Jahn-Teller distortion and dissociation of CCl4+ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge

Andrew D. Ross; Diptarka Hait; Valeriu Scutelnic; Eric A. Haugen; Enrico Ridente; Mikias B. Balkew; Daniel M. Neumark; Martin Head-Gordon; Stephen R. Leone

doi:10.1039/D2SC02402K

Jahn-Teller distortion and dissociation of CCl₄⁺ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge†

Andrew D. Ross,‡^ab Diptarka Hait,

‡^ab Valeriu Scutelnic,

^ab Eric A. Haugen,

^ab Enrico Ridente,^a Mikias B. Balkew,

^ca Daniel M. Neumark,

^ab Martin Head-Gordon

^ab and Stephen R. Leone

*^abd

Author affiliations

* Corresponding authors

^a Department of Chemistry, University of California, Berkeley, CA, USA
E-mail: diptarka@stanford.edu

^b Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

^c School of Physics, Georgia Institute of Technology, Atlanta, GA, USA

^d Department of Physics, University of California, Berkeley, CA, USA

Abstract

X-ray Transient Absorption Spectroscopy (XTAS) and theoretical calculations are used to study CCl₄⁺ prepared by 800 nm strong-field ionization. XTAS simultaneously probes atoms at the carbon K-edge (280–300 eV) and chlorine L-edge (195–220 eV). Comparison of experiment to X-ray spectra computed by orbital-optimized density functional theory (OO-DFT) indicates that after ionization, CCl₄⁺ undergoes symmetry breaking driven by Jahn–Teller distortion away from the initial tetrahedral structure (T_d) in 6 ± 2 fs. The resultant symmetry-broken covalently bonded form subsequently separates to a noncovalently bound complex between CCl₃⁺ and Cl over 90 ± 10 fs, which is again predicted by theory. Finally, after more than 800 fs, L-edge signals for atomic Cl are observed, indicating dissociation to free CCl₃⁺ and Cl. The results for Jahn–Teller distortion to the symmetry-broken form of CCl₄⁺ and formation of the Cl–CCl⁺₃ complex characterize previously unobserved new species along the route to dissociation.

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DOI: https://doi.org/10.1039/D2SC02402K
Article type: Edge Article
Submitted: 28 Apr 2022
Accepted: 18 Jul 2022
First published: 19 Jul 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2022,13, 9310-9320

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Jahn-Teller distortion and dissociation of CCl₄⁺ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge

A. D. Ross, D. Hait, V. Scutelnic, E. A. Haugen, E. Ridente, M. B. Balkew, D. M. Neumark, M. Head-Gordon and S. R. Leone, Chem. Sci., 2022, 13, 9310 DOI: 10.1039/D2SC02402K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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Jahn-Teller distortion and dissociation of CCl₄⁺ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge†

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Jahn-Teller distortion and dissociation of CCl₄⁺ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge

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