The inelastic tunneling process of electrons between the tip of an STM and the target molecule can lead to various dynamical processes at surfaces such as desorption, lateral hopping, rotation and chemical reaction via the excitation of vibrational modes of adsorbed molecules. The vibrational mode that are excited through the process could be defined through the response of the molecular motion to the applied bias voltage, i.e. action spectrum. Action spectra for hopping motion of cis-2-butene on Pd(110), cleavage of dimethl-disulfide on Cu(111) and hopping motion of cleaved product methyl-thiol show clear thresholds in bias voltage that are equivalent to certain vibration modes, the excitation mechanism of which can be understood by the resonant tunneling mechanism. When the electron jumps into or out of a certain molecular orbital, molecules will temporally go through the negative or positive ion state. And vibration states can be excited, during the relaxation process. Inelastic process that leads to vibrational excitation has attracted much attention of since the conductivity of molecules bridging the electrodes is found to be strongly affected when they are vibrationally excited. Considering that the conduction electrons passes through the electronic state crossing the Fermi level or hopping through the HOMO or LUMO state of the molecule, the electronic state of adsorbate should play a crucial role in the molecular electronics as well as the chemical reactions at surfaces.