Quantum Monte Carlo Simulations of the Vibrational Wavefunction of the Aromatic Cyclo[10]carbon Using a Full Dimensional Permutationally Invariant Potential Energy Surface.

Abstract

New experimental measurements [Sun et al., Nature 2023, 623, 972] of the cyclic C10 reveal a cumulenic pentagon-like D5h structure at ∼5 K. However, the long-standing presumption that a large zero-point vibrational energy combined with an extremely flat D5h ↔ D10h ↔ D5h isomerization pathway washes out the pentagonal D5h structure and yields a symmetric D10h decagon remains at odds with the experiment. We resolve this issue with our fitting approach based on a bond-order charge-density matrix expressed in permutationally invariant polynomials. We train the model on τHCTH/cc-pVQZ data morphed to reproduce a relativistic all-electron CCSDT(Q)/CBS D5h-D10h potential energy barrier (benchmarked previously by others). Large scale diffusion Monte Carlo simulations in full dimensionality show that the vibrational ground state of C10 has compositional character of more than 96% D5h, fully reflecting the experimental imaging data. Quantum mechanical variational calculations in 1-D further suggest persistence of the D5h symmetry structure at higher temperatures.