Frequency factors and isotope effects in solid state rate processes

Hydrogen bonding in solids correlation of spectroscopic and crystallographic data

Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = ⟨cos θ ⟩/⟨cos3 θ⟩, and comparison between the PNA me...

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

Among many various kinds of molecular interactions, the H-bond has a special position. The term is ubiquitous in the world that surrounds us, but also it is often applied in different ways. The H-bond is of great importance in natural sciences. This relates particularly to biological aspects, such as molecular recognition that could be a basis for the creation of life,1-4 formation of higher order structures of peptides and nucleic acids,5 and biochemical processes, particularly the enzymes catalyzed.6,7 One can say that the H-bond plays a double role in biological systems: on one hand, as a relatively strong directional interaction, it leads to relatively stable supramolecular structures, and on the other hand, because of dynamic features of the proton, it is an active site for initiation of chemical reactions. H-bonds are the source of specific properties of associated liquids, with water being the most popular among them.8 Water as a medium in which life was most probably created is saturated by H-bonds with highly mobile protons in between, even in the solid state.9 In many crystal lattices of organic compounds, the H-bonds are a decisive factor governing packing.10 In designing new interesting crystal structures, which is the subject of fast developing crystal engineer* To whom correspondence should be addressed. E-mail: slagra@ uni.lodz.pl or slagra@ccmsi.us. Fax: +48-42-6790447. 3513 Chem. Rev. 2005, 105, 3513−3560

Interrelation between H-bond and Pi-electron delocalization.

An examination of linear solvation energy relationships

Spectre infrarouge et attribution des vibrations des toluènes C6H5CH8, C6H5CD8 et C6D5CD3

An Infrared Spectroscopic Study of the Carbonyl Stretching Frequency in Some Groups of Ketones and Quinones

The three‐micron infrared absorption bands assigned to the NH stretching vibration have been studied in pyrrole, indole, carbazole, diphenylamine, and aniline Spectra have been obtained in solution in carbon tetrachloride, carbon disulfide, chloroform, and benzene over a wide range of concentrations In pyrrole and indole with increasing concentration the sharp NH band fades out and a broader band to lower frequencies appears While the results are not as clearcut for diphenylamine and aniline, for these four compounds hydrogen bonding satisfactorily explains the observed data This conclusion, for pyrrole and indole, sets aside the infrared spectroscopic basis for Pauling's hypothesis of two species of molecules Carbazole was not soluble enough to make association studies possible The relation of both the solvent and the solute molecular structure to the position of the associated and unassociated frequencies is discussed

The NH Stretching Vibration and NH–N Hydrogen Bonding in Several Aromatic Compounds

This paper reports on an experimental study of the C=O stretching vibration frequency in a large number of quinonoid compounds, both substituted and unsubstituted. For nonsubstituted ortho and para quinones, relationships between the carbonyl frequency and (a) the number of fused rings, (b) the oxidation‐reduction potential, and (c) the index of free valence on the parent hydrocarbon are pointed out and discussed. It is shown that for a six‐atom quinonoid ring the C=O frequency is, to a first approximation, a function of the C=O bond order. For substituted quinones, the variation in the carbonyl frequency is related to the induction effect of the substituent in the same way as is the variation in oxidation‐reduction potential. Certain hydroxy‐substituted quinones show spectral anomalies which do not seem to fit into the usual category of hydrogen bonded compounds.

An Infrared Spectroscopic Study of the Carbonyl Stretching Frequency in a Group of Ortho and Para Quinones

Les spectres infrarouges de douze especes isotopiques d'ethanol a l’etat gazeux ou en solution diluee, ont ete enregistres et analyses entre 3 000 et 500 cm–1 . Une attribution basee sur les substitutions isotopiques est proposee. Elle montre en particulier l’evolution des couplages de la vibration δ(COH) selon les especes isotopiques. Le probleme de l’isomerie de rotation est discute.

Marie-Louise Josien

Papers

Spectre infrarouge et attribution des vibrations des toluènes C6H5CH8, C6H5CD8 et C6D5CD3

An Infrared Spectroscopic Study of the Carbonyl Stretching Frequency in Some Groups of Ketones and Quinones

The NH Stretching Vibration and NH–N Hydrogen Bonding in Several Aromatic Compounds

An Infrared Spectroscopic Study of the Carbonyl Stretching Frequency in a Group of Ortho and Para Quinones

I. — Étude des spectres vibrationnels de douze espèces isotopiques d’éthanols monomères