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

Literature Information

Publication Date 2016-09-05
DOI 10.1039/C6CP04916H
Impact Factor 3.676
Authors

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


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Abstract

Proton transfer in aqueous media is a ubiquitous process, occurring in acid–base chemistry, biology, and in atmospheric photochemistry. Photoionization mass spectrometry coupled with theoretical calculations demonstrate that a relay-type proton transfer mechanism is operational for single-water-molecule-assisted proton transfer between two acetaldehyde molecules in the gas phase. Threshold photoionization of acetaldehyde–water clusters leads to proton transfer between the formyl groups (–CHO) of one acetaldehyde molecule to another, and the subsequent formation of cationic moieties. Density functional theory computations reveal several plausible pathways of proton transfer in mixed cluster cations. Among these pathways, water-mediated proton transfer is energetically favored. Mass spectra and photoionization efficiency curves confirm these theoretical findings and also demonstrate the increased stability of cluster cations where acetaldehyde molecules are symmetrically bonded to the hydronium ion.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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