The influence of the surface structure on the formation of polyatomic potassium clusters on the surface of a single crystal of tungsten has been found. The cluster composition was identified using time-of-flight mass spectrometric analysis of ions formed during field desorption. The surface structure was changed by build-up the tip by heating in an electric field, in which the hemispherical tip of the tip turns into a polyhedron. It is shown that the build-up leads to a sharp decrease in the number of polyatomic clusters. Only monatomic (K⁺) and diatomic (K₂⁺) ions were detected, whereas on the smoothed tip the number of atoms in clusters reached eight. Most likely, the detected changes are related to the disappearance of steps on the surface. It is assumed that the formation of clusters is facilitated by an increase in the concentration of adsorbed potassium atoms at the edge of the stage due to a reflecting barrier and a potential energy well, as well as the dragging of atoms with a dipole moment into the field inhomogeneity region. Keywords: adsorption, surface diffusion, field desorption, crystal steps, microscopy, mass spectrometry.

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