Continuous Topological Transition and Bandgap Tuning in Ethynylene-Linked Acene π-Conjugated Polymers through Mechanical Strain.

Abstract

By variation of the chemical repeat units of conjugated polymers, only discrete tuning of essential physical parameters is possible. A unique property of a class of π-conjugated polymers, where polycyclic aromatic hydrocarbons are linked via ethynylene linkers, is their topological aromatic to quinoid phase transition discovered recently by Cirera et al. and González-Herrero et al., which is controllable in discrete steps by chemical variations. We have discovered by means of density functional theory computations that such a phase transition can be achieved by applying continuous variations of longitudinal strain, allowing us to tune the bond length alternation and bandgap. At a specific strain value, the bandgap becomes zero due to an orbital level crossing between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Our hypothesis provides a perspective on the design of organic electronic materials and provides a novel insight into the properties of a continuous phase transition in topological semiconducting polymers.