Atomic and electronic structure of styrene on Ge(100)

► The possibility of cycloaddition through phenyl ring is completely excluded. ► The spatial orientation of phenyl ring affects the thermodynamic stability. ► Buckling properties of surface Ge dimer affect the interaction of phenyl ring. ► Simulated image for the empty-state successfully confirms the adsorption structure. ► Detailed electronic structures investigated through PDOS analysis explain STM images.