroscopy, LSER analysis, and theoretical ab initio calculations performed with acetaminophen-(ethanol) n and acetaminophen-(acetone) n complexes. It comes out that the distinct perturbation experienced by the cybotactic region of acetaminophen in "CO 2-expanded ethanol" and "CO 2-expanded acetone" when CO 2 content increases is basically a consequence of the higher sensitivity to solvent composition changes of the dipole-dipole interactions, established between the acetaminophen carbonyl group and acetone solvent molecules, in relation to that of the hydrogen bond interactions existing between this group and ethanol solvent molecules.

Etude par simulation des solutions de complexes de transfert de charge de types i#2-bz (complexe faible) et i#2-py (complexe fort)

Http Www Theses Fr, 1992

Correction to “Carbonyl-Based Redox-Active Compounds as Organic Electrodes for Batteries: Escape from Middle–High Redox Potentials and Further Improvement?”

The Journal of Physical Chemistry A

Carbonyl-Based Redox-Active Compounds as Organic Electrodes for Batteries: Escape from MiddleHigh Redox Potentials and Further Improvement?

L'eau supercritique: ordre local et dynamique moléculaire

Atomic Group Decomposition of Charge Transfer Excitation Global Indexes

The Journal of Physical Chemistry A

into molecular subdomains contributions is presented and a software, DOCTRINE (atomic group Decom... more into molecular subdomains contributions is presented and a software, DOCTRINE (atomic group Decomposition Of the Charge TRansfer INdExes) for the implementation of this novel model has been coded. Although our method applies to any fuzzy or to any disjoint exhaustive partitioning of the real space, it is here applied using a definition of chemically relevant molecular subdomains based on the Atoms in Molecules Bader basins. This choice has the relevant advantage of associating intra or inter subdomain contributions to rigorously defined quantum objects, yet bearing a clear chemical meaning. Our method allows for a quantitative evaluation of the subdomain contributions to the charge transfer, the charge transfer excitation length and the dipole moment change upon excitation. All these global indexes may be obtained either from the electron density increment or the electron density depletion upon excitation. However, the subdomain contributions obtained from the two distributions generally differ, therefore allowing to distinguish whether the contribution to a given property of a given subdomain is dominated by one of the two distributions or if both are playing a significant role. As a toy system for the first application of our model, a typical [D−π−A, π = conjugated bridge] compound belonging to the merocyanine dyes family is selected, and the first four excited states of this compound in a strongly polar protic solvent and in a weakly polar solvent are thoroughly investigated.

Seeking for Optimal Excited States in Photoinduced Electron-Transfer ProcessesThe Case Study of Brookers Merocyanine

rational and rotational relaxation of hexafluorobenzene studied by Raman scattering in the supercritical domain

HAL (Le Centre pour la Communication Scientifique Directe), 2006

Assessing the non-ideality of the CO2-CS2system at molecular level: A Raman scattering study

The Journal of Chemical Physics, 2013

The dense phase of CO 2-CS 2 mixtures has been analysed by Raman spectroscopy as a function of th... more The dense phase of CO 2-CS 2 mixtures has been analysed by Raman spectroscopy as a function of the CO 2 concentration (0.02-0.95 mole fractions) by varying the pressure (0.5 MPa up to 7.7 MPa) at constant temperature (313 K). The polarised and depolarised spectra of the induced (ν 2 , ν 3) modes of CS 2 and of the ν 1-2ν 2 Fermi resonance dyad of both CO 2 and CS 2 have been measured. Upon dilution with CO 2 , the evolution of the spectroscopic observables of all these modes displays a "plateau-like" region in the CO 2 mole fraction 0.3-0.7 never previously observed in CO 2organic liquids mixtures. The bandshape and intensity of the induced modes of CS 2 are similar to those of pure CS 2 up to equimolar concentration, after which variations occur. The preservation of the local ordering from pure CS 2 to equimolar concentration together with the non-linear evolution of the spectroscopic observables allows inferring that two solvation regimes exist with a transition occurring in the plateau domain. In the first regime, corresponding to CS 2 concentrated mixtures, the liquid phase is segregated with dominant CS 2 clusters, whereas, in the second one, CO 2 monomers and dimers and CO 2-CS 2 hetero-dimers coexist dynamically on a picosecond timescale. It is demonstrated that the subtle interplay between attractive and repulsive interactions which provides a molecular interpretation of the non-ideality of the CO 2-CS 2 mixture allows rationalizing the volume expansion and the existence of the plateau-like region observed in the pressure-composition diagram previously ascribed to the proximity of an upper critical solution temperature at lower temperatures.

Breaking the Structure of Liquid Hydrogenated Alcohols Using Perfluorinated tert-Butanol: A Multitechnique Approach (Infrared, Raman, and Xray Scattering) Analyzed by DFT and Molecular Dynamics Calculations

The state of aggregation at room temperature of tert-butanol (TBH) and perfluoro tert-butanol (TB... more The state of aggregation at room temperature of tert-butanol (TBH) and perfluoro tert-butanol (TBF) liquid mixtures is assessed by vibrational spectroscopy (Raman and infrared) and X-ray diffraction and analyzed using density functional theory (DFT) and molecular dynamics (MD) simulations. It is shown that larger clusters (mostly tetramers) of TBH are destroyed upon dilution with TBF. Small oligomers, monomers, and mainly heterodimers are present at the equimolar concentration. At variance with slightly interacting solvents, the signature of hetero-oligomers is shown by the appearance of a new broad band detected in the infrared region. The same spectral observation is detected for mixtures of other hydrogenated alcohols (methanol and 1-butanol). The new infrared feature is unaffected by dilution in a polar solvent (CDCl3) in a high-concentration domain, allowing us to assign it to the signature of small hetero-oligomers. MD simulations are used to assess the nature of the species present in the mixture (monomers and small hetero-oligomers) and to follow the evolution of their population upon the dilution. Combining MD simulations with DFT calculations, the infrared spectral profile is successfully analyzed in equimolecular mixtures. This study shows that TBF is a structure breaker of hydrogen-bonded alcohol networks and that the TBF (donor)-TBH (acceptor) heterodimer is the dominant species in an extended range of concentration, centered in the vicinity of the equimolar fraction.

The structure of liquid perfluoro Tert-Butanol using Infrared, Raman and X-Ray scattering analyzed by quantum DFT calculations and molecular Dynamics

Chemical Physics Letters, 2021

Abstract The state of aggregation of room temperature liquid perfluoro tert-butanol (TBF) has bee... more Abstract The state of aggregation of room temperature liquid perfluoro tert-butanol (TBF) has been assessed in comparison with that of its hydrogenated homologue (TBH). This study has been performed using vibrational spectroscopy (Raman scattering and infrared absorption) and X-ray diffraction, analyzed by quantum DFT calculations and Molecular Dynamics simulations. In contrast with TBH, in which large oligomers (aggregates of 4 to 6 molecules) predominate, TBF was found to mainly consist of monomers and dimers. The strongly acidic properties of this molecule, due to the electron-withdrawing effect of its CF3 groups, plays a relevant role in making it a poorly associated alcohol.

Etude par simulation des solutions de complexes de transfert de charge de types i#2-bz (complexe faible) et i#2-py (complexe fort)

On developpe un potentiel realiste entre l'halogene et la molecule aromatique capable de decr... more On developpe un potentiel realiste entre l'halogene et la molecule aromatique capable de decrire les forces intermoleculaires classiques en phase liquide de repulsion, de dispersion et electrostatiques et de prendre en compte les processus de polarisation et de transfert de charge dans les cas des systemes i#2-bz et i#2-py. L'accent est mis egalement sur les proprietes physiques des complexes a l'etat electronique fondamental en phase gazeuse. Les proprietes structurales et thermodynamiques sont calculees par dynamique moleculaire pour les solutions d'iode diluee dans le benzene et dans la pyridine. On s'interesse plus precisement aux effets engendres par la dissolution de l'iode dans ces solvants, mais aussi aux proprietes specifiques comme la presence eventuelle de complexes en solution. Dans l'affirmative, leur structure et leur concentration sont determinees. On analyse les profils de bande (i. R. L. ) des solutions i#2/bz et i#2/py simulee et on s&#3...

Experimental and theoretical studies of tetraethoxysilane gelation doped with Mn (II)

Materials Chemistry and Physics, 1992

Tetraethoysilane (TEOS) gelation at pH 9, in a solution of MnSO,.H,O is studied. Mn (II) species ... more Tetraethoysilane (TEOS) gelation at pH 9, in a solution of MnSO,.H,O is studied. Mn (II) species in the reactive medium cause an important acceleration in the gelation rate. Gels are thermally treated at 200, 400, 600 and 800 "C for 72 hours. The solids are studied by IR spectroscopy, UV-Vis (diffuse reflectance) and XRD techniques. The structure of the solids are optimized by using the Extended Hiickel theoretical method. The results show the formation of the octahedral manganese species in the silica network, which favors the formation of internal hydrogen bonds and explains the observed hydroxylation which remains even at high temperatures.

Infrared spectroscopic study of hydrogen bonding: Hydrogen bond association of phenols with dioxan

Australian Journal of Chemistry, 1966

A tool for deciphering the redox potential ranking of organic compounds: the case study of biomass extracted quinones for sustainable energy

Physical Chemistry Chemical Physics

Carbonyl compounds have emerged as promising organic electrodes for sustainable energy storage. A... more

Interaction of Water Highly Diluted in 1-Alkyl-3-methyl Imidazolium Ionic Liquids with the PF6− and BF4− Anions

The Journal of Physical …, 2009

We have investigated water highly diluted in 1-alkyl-3-methyl imidazolium ionic liquids (ILs) wit... more We have investigated water highly diluted in 1-alkyl-3-methyl imidazolium ionic liquids (ILs) with hexafluorophosphate {PF(6)(-)} and tetrafluoroborate {BF(4)(-)} anions using vibrational spectroscopic measurements in the nu(OH) spectral domain of water (3600-3800 cm(-1)) and DFT calculations. The measured profiles exhibit two well-defined bands at coinciding vibrational transitions assigned with the nu(1) symmetric and nu(3) antisymmetric OH stretching modes of monodispersed water. The local organization and the vibrational spectra of water diluted in ILs have been assessed by DFT calculations (using the B3LYP functional and 6-31+G** basis set). We show that the predicted structures of water interacting (minimally) with two anions in nearly &amp;amp;quot;symmetric&amp;amp;quot; structures of type (A...H-O-H...A) lead to spectral features consistent with the previous spectroscopic observations as well as with those reported here. We emphasize the role of the non additive interaction forces (especially the 3-bodies electrostatic interactions) in the structural organization taking place between the cation-anion couples and for determining preferentially (A...H-O-H...A) associations of water with the anions as well as their consequences on the vibrational spectra of water. We show that the doubly hydrogen-bonded character of water in such associations leads to well-defined spectral features, which are the shifts of the nu(1) and nu(3) stretching modes of water, the separation Delta nu(13) between them (about 80 cm(-1)), and the intensity ratio estimates R = I nu(3)/I nu(1) (IR absorption and Raman). Finally, we evoke the fact that the H-bond interactions of water diluted in these ILs involve a more noticeable electrostatic character than for H-bond interactions of water in usual molecular solvents. In this context, we emphasize that the appearance of the Raman band of the nu(3) mode of water originates from a significant polarization of water due to the local electrostatic fields induced by surrounding ions.

Gaseous hetero dimers of perfluoro tert-butyl alcohol with hydrogenated alcohols by infrared spectroscopy and quantum DFT calculations

Infrared spectroscopy shows that perfluoro tert-butyl alcohol (TBF) forms hydrogen bonded hetero ... more Infrared spectroscopy shows that perfluoro tert-butyl alcohol (TBF) forms hydrogen bonded hetero dimers with hydrogenated alcohols (Methanol, 1-butanol and Tert-butanol) in the gas phase at room temperature. DFT calculations confirm these findings providing structures, stabilization energies and allow a first analysis of the νOH spectra by considering only the diagonal term of the anharmonicity of the vibration. The broad band-shapes of νOH vibration of the TBF molecule engaged in the heterodimer are discussed, considering vibrational phase relaxation.

Far Infrared Spectroscopic Investigations of Liquid Mixtures

Collision- and Interaction-Induced Spectroscopy, 1995

Investigations of induced far infrared profiles of non polar neat liquids and solutions (Van der ... more Investigations of induced far infrared profiles of non polar neat liquids and solutions (Van der Waals and electron donor acceptor binary mixtures) are reported and critically analysed by a multitechnique approach in order to better assess the concept of complex. For neat liquids (benzene and its fluorinated derivatives), the rotational and translational collective diffusive processes affect the spectral density while the ‘packing’ of the molecules governs the short-time dynamic reflected in the α(ω) profiles. In Van der Waals mixtures (C6H6-C6F6), the departures of induced bandshapes (excess intensity) from those of the pure components, might be ascribed to the spectral ‘signature’ of complexes. Finally, in solutions of weak charge transfer complexes (I2-Bz), both electrostatic and charge transfer interactions are found to coexist playing a major role respectively in the long-time and short-time dynamical behaviour of the intermolecular interactions. We emphasise that the studies of the previous solutions are relevant in the context of vibrational spectroscopic investigations of reactive fluids.

Simple method of preparation of novel hydrophobic ionic liquid with a per-fluoro-tert-butoxide anion

New J. Chem., 2016

A simple and atom-economic method for preparation of a novel hydrophobic ionic liquid based on th... more

Solute–solvent interactions governing preferential solvation phenomena of acetaminophen in CO 2-expanded organic solutions

J Supercrit Fluid, 2006

The present work aims to characterize the nature and intensity of the specific and non-specific s... more The present work aims to characterize the nature and intensity of the specific and non-specific solute-solvent interactions responsible for the different solvating behaviour of "CO 2-expanded ethanol" and "CO 2-expanded acetone" towards acetaminophen, an analgesic drug commercially known as paracetamol. The intermolecular interactions between acetaminophen and solvent molecules involved in these expanded media and its sensitivity to solvent composition changes, have been analyzed by high-pressure IR spectroscopy, LSER analysis, and theoretical ab initio calculations performed with acetaminophen-(ethanol) n and acetaminophen-(acetone) n complexes. It comes out that the distinct perturbation experienced by the cybotactic region of acetaminophen in "CO 2-expanded ethanol" and "CO 2-expanded acetone" when CO 2 content increases is basically a consequence of the higher sensitivity to solvent composition changes of the dipole-dipole interactions, established between the acetaminophen carbonyl group and acetone solvent molecules, in relation to that of the hydrogen bond interactions existing between this group and ethanol solvent molecules.

Solute–solvent interactions governing preferential solvation phenomena of acetaminophen in CO2-expanded organic solutionsA spectroscopic and theoretical study

J Supercrit Fluid, 2006

The present work aims to characterize the nature and intensity of the specific and non-specific s... more The present work aims to characterize the nature and intensity of the specific and non-specific solute-solvent interactions responsible for the different solvating behaviour of "CO 2-expanded ethanol" and "CO 2-expanded acetone" towards acetaminophen, an analgesic drug commercially known as paracetamol. The intermolecular interactions between acetaminophen and solvent molecules involved in these expanded media and its sensitivity to solvent composition changes, have been analyzed by high-pressure IR spectroscopy, LSER analysis, and theoretical ab initio calculations performed with acetaminophen-(ethanol) n and acetaminophen-(acetone) n complexes. It comes out that the distinct perturbation experienced by the cybotactic region of acetaminophen in "CO 2-expanded ethanol" and "CO 2-expanded acetone" when CO 2 content increases is basically a consequence of the higher sensitivity to solvent composition changes of the dipole-dipole interactions, established between the acetaminophen carbonyl group and acetone solvent molecules, in relation to that of the hydrogen bond interactions existing between this group and ethanol solvent molecules.

Etude par simulation des solutions de complexes de transfert de charge de types i#2-bz (complexe faible) et i#2-py (complexe fort)

Http Www Theses Fr, 1992