Proton transfer in acetaldehyde–water clusters mediated by a single water molecule

Kostko, Oleg; Troy, Tyler P.; Bandyopadhyay, Biswajit; Ahmed, Musahid

doi:10.1039/c6cp04916h

Cited by 17 publications

(13 citation statements)

References 25 publications

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“…We used acetaldehyde-water clusters photoionization to probe the nature of these processes. 88 VUV photoionization of an acetaldehyde-water expansion generated a series of protonated acetaldehyde and protonated acetaldehyde water clusters ( Fig. 11).…”

Section: Proton Transfer Pathways In Acetaldehyde Water Clustersmentioning

confidence: 99%

“…The blue arrow shows the calculated appearance energy for "conventional proton transfer" also marked with a blue circle in the figure, the red arrow shows the calculated "water mediated" proton transfer pathway marked with a red circle in the figure, the black arrow shows the experimental onset. Adapted from ref 88. with permission from the PCCP Owner Societies.…”

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confidence: 99%

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From atoms to aerosols: probing clusters and nanoparticles with synchrotron based mass spectrometry and X-ray spectroscopy

Ahmed

Kostko

2020

Phys. Chem. Chem. Phys.

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Section: Proton Transfer Pathways In Acetaldehyde Water Clustersmentioning

confidence: 99%

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confidence: 99%

From atoms to aerosols: probing clusters and nanoparticles with synchrotron based mass spectrometry and X-ray spectroscopy

Ahmed

Kostko

2020

Phys. Chem. Chem. Phys.

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“…Along with these transformations, the partial charges residing in PhO and DMF change from δ(PhO) ≈ +0.394 and δ(DMF) ≈ +0.052 at the FC structures to δ(PhO) ≈ +0. 15 and δ(DMF) ≈ +0.31 at the optimized structures of B + , whereas the partial charge residing on the "proton" does not change much. These features clearly indicate that the B + isomer corresponds to a full PT structure.…”

Section: Methodsmentioning

confidence: 73%

Ultrafast Protonation of an Amide: Photoionization-Induced Proton Transfer in Phenol-Dimethylformamide Complex Cation

Cheng

2019

J. Phys. Chem. A

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In this study we explore the photoionization-induced proton transfer (PT) dynamics in the hydrogen-bonded complex of phenol (PhOH) and a simple amide, dimethylformamide (DMF). Neutral PhOH-DMF complexes produced in a supersonic expansion are photoionized by femtosecond 1 + 1 resonance-enhanced multiphoton ionization via its S1 state, and the subsequent PT dynamics occurring in the [PhOH-DMF]+ cation is probed by delayed pulses that lead to ion fragmentation. The experiments and density functional theory calculations reveal that the photoionization-induced PT proceeds in two consecutive steps of very different time scales. Upon femtosecond ionization the [PhOH-DMF]+ cation is initially prepared with a non-PT geometry close to that of the dominant neutral complex. The ionic system then rapidly relaxes into a configuration possessing both non-PT and PT characteristics in ∼0.5 ps. This partial-PT intermediate then undergoes a much slower barrier crossing in ∼25 ps to a more stable structure in which PT is more complete. The slow isomerization step not only corresponds to PT but also to a hydrogen-bonding site switching. The present study simulates a scenario of suddenly bringing a strong acid to the close vicinity of an amide to watch how protonation occurs. Our results suggest that the initial protonation of a peptide-like unit in acid-induced protein processes requires a relaxation time of ∼0.5 ps, which must be taken into account in complete descriptions of protein dynamics.

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“…Previous studies proposed that hydrogenation of an organic molecule dimer could be attained with a three-body reaction or intracluster hydrogen transfer of a ternary molecule cluster followed by dissociation into two moieties. ,,, In view of this, we have configured a trimolecular model for the acetone–ethanol system. For the three local-minimum energy isomers, the interactions are plotted by IGM analysis (Figure d) for which the green patterns indicate weak van der Waals interactions, while blue and red refer to stronger stabilizing and destabilizing interactions.…”

Section: Resultsmentioning

confidence: 99%

Acetone Dimer Hydrogenation under Vacuum Ultraviolet: An Intracluster Trimolecular Dissociation Mechanism

Guo

Yang

et al. 2019

J. Phys. Chem. A

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Hydrogenation of organic chemicals is one of the most frequent things that people take for granted in mass spectroscopy; however, it could provide important information on spontaneous or stimulated hydrogen transfer in initiating chemical reactions and in determining the product selectivity and conversion efficiency. Here, we present a study of hydrogenation of acetone via vacuum ultraviolet laser ionization mass spectrometry (VUV-LIMS) and density functional theory (DFT) calculations. It is interestingly found that acetone dimer readily captures a hydrogen to form (C3H6O)2H+ in the presence of alcohols, shedding light on the intracluster hydrogen atom transfer via a trimolecular mechanism. This is well consistent with the DFT calculation results of energetics and reaction kinetics. It is worth noting that, although the hydrogen bond interaction of O–H···O is stronger than that of C–H···O, the hydrogen atom transfer (HAT) tends to proceed from the methyl group of the alcohols to acetone. We fully demonstrate the intracluster HAT reactivity of such a simple system and provide new insights into hydrogen bond interactions and molecular cluster chemistry.

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Proton transfer in acetaldehyde–water clusters mediated by a single water molecule

Abstract: Bridging molecules: a single water molecule enhances the stability of symmetric acetaldehyde water clusters, and acts as a bridge for the transport of a proton between two acetaldehyde molecules.

Cited by 17 publications

References 25 publications

From atoms to aerosols: probing clusters and nanoparticles with synchrotron based mass spectrometry and X-ray spectroscopy

From atoms to aerosols: probing clusters and nanoparticles with synchrotron based mass spectrometry and X-ray spectroscopy

Ultrafast Protonation of an Amide: Photoionization-Induced Proton Transfer in Phenol-Dimethylformamide Complex Cation

Acetone Dimer Hydrogenation under Vacuum Ultraviolet: An Intracluster Trimolecular Dissociation Mechanism

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