Mapping Transient Structures of Cyclo[18]Carbon by Computational X-Ray Spectra

Abstract

The structure of cyclo[18]carbon (C$_{18}$), whether in its polyynic form with bond length alternation (BLA) or its cumulenic form without BLA, has long fascinated researchers, even prior to its successful synthesis. Recent studies suggest a polyynic ground state and a cumulenic transient state; however, the dynamics remain unclear and lack experimental validation. This study presents a first-principles theoretical investigation of the bond lengths ($R_1$ and $R_2$) dependent two-dimensional potential energy surfaces (PESs) of C$_{18}$, concentrating on the ground state and carbon 1s ionized and excited states. We examine the potential of X-ray spectra for determining bond lengths and monitoring transient structures, finding that both X-ray photoelectron (XPS) and absorption (XAS) spectra are sensitive to these variations. Utilizing a library of ground-state minimum structures optimized with 14 different functionals, we observe that core binding energies predicted with the $\omega$B97XD functional can vary by 0.9 eV (290.3--291.2 eV). Unlike the ground state PES, which predicts minima at alternating bond lengths, the C1s ionized state PES predicts minima with equivalent bond lengths. In the XAS spectra, peaks 1$\pi^*$ and 2$\pi^*$ show a redshift with increasing bond lengths along the line where $R_1 = R_2$. Additionally, increasing $R_2$ (with $R_1$ fixed) results in an initial redshift followed by a blueshift, minimizing at $R_1 = R_2$. Major peaks indicate that both 1$\pi^*$ and 2$\pi^*$ arise from two channels: C1s$\rightarrow\pi^*_{z}$ (out-of-plane) and C1s$\rightarrow\pi^*_{xy}$ (in-plane) transitions at coinciding energies.