A dramatic difference between the electron-driven dissociation of alcohols and ethers and its relation to Rydberg states

Physical Chemistry Chemical Physics : PCCP
Bogdan C Ibănescu, Michael Allan

Abstract

A difference was observed in the reactivity of alcohols and ethers toward free electrons. Whereas the lowest core-excited state of the negative ion-a 2(n,3s2) Feshbach resonance-of the alcohols readily dissociates by losing a hydrogen atom, ethers show no observable signal from this resonance. This difference in reactivity has a parallel in the anomalous shapes and energies of the parent states of the Feshbach resonances, the 1(n,3s) Rydberg states of the neutral alcohols. We explained this anomaly using potential surfaces of the alcohols and ethers calculated using the TD-DFT method as a function of the dissociation coordinate. The lowest excited state of alcohols was found to be repulsive, whereas a barrier to dissociation was found in the ethers. Rydberg-valence mixing and avoided crossings are decisive in determining the shapes of the potential surfaces. It is concluded that the reactivities of alcohols and ethers toward free electrons are rationalized by assuming that the potential surfaces of the daughter Feshbach resonances closely follow those of the parent Rydberg states, i.e., the lowest Feshbach resonance is repulsive, but a barrier occurs in ethers. The potential surfaces of both the Rydberg states and the Feshbach ...Continue Reading

References

Jun 5, 2007·The Journal of Physical Chemistry. a·Ilaria Ciofini, Carlo Adamo
Jul 7, 2007·Physical Chemistry Chemical Physics : PCCP·Bogdan C IbănescuMichael Allan
Oct 19, 2007·The Journal of Physical Chemistry. a·Andrzej L Sobolewski, Wolfgang Domcke
Oct 24, 2007·The Journal of Chemical Physics·Stefan Grimme, Frank Neese
Mar 11, 2008·Physical Chemistry Chemical Physics : PCCP·Bogdan C IbănescuMichael Allan

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Citations

Jun 4, 2010·Physical Chemistry Chemical Physics : PCCP·Y YildirimL Sanche
Apr 15, 2014·The Journal of Chemical Physics·Xinglan LuoLéon Sanche
Jan 13, 2015·Annual Review of Physical Chemistry·Elahe AlizadehLéon Sanche
Jun 13, 2013·The Journal of Physical Chemistry. a·Vanusa Bezerra Pachêco, Puspitapallab Chaudhuri
Jan 10, 2014·The Journal of Physical Chemistry. a·D AlmeidaP Limão-Vieira
Dec 3, 2009·Physical Chemistry Chemical Physics : PCCP·Bogdan C Ibănescu, Michael Allan
Mar 9, 2018·Beilstein Journal of Nanotechnology·Michal LackoŠtefan Matejčík
May 10, 2020·The Journal of Chemical Physics·M ZawadzkiJ Kopyra
Feb 2, 2010·Physical Chemistry Chemical Physics : PCCP·Michael N R AshfoldAlan G Sage
Oct 31, 2020·The Journal of Physical Chemistry. a·Mateusz ZawadzkiJaroslav Kočišek
Dec 5, 2013·Journal of the American Chemical Society·Chenbiao XuXueming Yang

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