From high resolution spectroscopy to the modeling of potential energy surfaces

Methods and recipes used to establish potential energy surfaces in condensed molecular phases are discussed. The reliability of calculations is tested by confrontation with spectroscopic measurements in crystals. Optical spectroscopy, in particular, hole burning as a line-narrowing technique, as well as high resolution inelastic neutron scattering (INS), are used to resolve tunneling level structures corresponding to large-amplitude atomic and molecular motions. Rotational tunneling of methyl groups is discussed, and new measurements by INS are presented for crystals that are proposed as suitable candidates for optical studies. Translational tunneling in benzoic acid crystals and the role of promoting modes are reviewed, and new measurements of vibrational spectra by inelastic x-ray scattering are compared with INS and Raman spectra.