Role of tip size, orientation, and structural relaxations in first-principles studies of magnetic exchange force microscopy and spin-polarized scanning tunneling microscopy

Using first-principles calculations based on density functional theory (DFT), we investigate the exchange interaction between a magnetic tip and a magnetic sample which is detected in magnetic exchange force microscopy (MExFM) and also occurs in spin-polarized scanning tunneling microscopy (SP-STM) experiments. As a model tip-sample system, we choose Fe tips and one monolayer Fe on W(001) which exhibits a checkerboard antiferromagnetic structure and has been previously studied with both SP-STM and MExFM. We calculate the exchange forces and energies as a function of tip-sample distance using different tip models ranging from single Fe atoms to Fe pyramids consisting of up to 14 atoms. We find that modelling the tip by a single Fe atom leads to qualitatively different tip-sample interactions than using clusters consisting of several atoms. Increasing the cluster size changes the calculated forces quantitatively enhancing the detectable exchange forces. Rotating the tip with respect to the surface unit cell has only a small influence on the tip-sample forces. Interestingly, the exchange forces on the tip atoms in the nearest and next-nearest layers from the apex atom are non-negligible and can be opposite to that on the apex atom for a small tip. In addition, the apex atom interacts not only with the surface atoms underneath but also with nearest-neighbors in the surface. We find that structural relaxations of tip and sample due to their interaction depend sensitively on the magnetic alignment of the two systems. As a result the onset of significant exchange forces is shifted towards larger tip-sample separations which facilitates their measurement in MExFM. At small tip-sample separations, structural relaxations of tip apex and surface atoms can either enhance or reduce the magnetic contrast measured in SP-STMComment: 14 pages, 13 figure

Role of the van der Waals interactions on the bonding mechanism of pyridine on Cu(110) and Ag(110) surfaces: A first-principles study

We performed density-functional calculations aimed to investigate the adsorption mechanism of a single pyridine (C5H5N) molecule on Cu(110) and Ag(110) surfaces. Our ab initio simulations show that, in the ground state, the pyridine molecule adsorbs with its molecular plane perpendicular to these substrates and is oriented along the [001] direction. In this case, the bonding mechanism involves a sigma bond through the lone-pair electrons of the nitrogen atom. When the heterocyclic ring is parallel to the surface, the bonding takes place via pi-like molecular orbitals. However, depending on the position of the N atom on the surface, the planar adsorption configuration can relax to a perpendicular geometry. The role of the long-range van der Waals interactions on the adsorption geometries and energies was analyzed in the framework of the semiempirical method proposed by Grimme [J. Comput. Chem. 27, 1787 (2006)]. We demonstrate that these dispersion effects are very important for geometry and electronic structure of flat adsorption configurations

Interface-engineered templates for molecular spin memory devices

The use of molecular spin state as a quantum of information for storage, sensing and computing has generated considerable interest in the context of next-generation data storage and communication devices(1, 2), opening avenues for developing multifunctional molecular spintronics(3). Such ideas have been researched extensively, using single-molecule magnets(4, 5) and molecules with a metal ion(6) or nitrogen vacancy(7) as localized spin-carrying centres for storage and for realizing logic operations(8). However, the electronic coupling between the spin centres of these molecules is rather weak, which makes construction of quantum memory registers a challenging task(9). In this regard, delocalized carbon-based radical species with unpaired spin, such as phenalenyl(10), have shown promise. These phenalenyl moieties, which can be regarded as graphene fragments, are formed by the fusion of three benzene rings and belong to the class of open-shell systems. The spin structure of these molecules responds to external stimuli(11, 12) (such as light, and electric and magnetic fields), which provides novel schemes for performing spin memory and logic operations. Here we construct a molecular device using such molecules as templates to engineer interfacial spin transfer resulting from hybridization and magnetic exchange interaction with the surface of a ferromagnet ; the device shows an unexpected interfacial magnetoresistance of more than 20 per cent near room temperature. Moreover, we successfully demonstrate the formation of a nanoscale magnetic molecule with a well-defined magnetic hysteresis on ferromagnetic surfaces. Owing to strong magnetic coupling with the ferromagnet, such independent switching of an adsorbed magnetic molecule has been unsuccessful with single-molecule magnets(13). Our findings suggest the use of chemically amenable phenalenyl-based molecules as a viable and scalable platform for building molecular-scale quantum spin memory and processors for technological development