The energy loss of Ne 1 ions with keV energies scattered under grazing incidence from a LiF(001) surface is studied with a time-of-flight technique. Since charge exchange in front of the wide-bandgap insulator is widely suppressed, the energy loss of slow ions moving in front of the solid can be investigated under specific interaction conditions. From the theoretical analysis of data we find evidence for an energy loss mechanism based on the excitations of optical phonons in the insulator. PACS numbers: 79.20.Rf, 34.50.Bw When atomic particles collide with solid matter, excitations in projectile and target give rise to stopping phenomena. For slow ions electronic excitations, charge exchange, and binary collisions with target atoms ("nuclear stopping") clearly dominate the dissipation of energy in ion-solid collisions [1]. Whereas nuclear stopping can be described in a straightforward manner, the treatment of electronic processes is a more intricate subject. For metal targets, considerable progress in the theoretical description of electronic stopping has been achieved over about the last decade [2]. Excitation of electron-hole pairs is the primary mechanism for electronic stopping of slow ions, i.e., projectiles with velocities y ø y 0 (y 0 Bohr velocity 1 atomic unit 1 a.u.). In the framework of corresponding theories, characteristic features for the stopping of slow ions by metal targets, e.g., a linear dependence of the stopping power 2dE͞dx on the projectile velocity y or oscillations of 2dE͞dx with atomic number of the projectiles Z 1 ("Z 1 oscillations"), can be described on a quantitative level [3].An interesting aspect concerning the stopping of slow ions is the role of collective excitations. Whereas at higher projectile velocities excitations of plasmons (typical energieshv ഠ 10 eV) result in substantial contributions to energy loss [2,4], these excitations will have small effects on the stopping of slow ions [5]. From a theoretical analysis Echenique and Howie [6] concluded that at low velocities only collective excitations at low frequencies, as, e.g., optical phonons in ionic insulators (typical energieshv ph ഠ some 10 meV [7]) will contribute. In order to observe this mode of stopping, other sources for dissipation of energy of slow ions (single excitations, charge exchange, nuclear stopping) has to be reduced. To our knowledge, corresponding experimental work has not been reported so far.In this Letter, we report on joint experimental and theoretical studies where unequivocal evidence for the stopping of slow ions in front of an ionic insulator by excitation of optical phonons is obtained. We will demonstrate that under specific experimental conditions for collisions of ions with solid matter, the excitations of phonons clearly dominate the stopping process. Our experiments are performed with Ne 1 ions at keV energies ͑y # 0.1 a.u.͒ scattered under grazing angles of incidence (typically F in ഠ 1 ± ) from a clean and flat LiF(001) surface. Under these scattering conditions ("planar surface chann...