Metallic Organometallic and Semiconducting Covalent Phases of Free-Standing $γ$-Graphdiyne Molecular Wires

Abstract

One-dimensional carbon allotropes combining sp and sp2 hybridizations provide a versatile platform for atomically precise quantum wires with tunable electronic, vibrational, and mechanical responses. Recent on-surface synthesis has realized the $γ$-graphdiyne molecular wire on Au(100) in two interconvertible phases sharing an identical aromatic backbone but distinct linkage chemistry: an organometallic intermediate with C-Au-C bridges and a fully covalent product with diacetylenic linkages. While experimental techniques characterize the on-surface periodicity and C$\equiv$C Raman signatures, the intrinsic properties of the free-standing wires remain inaccessible. Here, we address this gap using hybrid-functional first-principles calculations. The covalent phase is a semiconductor with a direct band gap of 2.02 eV, a polyynic bond-length alternation of 0.117 Å, and a chain periodicity reproducing experiment within -0.5%. Conversely, the organometallic phase exhibits partial cumulenization and 1D metallic behavior, with spin channels crossing the Fermi level. Both isolated polymers demonstrate dynamic stability with Young's moduli of 995 nN and 861 nN, respectively, where the C-Au-C bridge acts as a soft link absorbing 9.2% of axial deformation at +6% macroscopic strain. Species-resolved vibrational analysis identifies an effective-conjugation-coordinate band at 1408 cm$^{-1}$ for the covalent phase and Au-projected modes below 400 cm$^{-1}$ for the intermediate, offering diagnostic fingerprints for phase discrimination during thermal or chemical conversion.