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We show that two seemingly unrelated problems - the trapping of an atom in an optical superlattice (OSL) and the libration of a planar rigid rotor in combined electric and optical fields - have isomorphic Hamiltonians. Formed by the interference of optical lattices whose spatial periods differ by a factor of two, OSL gives rise to a periodic potential that acts on atomic translation via the AC Stark effect. The latter system, also known as the generalized planar pendulum (GPP), is realized by subjecting a planar rigid rotor to combined orienting and aligning interactions due to the coupling of the rotor's permanent and induced electric dipole moments with the combined fields. The mapping makes it possible to establish correspondence between concepts developed for the two eigenproblems individually, such as localization on the one hand and orientation/alignment on the other. Moreover, since the GPP problem is conditionally quasi-exactly solvable (C-QES), so is atomic trapping in an OSL. We make use of both the correspondence and the quasi-exact solvability to treat ultracold atoms in an optical superlattice as a semifinite-gap system. The band structure of this system follows from the eigenenergies and their genuine and avoided crossings obtained previously for the GPP as analytic solutions of the Whittaker-Hill equation. These solutions characterize both the squeezing and the tunneling of atoms trapped in an optical superlattice and pave the way to unraveling their dynamics in analytic form.