skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrogen bond dynamics in bulk alcohols

Abstract

Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics–quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid—alcohols—has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve themore » interplay of hydrophobic and hydrophilic groups.« less

Authors:
; ; ;  [1]
  1. Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (Netherlands)
Publication Date:
OSTI Identifier:
22415916
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CHEMICAL BONDS; CHEMISTRY; DIFFUSION; ETHANOL; INFRARED SPECTRA; LIQUIDS; METHANOL; MOLECULAR DYNAMICS METHOD; MOLECULES; POLARIZATION; PROPANOLS; QUANTUM MECHANICS; SOLVENTS; WATER

Citation Formats

Shinokita, Keisuke, Cunha, Ana V., Jansen, Thomas L. C., and Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl. Hydrogen bond dynamics in bulk alcohols. United States: N. p., 2015. Web. doi:10.1063/1.4921574.
Shinokita, Keisuke, Cunha, Ana V., Jansen, Thomas L. C., & Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl. Hydrogen bond dynamics in bulk alcohols. United States. doi:10.1063/1.4921574.
Shinokita, Keisuke, Cunha, Ana V., Jansen, Thomas L. C., and Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl. Sun . "Hydrogen bond dynamics in bulk alcohols". United States. doi:10.1063/1.4921574.
@article{osti_22415916,
title = {Hydrogen bond dynamics in bulk alcohols},
author = {Shinokita, Keisuke and Cunha, Ana V. and Jansen, Thomas L. C. and Pshenichnikov, Maxim S., E-mail: Maxim.Pchenitchnikov@RuG.nl},
abstractNote = {Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics–quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid—alcohols—has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.},
doi = {10.1063/1.4921574},
journal = {Journal of Chemical Physics},
number = 21,
volume = 142,
place = {United States},
year = {Sun Jun 07 00:00:00 EDT 2015},
month = {Sun Jun 07 00:00:00 EDT 2015}
}
  • Methods of IR and PMR spectroscopy revealed the presence of an intermolecular hydrogen bond of the type Cl/sub 2/CR-H...O-H in solutions of diasterioisomeric (acetylacetonato)(1-(norbornadien-2-yl)ethanol)rhodium complexes in the proton-donor solvent Cl/sub 2/CRH (R = Cl, H). It was shown that the formation of a hydrogen bond with the solvent raises the strength of the intramolecular hydrogen bond O-H...O(acac) already present in the diasterioisomeric alcohols.
  • Diastereomerically pure secondary alcohols epimerize to mixtures of diasteromers in C{sub 6}H{sub 5}R at 65-90 {degrees}C in the presence of 10 mol% ({eta}{sup 5}C{sub 5}R{sub 5})Re(NO)(PPh{sub 3})(OCH{sub 3}) (1; R = H, Me). The methoxide ligand of 1 first exchanges with the alcohol substrate to give alkoxide complexes {eta}{sup 5}-C{sub 5}R{sub 5})Re(NO)(PPh{sub 3})(OCHR{prime}R{double_prime} is derived from (+)- and (-)-, exo- and endo-borneol. NMR data show that epimerization occurs first at rhenium (ca. 35 {degrees}C) and then at carbon (ca. 65 {degrees}C). Substitution reactions and rate experiments show that PPh{sub 3} initially dissociates from 2 with anchimeric assistance by alkoxide oxygenmore » lone pairs. An intermediate with a trigonal-planar rhenium which can either return to 2 (with epimerization at rhenium) or undergo {beta}-hydride elimination to a ketone hydride complex (leading to epimerization at carbon), is proposed. Accordingly, rates of epimerization at carbon (but not rhenium) are strongly inhibited by added PPh{sub 3}, and show a significant k{sub H}/k{sub D}. 38 refs., 7 figs., 3 tabs.« less
  • The relation between enthalpies of solvation of onium ions, BH/sup +/, by one water molecule, -..delta..H/sup 0//sub 0/ /sub 1/, and by four water molecules, -..delta..H/sup 0//sub 0/ /sub 4/, is constant for most onium ions: ..delta..H/sup 0//sub 0/ /sub 4//..delta..H/sup 0//sub 0/ /sub 1/ is 2.8 +/- 0.1 for all oxonium ions and monoprotonic ammonium and pyridium ions, and 3.1 +/- 0.1 for polyprotonic ammonium ions. These relations, in conjunction with the correlation between ..delta..H/sup 0//sub 0/ /sub 1/ and the proton affinity difference (..delta..PA = PA(B) - PA(H/sub 2/O)), allow the prediction of the total four-molecule specific hydrationmore » energy -..delta..H/sup 0//sub 0/ /sub 4/ for all onium ions within the experimental accuracy of +/-3 kcal mol/sup -1/. The observed (or predicted) fourfold specific relative hydration energies simulate closely the relative bulk hydration enthalpies for most ions. In other words, for most onium ions differential hydration effects are determined by specific hydrogen-bonding interactions. Deviations are useful to identify bulk solvation effects. For example, such deviations indicate attenuated bulk solvation of ions with phenyl substituents. 5 figures, 2 tables.« less
  • Highlights: • Proton transport pathway in bilirubin oxidase was mutated. • Two intermediates in the dioxygen reduction steps were trapped and characterized. • A specific glutamate for dioxygen reduction by multicopper oxidases was identified. - Abstract: The hydrogen bond network leading from bulk water to the trinuclear copper center in bilirubin oxidase is constructed with Glu463 and water molecules to transport protons for the four-electron reduction of dioxygen. Substitutions of Glu463 with Gln or Ala were attributed to virtually complete loss or significant reduction in enzymatic activities due to an inhibition of the proton transfer steps to dioxygen. The singlemore » turnover reaction of the Glu463Gln mutant afforded the highly magnetically interacted intermediate II (native intermediate) with a broad g = 1.96 electron paramagnetic resonance signal detectable at cryogenic temperatures. Reactions of the double mutants, Cys457Ser/Glu463Gln and Cys457Ser/Glu463Ala afforded the intermediate I (peroxide intermediate) because the type I copper center to donate the fourth electron to dioxygen was vacant in addition to the interference of proton transport due to the mutation at Glu463. The intermediate I gave no electron paramagnetic resonance signal, but the type II copper signal became detectable with the decay of the intermediate I. Structural and functional similarities between multicopper oxidases are discussed based on the present mutation at Glu463 in bilirubin oxidase.« less
  • A molecular-level description of the unique properties of hydrogen-bond networks is critical for understanding many fundamental physico-chemical processes in aqueous environments. In this article a novel simulation approach, combining an ab-initio based force field for water with a quantum treatment of the nuclear motion, is applied to investigate hydrogen-bond dynamics in liquid water with a specific focus on the relationship of these dynamics to vibrational spectroscopy. Linear and nonlinear infrared (IR) spectra are calculated for liquid water, HOD in D2O and HOD in H2O and discussed in the context of the results obtained using other approaches that have been employedmore » in studies of water dynamics. A comparison between the calculated spectra and the available experimental data yields an overall good agreement, indicating the accuracy of the present simulation approach in describing the properties of liquid water at ambient conditions. Possible improvements on the representation of the underlying water interactions as well as the treatment of the molecular motion at the quantum-mechanical level are also discussed. This research was supported by the Division of Chemical Sciences, Biosciences and Geosciences, US Department of Energy. Battelle operates the Pacific Northwest National Laboratory for the US Department of Energy.« less