Core-Level Spectroscopy Decodes Bond-Alternation Dynamics of Cyclo[18]Carbon

Abstract

The advent of X-ray free-electron lasers and high-harmonic generation has made time-resolved X-ray spectroscopy a powerful tool for probing local atomic environments, yet whether localized core excitations can report on global collective distortions remains open. Cyclo[18]carbon (C$_{18}$), with its polyynic ground state (D$_\text{9h}$) and cumulenic transition state (D$_\text{18h}$), provides an ideal model to address this long-standing issue in bond-length alternation (BLA) dynamics. Mapping two-dimensional potential energy surfaces by first-principles simulations, we find that core ionization symmetrizes the ground-state double-well potential along the BLA coordinate. Our calculated X-ray spectra reveal remarkable sensitivity to bond-length variations: C1s ionization potentials vary by up to 2.4~eV across the BLA coordinate (1.1--1.4~\AA), with a 0.9~eV variation for minima predicted by different functionals, while NEXAFS $\pi^*$ peaks shift by up to 4~eV across the same coordinate. These predicted signatures provide a quantitative spectroscopy--structure dictionary for decoding transient structures in future ultrafast X-ray experiments and monitoring bond-alternation dynamics in real time.