title: Study of polarized IR spectra of the hydrogen bond system in crystals of styrylacetic acid.
abstract: We have investigated the polarized IR spectra of the hydrogen bond system in crystals of trans-styrylacetic acid C(6)H(5)CHCHCH(2)COOH, and also in crystals of the following three deuterium isotopomers of the compound: C(6)H(5)CHCHCH(2)COOD, C(6)H(5)CHCHCD(2)COOH and C(6)H(5)CHCHCD(2)COOD. The spectra were measured at room temperature and at 77K by a transmission method. The spectral studies were preceded by determination of the X-ray crystal structure. Theoretical analysis of the results concerned linear dichroic effects, the H/D isotopic and temperature effects, observed in the solid-state IR spectra of the hydrogen and of the deuterium bond, at the frequency ranges of the nu(OH) and the nu(OD) bands, respectively. Basic spectral properties of the crystals can be interpreted satisfactorily in terms of the "strong-coupling" theory, when based on a hydrogen bond dimer model. This model sufficiently explained not only a two-branch structure of the nu(OH) and the nu(OD) bands, and temperature-induced evolution of the crystalline spectra, but also the linear dichroic effects observed in the band frequency ranges. A vibronic mechanism was analyzed, responsible for promotion of the symmetry-forbidden transition in the IR for the totally symmetric proton stretching vibrations in centrosymmetric hydrogen bond dimers. It was found to be of minor importance, when compared with analogous spectral properties of arylcarboxylic acid, or of cinnamic acid crystals. These effects were ascribed to a substantial weakening of electronic couplings between the hydrogen bonds of the associated carboxyl groups and the styryl radicals, associated with the separation of these groups in styrylacetic acid molecules by methylene groups in the molecules.
authors.affiliation: Institute of Chemistry, University of Silesia, 9 Szkolna Street, Pl-40-006 Katowice, Poland. flakus@ich.us.edu.pl
authors.forename: Henryk T
authors.initials: HT
authors.lastname: Flakus
authors.forename: Magdalena
authors.initials: M
authors.lastname: Jabłońska
authors.forename: Peter G
authors.initials: PG
authors.lastname: Jones
mesh_terms: D055598:Chemical Phenomena; D002627:Chemistry, Physical; D003460:Crystallization; D018360:Crystallography, X-Ray; D005229:Fatty Acids, Monounsaturated / Q000737:chemistry*; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D013696:Temperature; D014732:Vibration
chemical_list: D005229:Fatty Acids, Monounsaturated; C064180:4-phenyl-3-butenoic acid