Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

The Journal of Chemical Physics
Bruce L YoderRuth Signorell

Abstract

We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME - h6)n and (DME - d6)n n = 1 and 2, in the 9-14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C-H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH3OHCH3 (+) by the loss of CH2OCH3 with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME - h6)2 and deuterated (DME - d6)2, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME - d6 monomer.

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Citations

May 16, 2015·The Journal of Physical Chemistry. a·Min XieAsuka Fujii
Mar 17, 2016·Annual Review of Physical Chemistry·Oleg KostkoMusahid Ahmed
Aug 13, 2015·Physical Chemistry Chemical Physics : PCCP·Andras BodiJames P Kercher
May 4, 2016·Physical Chemistry Chemical Physics : PCCP·Yanmin TaoLiusi Sheng
Jul 15, 2016·Physical Chemistry Chemical Physics : PCCP·Demian Marchione, Martin R S McCoustra
Jul 13, 2016·Physical Chemistry Chemical Physics : PCCP·Jan Chalabala, Petr Slavíček
Aug 25, 2015·Physical Chemistry Chemical Physics : PCCP·Masato MoritaKaito Takahashi
Mar 25, 2017·Physical Review Letters·Sebastian HartwegRuth Signorell
Nov 30, 2018·Physical Chemistry Chemical Physics : PCCP·Jan PoštulkaJaroslav Kočišek
Mar 3, 2017·The Journal of Chemical Physics·Piyali ChatterjeeTapas Chakraborty
Nov 26, 2019·The Journal of Physical Chemistry. a·Mengdi GuoZhixun Luo
Sep 14, 2017·The Journal of Physical Chemistry Letters·Tomoya EndoAsuka Fujii

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