Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

The Journal of Chemical Physics
Zeb C KramerRex T Skodje

Abstract

The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.

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Citations

Jun 26, 2012·Journal of the American Chemical Society·Marilia T C Martins-CostaManuel F Ruiz-Lopez
Nov 4, 2016·The Journal of Physical Chemistry. a·Jonathan R Church, Rex T Skodje
May 17, 2017·The Journal of Physical Chemistry. a·Rebecca J RapfVeronica Vaida
May 18, 2017·The Journal of Physical Chemistry. a·Manoj KumarJoseph S Francisco
Nov 28, 2013·Physical Chemistry Chemical Physics : PCCP·V Vaida, D J Donaldson
Jan 22, 2021·The Journal of Physical Chemistry. a·Keaten J KappesVeronica Vaida
Jul 1, 2021·Physical Chemistry Chemical Physics : PCCP·Hung-Yang JianLi-Kang Chu
May 15, 2015·The Journal of Physical Chemistry. a·Satoshi Inaba
Aug 6, 2019·The Journal of Physical Chemistry. a·Michael R AlvesVicki H Grassian
May 9, 2013·The Journal of Physical Chemistry. a·Srihari Keshavamurthy
Jun 30, 2018·The Journal of Physical Chemistry. a·Arathala ParandamanAmitabha Sinha
Dec 31, 2020·The Journal of Physical Chemistry. a·Benjamin N FrandsenVeronica Vaida

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