title: Conjugated Molecules Described by a One-Dimensional Dirac Equation.
abstract: Starting from the Hückel Hamiltonian of conjugated hydrocarbon chains (ethylene, allyl radical, butadiene, pentadienyl radical, hexatriene, etc.), we perform a simple unitary transformation and obtain a Dirac matrix Hamiltonian. Thus already small molecules are described exactly in terms of a discrete Dirac equation, the continuum limit of which yields a one-dimensional Dirac Hamiltonian. Augmenting this Hamiltonian with specially adapted boundary conditions, we find that all the orbitals of the unsaturated hydrocarbon chains are reproduced by the continuous Dirac equation. However, only orbital energies close to the highest occupied molecular orbital/lowest unoccupied molecular orbital energy are accurately predicted by the Dirac equation. Since it is known that a continuous Dirac equation describes the electronic structure of graphene around the Fermi energy, our findings answer the question to what extent this peculiar electronic structure is already developed in small molecules containing a delocalized π-electron system. We illustrate how the electronic structure of small polyenes carries over to a certain class of rectangular graphene sheets and eventually to graphene itself. Thus the peculiar electronic structure of graphene extends to a large degree to the smallest unsaturated molecule (ethylene).
authors.affiliation: Département de Chimie, Université de Montréal, C. P. 6128 Succursale A, Montréal, Québec H3C 3J7, Canada.
authors.forename: Matthias
authors.initials: M
authors.lastname: Ernzerhof
authors.affiliation: Département de Chimie, Université de Montréal, C. P. 6128 Succursale A, Montréal, Québec H3C 3J7, Canada.
authors.forename: Francois
authors.initials: F
authors.lastname: Goyer