The gas phase i.r. spectrum of 4H-pyran-4-one (hereafter called γ-pyrone) has been recorded in the 4000-400 cm −1 region by a Nicolet 7199 FTIR spectrometer and interpreted using a general valence force field calculated quantum mechanically at the ab initio level with a split-valence 4–21 basis. Assignment of certain fundamentals was facilitated by information gained from the i.r. and Raman spectra of the melt and from the i.r. spectrum of the saturated solution in CCl 4. To account for systematic computational errors, the theoretical ab initio force field was scaled using a set of constants derived by the empirical fitting of force fields computed for related molecules to their observed spectra. Either the scale factors derived for a family of open-chain molecules or, better, for benzene could be used to yield a scaled force field which gave unequivocal assignments for γ-pyrone. The method promises to be of general applicability for molecules of this complexity.