title: OH-stretching in synthetic hydrogen-bonded chains.
abstract: We study hydrogen bond dynamics in stereoselectively synthesized polyalcohols by combining linear and two-dimensional (2D) infrared spectroscopy experiments with simulations. We consider two variants of the polyalcohols: the all-syn and all-anti tetrol, which because of their different stereochemistry of the hydroxyl groups form a linear hydrogen-bonded chain that is stable for tens of picoseconds or a system where hydrogen bonds are formed and broken on a picosecond timescale, respectively. The differences in structure and hydrogen bond dynamics gives rise to significant differences in the linear spectra for the two compounds. Furthermore, we show that the stronger hydrogen bonding for the all-syn variant leads to faster fluctuations of the site frequencies than for the all-anti one, which is reflected in the higher degree of homogeneous broadening in the 2D spectra. Because of the different stereochemistry, the coupling in the all-syn molecule is stronger than for the all-anti one, which leads to a faster delocalization of a local excitation. This explains the previously observed pump-frequency independent vibrational lifetime for the all-syn variant, since the excitation loses the memory of the pump frequency before relaxation. For the all-anti form, the coupling is weak and the excitation remains in the initially excited state, maintaining the memory of the pump frequency.
authors.affiliation: Zernike Institute for Advanced Materials, University of Groningen , Nijenborgh 4, 9747 AG Groningen, The Netherlands.
authors.forename: C P
authors.initials: CP
authors.lastname: van der Vegte
authors.forename: S
authors.initials: S
authors.lastname: Knop
authors.forename: P
authors.initials: P
authors.lastname: Vöhringer
authors.forename: J
authors.initials: J
authors.lastname: Knoester
authors.forename: T L C
authors.initials: TL
authors.lastname: Jansen
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D016014:Linear Models; D008956:Models, Chemical; D010100:Oxygen / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014732:Vibration
chemical_list: D000438:Alcohols; D006859:Hydrogen; D010100:Oxygen