Issue 48, 2021

Infrared spectra of carbocations and CH4+ in helium

Abstract

Infrared (IR) spectra of several hydrocarbon cations are reported, namely CH3+, CH4+, CH5+, CH5+(CH4) and C2H5+. The spectra were generated from weakly-bound helium-cation complexes formed by electron ionization of helium nanodroplets doped with a neutral hydrocarbon precursor. Spectroscopic transitions were registered by photoexcitation of the complexes coupled with mass spectrometric detection of the bare ions. For CH3+, we provide evidence showing that the helium-bound complexes contain 10–20 helium atoms (on average) and have a rotational temperature of ∼5 K. We show that this technique is well-suited to the study of highly symmetric or fluxional ionic species, as these intrinsic properties are preserved in the helium environment. This is in contrast to conventional tagging methods that use a single atom or molecule, which can change the point group or rigidity of the core ion and therefore the spectral profile. We demonstrate this for the highly fluxional molecular ion CH5+, whose spectrum in the current study matches that of the gas phase ion, whereas the fluxionality is lost when a methane tag is added. Finally, we present the first IR spectrum of methane cation, CH4+. The spectrum of this fundamental organic ion shows CH stretching bands consistent with a non-tetrahedral structure, a consequence of Jahn–Teller distortion.

Graphical abstract: Infrared spectra of carbocations and CH4+ in helium

Supplementary files

Article information

Article type
Paper
Submitted
09 Jul 2021
Accepted
24 Nov 2021
First published
26 Nov 2021

Phys. Chem. Chem. Phys., 2021,23, 27449-27459

Infrared spectra of carbocations and CH4+ in helium

J. A. Davies, S. Yang and A. M. Ellis, Phys. Chem. Chem. Phys., 2021, 23, 27449 DOI: 10.1039/D1CP03138D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements