Jahn-Teller Distortion and Dissociation of CCl${}_4^{+}$ by Transient X-ray Spectroscopy Simultaneously at the Carbon K- and Chlorine L-Edge

Abstract

X-ray Transient Absorption Spectroscopy (XTAS) and theoretical calculations are used to study CCl${}_4^{+}$ 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, CCl${}_4^{+}$ undergoes symmetry breaking driven by Jahn-Teller distortion away from the initial tetrahedral structure (T${}_d$) in 6$\pm$2 fs. The resultant symmetry-broken covalently bonded form subsequently separates to a noncovalently bound complex between CCl${}_3^{+}$ and Cl over 90$\pm$10 fs, which is again predicted by theory. Finally, after more than 800 fs, L-edge signals for atomic Cl are observed, indicating dissociation to free CCl${}_3^{+}$ and Cl. The results for Jahn-Teller distortion to the symmetry-broken form of CCl${}_4^{+}$ and formation of the Cl -- CCl${}_3^{+}$ complex characterize previously unobserved new species along the route to dissociation.

References in corpus (3)

• Orbital Optimized Density Functional Theory for Electronic Excited States
• Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining sub eV Error from a Restricted Open-Shell Kohn-Sham Approach
• Accurate prediction of core-level spectra of radicals at density functional theory cost via square gradient minimization and recoupling of mixed configurations

Cited by in corpus (7)

• Femtosecond Symmetry Breaking and Coherent Relaxation of Methane Cations at the Carbon K-Edge
• A benchmark study of core-excited states of organic molecules computed with the generalized active space driven similarity renormalization group
• Ultrafast X-ray Spectroscopy of Intersystem Crossing in Hexafluoroacetylacetone: Chromophore Photophysics and Spectral Changes in the Face of Electron Withdrawing Groups
• Generalization of one-center non orthogonal configuration interaction singles to open shell singlet reference states: Theory and application to valence-core pump-probe states in acetylacetone
• Core-excited states of SF${}_6$ probed with soft X-ray femtosecond transient absorption of vibrational wavepackets
• Measurement of Coherent Vibrational Dynamics with X-ray Transient Absorption Spectroscopy Simultaneously at the Carbon K- and Chlorine L${}_{2,3}$- Edges
• Locating Ab Initio Transition States via Approximate Geodesics on Machine Learned Potential Energy Surfaces