In molecular spintronics, the spin state of a molecule may be switched on and off by changing the molecular structure. Here, we switch on and off the molecular spin of a double-decker bis(phthalocyaninato)terbium(III) complex (TbPc2) adsorbed on an Au(111) surface by applying an electric current via a scanning tunnelling microscope. The dI/dV curve of the tunnelling current recorded onto a TbPc2 molecule shows a Kondo peak, the origin of which is an unpaired spin of a π-orbital of a phthalocyaninato (Pc) ligand. By applying controlled current pulses, we could rotate the upper Pc ligand in TbPc2, leading to the disappearance and reappearance of the Kondo resonance. The rotation shifts the molecular frontier-orbital energies, quenching the π-electron spin. Reversible switching between two stable ligand orientations by applying a current pulse should make it possible to code information at the single-molecule level.

We demonstrate electron-stimulated migration for carbon monoxide (CO) molecules adsorbed on the Pd(110) surface, which is initiated by the excitation of a high-frequency (HF) vibrational mode (C-O stretching mode) with inelastic tunneling electrons from the tip of scanning tunneling microscopy. The hopping phenomenon, however, cannot be detected for CO/Cu(110), even though the hopping barrier is lower than in the CO/Pd(110) case. A theoretical model, which is based on the anharmonic coupling between low-frequency modes (the hindered-translational mode related to the lateral hopping) and the HF mode combined with electron-hole pair excitation, can explain why the hopping of CO is observed on Pd(110) but not on Cu(110).

The crystal structures of double-decker single molecule magnets (SMM) LnPc(2) (Ln = Tb(III) and Dy(III); Pc = phthalocyanine) and non-SMM YPc(2) were determined by using X-ray diffraction analysis. The compounds are isomorphous to each other. The compounds have metal centers (M = Tb(3+), Dy(3+), and Y(3+)) sandwiched by two Pc ligands via eight isoindole-nitrogen atoms in a square-antiprism fashion. The twist angle between the two Pc ligands is 41.4 degrees. Scanning tunneling microscopy was used to investigate the compounds adsorbed on a Au(111) surface, deposited by using the thermal evaporation in ultrahigh vacuum. Both MPc(2) with eight lobes and MPc with four lobes, which has lost one Pc ligand, were observed. In the scanning tunneling spectroscopy images of TbPc molecules at 4.8 K, a Kondo peak with a Kondo temperature (T(K)) of approximately 250 K was observed near the Fermi level (V = 0 V). On the other hand, DyPc, YPc, and MPc(2) exhibited no Kondo peak. To understand the observed Kondo effect, the energy splitting of sublevels in a crystal field should be taken into consideration. As the next step in our studies on the SMM/Kondo effect in Tb-Pc derivatives, we investigated the electronic transport properties of Ln-Pc molecules as the active layer in top- and bottom-contact thin-film organic field effect transistor devices. Tb-Pc molecule devices exhibit p-type semiconducting properties with a hole mobility (mu(H)) of approximately 10(-4) cm(2) V(-1) s(-1). Interestingly, the Dy-Pc based devices exhibited ambipolar semiconducting properties with an electron mobility (mu(e)) of approximately 10(-5) and a mu(H) of approximately 10(-4) cm(2) V(-1) s(-1). This behavior has important implications for the electronic structure of the molecules.

Controlled chemical reaction of single trans-2-butene molecules on the Pd(110) surface was realized by dosing tunneling electrons from the tip of a scanning tunneling microscope at 4.7 K. The reaction product was identified as a 1,3-butadiene molecule by inelastic electron tunneling spectroscopy. Threshold voltage for the reaction is approximately 365 mV, which coincides with the vibrational excitation of the C-H stretching mode. The reaction was ascertained to be caused by C-H bond dissociation by multiple vibrational excitations of the C-H stretching mode via inelastic electron tunneling process.

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We have investigated the mechanism of the chemical reaction of the benzene molecule adsorbed on Cu(110) surface induced by the injection of tunneling electrons using scanning tunneling microscopy (STM). With the dosing of tunneling electrons of the energy 2-5 eV from the STM tip to the molecule, we have detected the increase of the height of the benzene molecule by 40% in the STM image and the appearance of the vibration feature of the nu(C-H) mode in the inelastic tunneling spectroscopy (IETS) spectrum. It can be understood with a model in which the dissociation of C-H bonds occurs in a benzene molecule that induces a bonding geometry change from flat-lying to up-right configuration, which follows the story of the report of Lauhon and Ho on the STM-induced change of benzene on the Cu(100) surface. [L. J. Lauhon and W. Ho, J. Phys. Chem. A 104, 2463 (2000)]. The reaction probability shows a sharp rise at the sample bias voltage at 2.4 V, which saturates at 3.0 V, which is followed by another sharp rise at the voltage of 4.3 V. No increase of the reaction yield is observed for the negative sample voltage up to 5 eV. In the case of a fully deuterated benzene molecule, it shows the onset at the same energy of 2.4 eV, but the reaction probability is 10(3) smaller than the case of the normal benzene molecule. We propose a model in which the dehydrogenation of the benzene molecule is induced by the formation of the temporal negative ion due to the trapping of the electrons at the unoccupied resonant states formed by the pi orbitals. The existence of the resonant level close to the Fermi level ( approximately 2.4 eV) and multiple levels in less than approximately 5 eV from the Fermi level, indicates a fairly strong interaction of the Cu-pi(*) state of the benzene molecule. We estimated that the large isotope effect of approximately 10(3) can be accounted for with the Menzel-Gomer-Redhead (MGR) model with an assumption of a shallow potential curve for the excited state.

Inelastically tunneled electrons from a scanning tunneling microscope (STM) were used to induce vibrationally mediated motion of a single cis-2-butene molecule among four equivalent orientations on Pd(110) at 4.8 K. The action spectrum obtained from the motion clearly detects more vibrational modes than inelastic electron tunneling spectroscopy with a STM. We demonstrate the usefulness of the action spectroscopy as a novel single molecule vibrational spectroscopic method. We also discuss its selection rules in terms of resonance tunneling.

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