Abstract
Noncovalent functionalization provides an effective way to modulate the electronic properties of graphene. Recent experimental work has demonstrated that hybrids of dipolar phototransductive molecules tethered to graphene are reversibly tunable in doping. We have studied the electronic structure characteristics of chromophore/graphene hybrids using dispersion-corrected density functional theory. The Dirac point of noncovalently fiinctionalized graphene shifts upward via cis-trans isomerism, which is attributed to a change in the chromophore's dipole moment. Our calculation results reveal that the experimentally observed reversible doping of graphene is attributed to the change in charge transfer between the light-switchable chromophore and graphene via isomerization. Furthermore, we show that by varying the electric field perpendicular to the supramolecular functionalized graphene, additional tailoring of graphene doping can be accomplished.