Magnetic organic molecules, such as 3d transition metal phthalocyanines (TMPc), exhibit properties which make them promising candidates for future applications in magnetic data storage or spin-based data processing. Due to their small size, however, TMPc molecules are prone to quantum effects. For example, the interaction of uncompensated molecular spins with conduction electrons of the substrate may lead to the formation of a many-body singlet state, which gives rise to the so-called Kondo effect. Although the Kondo effect of TMPc molecules has been the object of several investigations, a consistent picture to describe under which conditions a Kondo state is formed is still missing. Here, we study the Kondo properties of MnPc on Ag(001) by means of the low-temperature scanning tunneling spectroscopy (LT-STS) measurements. Differential conductance dI/dU spectra reveal a zero-bias peak that is localized on the Mn ion site. Ab initio calculations combined with a many-body treatment of the multiorbital interaction show that the local Hund coupling favors the high-spin configuration on the 3d shell of the central TM atom. Therefore, each orbital gets close to its individual half-filling creating the necessary condition for many of the 3d orbitals to contribute to the observed Kondo resonance. This, however, happens only for the 3dz(2) orbital, whose hybridization to the substrate is much stronger than for the other orbitals thanks to its shape and its orientation.
We present a detailed study of the tautomerization, that is, the switching of hydrogen protons, between different sites in the molecular frame of phthalocyanine (HPc) on a Ag(111) substrate by means of scanning tunneling microscopy (STM) and STM-based pump-and-sample techniques. Our data reveal that the symmetry mismatch between the substrate and the molecular frame lifts the energetic degeneracy of the two HPc tautomers. Their energy difference is so large that only one tautomer can be found in the ground state. Tip-induced tautomerization was triggered at sufficiently high bias voltages. The excited metastable HPc tautomer was found to exhibit a lifetime of at least several days, as derived from the fact that the molecule did not change back to the ground state within experimentally accessible time scales as long as noninvasive tunneling parameters were used to probe the state of the molecule. By the controlled removal of a hydrogen proton from the molecule, a four-level system was created. Pump-and-sample experiments reveal that the lifetime of the metastable positions amounts to seconds only. Current- and bias-dependent studies indicate that the presence of the STM tip modifies the potential barrier, thereby allowing for a controlled tuning of the metastable tautomer's lifetime.
We present a detailed analysis of the energetic landscape of phthalocyanine (H 2 Pc) tautomerization on Ag(111), i.e., the switching of protons between different sites in the molecular frame, which is induced and measured by a low-temperature scanning tunneling microscope (STM). We demonstrate that tautomerization of this molecule is preferentially triggered by the excitation of the N−H stretching mode. Interestingly, a step-like increase of the tautomerization rate is observed at a bias voltage that corresponds to the second harmonic of this vibrational mode, which we attribute to the crossover from quantum tunneling through the tautomerization barrier to an excitation over the barrier. This hypothesis is supported by the analysis of four modified versions of H 2 Pc, produced by single silver atom manipulation and/or deprotonation of the pristine H 2 Pc molecule. Depending on the particular modification, the step-like increase varies strongly, spanning the entire range from further enhancement to almost complete disappearance. We interpret this behavior in terms of different tautomerization barrier heights which for most molecules lies between the first and second harmonics of the N−H stretching mode but which is strongly reduced well below the first harmonic for deprotonated H 2 Pc.
We report the direct observation of a theoretically predicted magnetic ground state in a monolayer Fe on Rh(111), which is referred to as an up-up-down-down (↑↑↓↓) double-row-wise antiferromagnetic spin structure, using spin-polarized scanning tunneling microscopy. This exotic phase, which exists in three orientational domains, is revealed by experiments with magnetic probe tips performed in external magnetic fields. It is shown that a hitherto unconsidered four-spin-three-site beyond-Heisenberg interaction distinctly contributes to the spin coupling of atoms with S≥1 spins. The observation of the ↑↑↓↓ order substantiates the presence of higher-order, in particular, three-site interactions, in thin magnetic films of itinerant magnets.
Molecular electronics where single molecules perform basic functionalities of digital circuits is a fascinating concept that one day may augment or even replace nowadays semiconductor technologies. The tautomerization of molecules, that is, the bistable functional position of hydrogen protons within an organic frame, has recently been intensively discussed as a potential avenue toward nanoscale switches. It has been shown that tautomerization can be triggered locally or nonlocally, that is, by a scanning tunneling microscope (STM) tip positioned directly above or in close vicinity to the molecule. Whereas consensus exists that local switching is caused by inelastic electrons that excite vibrational molecular modes, the detailed processes responsible for nonlocal tautomerization switching and, even more important in the context of this work, methods to control, engineer, and potentially utilize this process are largely unknown. Here, we demonstrate for dehydrogenated HPc molecules on Ag(111) how to controllably decrease or increase the probability of nonlocal, hot electron-induced tautomerization by atom-by-atom designed Ag nanostructures. We show that Ag atom walls act as potential barriers that exponentially damp the hot electron current between the injection point and the molecule, reducing the switching probability by up to 83% for a four-atom wide wall. By placing the molecule in one and the STM tip in the other focal point of an elliptical nanostructure, we could coherently focus hot electrons onto the molecule that led to an almost tripled switching probability. Furthermore, single and double slit experiment based on silver atom structures were used to characterize the spatial extension of hot electron packets. The absence of any detectable interference pattern suggests that the coherence length of the hot electrons that trigger tautomerization processes is rather short. Our results demonstrate that the tautomerization switching of single molecules can remotely be controlled by utilizing suitable nanostructures and may pave the way for designing new tautomerization-based switches.
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