While bonding molecular orbitals exhibit constructive interference relative to atomic orbitals, antibonding orbitals show destructive interference. When full localization of occupied orbitals into bonds is possible, bonding and antibonding orbitals exist in 1:1 correspondence with each other. Antibonding orbitals play an important role in chemistry because they are frontier orbitals that determine orbital interactions, as well as much of the response of the bonding orbital to perturbations. In this work, we present an efficient method to construct antibonding orbitals by finding the orbital that yields the maximum opposite spin pair correlation amplitude in second order perturbation theory (AB2) and compare it with other techniques with increasing basis set size. We conclude the AB2 antibonding orbitals are a more robust alternative to the Sano orbitals as initial guesses for valence bond calculations due to having a useful basis set limit. The AB2 orbitals are also useful for efficiently constructing an active space, and they work as good initial guesses for valence excited states. In addition, when combined with the localized occupied orbitals, and relocalized, the result is a set of molecule-adapted minimal basis functions that is built without any reference to atomic orbitals of the free atom. As examples, they are applied to the population analysis of halogenated methane derivatives, H-Be-Cl, and SF6, where they show some advantages relative to good alternative methods.