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

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.

Dynamics of CCl₄⁺ prepared by 800 nm strong-field ionization, as studied with X-ray transient absorption spectroscopy (XTAS) and quantum chemical calculations.