Spectrum of Exfoliable 1D van der Waals Molecular Wires and Their Electronic Properties

Two-dimensional (2D) materials derived from van der Waals (vdW)-bonded layered crystals have been the subject of considerable research focus, but their one-dimensional (1D) analogues have received less attention. These bulk crystals consist of covalently bonded multiatom atomic chains with weak van der Waals bonds between adjacent chains. Using density-functional-theory-based methods, we find the binding energies of several 1D families of materials to be within typical exfoliation ranges possible for 2D materials. In addition, we compute the electronic properties of a variety of insulating, semiconducting, and metallic individual wires and find differences that could enable the identification of and distinction between 1D, 2D, and 3D forms during mechanical exfoliation onto a substrate. We find 1D wires from chemical families of the forms PdBr2, SbSeI, and GePdS3 are likely to be distinguishable from bulk materials via photoluminescence. Like 2D vdW materials, we find some of these 1D vdW materials have the potential to retain their bulk properties down to nearly atomic film thicknesses, including the structural families of HfI3 and PNF2, a useful property for some applications including electronic interconnects. We also study naturally occurring bulk crystalline heterostructures of 1D wires and identify two families that are likely to be exfoliable and identifiable as individual 1D wire subcomponents.