We examine the quantum tunneling of magnetization in molecular spin in weak interaction with a bath subject to Redfield master equation. By designing a microscopic model for a multilevel spin system using only a generic Hamiltonian and applying stationary approximation for excited doublets/singlets, we derive a key equation of motion for the quantum tunneling of magnetization process which is applicable in the whole temperature domain. From this equation, we find that in general three tunneling rates are needed to accurately describe the quantum tunneling process. More importantly, behavior of the quantum tunneling in the intermediate temperature domain where there exists a transition between incoherent and coherent quantum tunneling is also unraveled for the first time. Limiting cases at low and high temperature and/or low magnetic field are also worked out where some popular well-known results are reproduced. Last but not least, a new interpretation of the quantum tunneling of magnetization is proposed where we reveal the similarity between this relaxation process with a driven damped harmonic oscillator.
Single-molecule magnets facilitate the study of quantum tunneling of magnetization at the mesoscopic level. The spin-parity effect is among the fundamental predictions that have yet to be clearly observed. It is predicted that quantum tunneling is suppressed at zero transverse field if the total spin of the magnetic system is half-integer (Kramers degeneracy) but is allowed in integer spin systems. The Landau-Zener method is used to measure the tunnel splitting as a function of transverse field. Spin-parity dependent tunneling is established by comparing the transverse field dependence of the …
Magnetization versus field measurements were performed on single crystals of [(Pc)2TbIII0.02YIII0.98]^TBA+ and [(Pc)2DyIII0.02YIII0.98]^TBA+ (Pc: phthalocyaninato, TBA: tetrabutylammonium) at 0.04 K. The [(Pc)2TbIII] complex, the first lanthanide single-molecule magnet, exhibited clear staircase-like structures, which are assigned to resonant quantum tunneling between entangled states of the electron and nuclear spin systems.
We have performed single-atom magnetization curve (SAMC) measurements and inelastic scanning tunneling spectroscopy (ISTS) on individual Fe atoms on a Cu(111) surface. The SAMCs show a broad distribution of magnetic moments with $\unit[3.5]{μ_{\rm B}}$ being the mean value. ISTS reveals a magnetization excitation with a lifetime of $\unit[200]{fsec}$ which decreases by a factor of two upon application of a magnetic field of $\unit[12]{T}$. The experimental observations are quantitatively explained by the decay of the magnetization excitation into Stoner modes of the itinerant electron system a…
The first measurements of magnetization hysteresis loops on diluted single crystal of [(Pc)2Ho]-TBA+ (Pc: phthalocyaninato, TBA: tetrabutylammonium) in the subkelvin temperature range are reported. Characteristic staircase-like structure was observed, indicating the occurrence of the quantum tunneling of magnetization (QTM), which is a characteristic feature of SMMs. The quantum process in the new lanthanide SMMs is due to resonant quantum tunneling between entangled states of the electronic and nuclear spin systems, which is an essentially different mechanism from those of the known transitio…
We predict that the Curie temperature of a ferromagnetic resonant tunneling diode will decrease abruptly, by approximately a factor of two, when the downstream chemical potential falls below the quantum well resonance energy. This property follows from elementary quantum transport theory notions combined with a mean field description of diluted magnetic semiconductor ferromagnetism. We illustrate this effect by solving coupled non-equilibrium Green's function, magnetic mean-field, and electrostatic Poisson equations self-consistently to predict the bias voltage and temperature dependence of th…
We present magnetization measurements on the single molecule magnet Mn6, revealing various tunnel transitions inconsistent with a giant-spin description. We propose a dimeric model of the molecule with two coupled spins S=6, which involves crystal-field anisotropy, symmetric Heisenberg exchange interaction, and antisymmetric Dzyaloshinskii-Moriya exchange interaction. We show that this simplified model of the molecule explains the experimentally observed tunnel transitions and that the antisymmetric exchange interaction between the spins gives rise to tunneling processes between spin states be…
The effects of the spin-orbit interaction on the tunneling magnetoresistance of ferromagnet/semiconductor/normal metal tunnel junctions are investigated. Analytical expressions for the tunneling anisotropic magnetoresistance (TAMR) are derived within an approximation in which the dependence of the magnetoresistance on the magnetization orientation in the ferromagnet originates from the interference between Bychkov-Rashba and Dresselhaus spin-orbit couplings that appear at junction interfaces and in the tunneling region. We also investigate the transport properties of ferromagnet/semiconductor/…
The influence of insertion of an ultra-thin NiO layer between the MgO barrier and ferromagnetic electrode in magnetic tunnel junctions has been investigated by measuring the tunneling magnetoresistance and the X-ray magnetic circular dichroism (XMCD). The magnetoresistance shows a high asymmetry with respect to bias voltage, giving rise to a negative value of -16% at 2.8 K. We attribute this to the formation of non-collinear spin structures in the NiO layer as observed by XMCD. The magnetic moments of the interface Ni atoms tilt from the easy axis due to exchange interaction and the tilting an…
We investigate theoretically the spin-independent tunneling magnetoresistance effect in a graphene monolayer modulated by two parallel ferromagnets deposited on a dielectric layer. For the parallel magnetization configuration, Klein tunneling can be observed in the transmission spectrum, but at specific oblique incident angles. For the antiparallel magnetization configuration, the transmission can be blocked by the magnetic-electric barrier provided by the ferromagnets. Such a transmission discrepancy results in a tremendous magnetoresistance ratio and can be tuned by the inclusion of an elect…
Nonexponential relaxation of magnetization at resonant tunneling points of nanoscale molecular magnets is interpreted to be an effect of fluctuating random field around the applied field. We demonstrate such relaxation in Langevin equation analysis and clarify how the initial relaxation (square-root time) changes to the exponential decay. The scaling properties of the relaxation are also discussed.
We report on the enhancement of antiferromagnetic coupling in epitaxial Fe/Si/Fe structures by voltage-driven spin-polarized tunneling currents. Using the ballistic electron magnetic microscopy we established that the hot-electron collector current reflects magnetization alignment and the magnetocurrent exceeds 200% at room temperature. The saturation magnetic field for collector current corresponding to parallel alignment of magnetizations rises up with the tunneling current, thus demonstrating stabilization of the antiparallel alignment and increasing antiferromagnetic coupling. We connect t…
A Mn4 single-molecule magnet (SMM) is used to show that quantum tunneling of magnetization (QTM) is not suppressed by moderate three dimensional exchange coupling between molecules. Instead, it leads to an exchange bias of the quantum resonances which allows precise measurements of the effective exchange coupling that is mainly due to weak intermolecular hydrogen bounds. The magnetization versus applied field was recorded on single crystals of [Mn4]2 using an array of micro-SQUIDs. The step fine structure was studied via minor hysteresis loops.
We present a microscopic study of single-electron tunneling in nanomechanical double-barrier tunneling junctions formed using a vibrating scanning nanoprobe and a metallic nanoparticle connected to a metallic substrate through a molecular bridge. We analyze the motion of single electrons on and off the nanoparticle through the tunneling current, the displacement current and the charging-induced electrostatic force on the vibrating nanoprobe. We demonstrate the mechanical single-electron turnstile effect by applying the theory to a gold nanoparticle connected to the gold substrate through alkan…
A generalized Green's function theory is developed to simulate the inelastic electron tunneling spectroscopy (IETS) of molecular junctions. It has been applied to a realistic molecular junction with an octanedithiolate embedded between two gold contacts in combination with the hybrid density functional theory calculations. The calculated spectra are in excellent agreement with recent experimental results. Strong temperature dependence of the experimental IETS spectra is also reproduced. It is shown that the IETS is extremely sensitive to the intra-molecular conformation and to the molecule-met…
We consider the magnetic structure on the Fe(001) surface and theoretically study the scanning tunneling spectroscopy using a spin-polarized tip (SP-STM). We show that minority-spin surface states induce a strong bias dependence of the tunneling differential conductance which largely depends on the orientation of the magnetization in the SP-STM tip relative to the easy magnetization axis in the Fe(001) surface. We propose to use this effect in order to determine the spin character of the Fe(001) surface states. This technique can be applied also to other magnetic surfaces in which surface stat…
Two single-molecule magnets are coupled antiferromagnetically to form a supramolecule dimer. We study the coupling effect and tunneling process by means of the numerical exact diagonalization method, and apply them to the recently synthesized supramoleculer dimer [Mn4]2 The model parameters are calculated for the dimer based on the tunneling process. The absence of tunneling at zero field and sweeping rate effect on the step height in the hysterisis loops are understood very well in this theory.
We present a microscopic theory of single-electron tunneling through metallic nanoparticles connected to the electrodes through molecular bridges. It combines the theory of electron transport through molecular junctions with the description of the charging dynamics on the nanoparticles. We apply the theory to study single-electron tunneling through a gold nanoparticle connected to the gold electrodes through two representative benzene-based molecules. We calculate the background charge on the nanoparticle induced by the charge transfer between the nanoparticle and linker molecules, the capacit…
First-principles calculations of electron tunneling transport in Ni and Co break junctions reveal strong dependence of the conductance on the magnetization direction, an effect known as tunneling anisotropic magnetoresistance (TAMR). The origin of this phenomenon stems from resonant states localized in the electrodes near the junction break. The energy and broadening of these states is strongly affected by the magnetization orientation due to spin-orbit coupling, causing TAMR to be sensitive to bias voltage on a scale of a few mV. Our results bear a resemblance to recent experimental data and …
The tunneling magnetoresistance (TMR) of a hexagonal array of dipolar coupled anisotropic magnetic nanoparticles is studied using a resistor network model and a realistic micromagnetic configuration obtained by Monte Carlo simulations. Analysis of the field-dependent TMR and the corresponding magnetization curve shows that dipolar interactions suppress the maximum TMR effect, increase or decrease the field-sensitivity depending on the direction of applied field and introduce strong dependence of the TMR on the direction of the applied magnetic field. For off-plane magnetic fields, maximum valu…
The magnetic behavior of the Ca3Co2O6 spin chain compound is characterized by a large Ising-like character of its ferromagnetic chains, set on triangular lattice, that are antiferromagnetically coupled. At low temperature, T < 7K, the 3D antiferromagnetic state evolves towards a spin frozen state. In this temperature range, magnetic field driven magnetization of single crystals (H//chains) exhibits stepped variations. The occurrence of these steps at regular intervals of the applied magnetic field, Hstep=1.2T, is reminiscent of the quantum tunneling of the magnetization (QTM) of molecular base…
We present a comprehensive study of static and dynamic magnetic properties in the Ising-like dipolar antiferromagnet (AFM) DyScO$_3$\ by means of DC and AC magnetization measurements supported by classical Monte-Carlo calculations. Our AC-susceptibility data show that the magnetic dynamics exhibit a clear crossover from an Arrhenius-like regime to quantum tunneling of magnetization (QTM) at $T^* = 10$ K. Below $T_{\mathrm{N}} = 3.2$ K DyScO$_3$ orders in an antiferromagnetic $GxAy$-type magnetic structure and the magnetization dynamics slow down to the minute timescale. The low-temperature mag…
EPR spectra have been recorded in very high field, up to 25T, and at high frequency, up to 525 GHz, on a polycristalline sample of Mn12ac (see paper for detailed formula), the first example of molecular cluster behaving like a nanomagnet. The simulation of the spectra has provided an accurate determination of the parameters of the spin hamiltonian (see paper for formula and values of the various parameters). The presence of the fourth order term in the total spin justifies the irregularities in the spacing of the jumps, recently observed in the hysteresis loop of Mn12ac and attributed to accel…
Recent experiments on van der Waals antiferrmagnets such as CrI3, CrCl3 and MnPS3 have shown that using atomically thin layers as tunnel barriers and measuring the temperature ($T$) and magnetic field ($H$) dependence of the conductance allows their magnetic phase diagram to be mapped. In contrast, barriers made of CrBr3 -- the sole van der Waals ferromagnet investigated in this way -- were found to exhibit small and featureless magnetoconductance, seemingly carrying little information about magnetism. Here we show that -- despite these early results -- the conductance of CrBr3 tunnel barriers…
In a recent paper, cond-mat/0404041, J. Vanacken et al. reported experimental studies of crystals of Mn12-ac molecular nanomagnets in pulsed magnetic fields with sweep rates up to 4000 T/s. Steps in the magnetization curve were observed. The data were explained by collective dipolar relaxation. We give here an alternative explanation that is based on thermal avalanches triggered by defect molecules (faster relaxing species). These species are always present in Mn12-ac molecular nanomagnets. We propose a simple method to test this interpretation. Note that we do not question the possibility of …
We determine the conditions in which negative differential resistance (NDR) appears in the C$_{60}$-based molecular device of [Phys. Rev. Lett. {\bf 100}, 036807 (2008)] by means of ab-initio electron-transport simulations. Our calculations grant access to bias-dependent intrinsic properties of the molecular device, such as electronic levels and their partial widths. We show that these quantities depend on the molecule-molecule and molecule-electrode interactions of the device. Hence, NDR can be tuned by modifying the bias behavior of levels and widths using both types of interactions.
A clean Si(001) surface thermally purified in an ultrahigh vacuum molecular-beam epitaxy chamber has been investigated by means of scanning tunneling microscopy. The morphological peculiarities of the Si(001) surface have been explored in detail. The classification of the surface structure elements has been carried out, the dimensions of the elements have been measured, and the relative heights of the surface relief have been determined. A reconstruction of the Si(001) surface prepared in the molecular-beam epitaxy chamber has been found to be (8 x n). A model of the Si(001)-(8 x n) surface st…
We study inelastic electron tunneling through a molecular junction using the non-equilibrium Green function (NEGF) formalism. The effect of the mutual influence between the phonon and the electron subsystems on the electron tunneling process is considered within a general self-consistent scheme. Results of this calculation are compared to those obtained from the simpler Born approximation and the simplest perturbation theory approaches, and some shortcomings of the latter are pointed out. The self-consistent calculation allows also for evaluating other related quantities such as the power loss…
We present a theoretical study of the transport characteristics of molecular junctions, where first-row diatomic molecules are attached to (001) gold and platinum electrodes. We find that the conductance of all of these junctions is of the order of the conductance quantum unit $G_0$, spelling out that they belong to the transparent regime. We further find that the transmission coefficients show wide plateaus as a function of the energy, instead of the usual sharp resonances that signal the molecular levels in the tunneling regime. We use Caroli's model to show that this is a rather generic pro…
We show that resonant quantum tunneling of the magnetization, until now observed only in zero-dimensional (0D) cluster systems, occurs in the molecular Ising spin chain $[(CH_3)_3NH]CoCl_3\cdot 2H_2O$, which orders as a canted 3D-antiferromagnet at $T_C=4.15 K$. We present three features that prove unambigously the existence of resonant quantum tunneling below $0.3 K$ ($T_C/12$): Temperature independent relaxation of the magnetization, speeding up of the relaxation at a well defined field ($1025 Oe$) and increase of the magnetization each time this field is crossed during a succession of minor…
We report resistance versus magnetic field measurements for a La0.65Sr0.35MnO3/SrTiO3/La0.65Sr0.35MnO3 tunnel junction grown by molecular-beam epitaxy, that show a large field window of extremely high tunneling magnetoresistance (TMR) at low temperature. Scanning the in-plane applied field orientation through 360^/circ, the TMR shows 4-fold symmetry, i.e. biaxial anisotropy, aligned with the crystalline axes but not the junction geometrical long axis. The TMR reaches ~ 1900% at 4K, corresponding to an interfacial spin polarization of > 95% assuming identical interfaces. These results show that…
Field-tuned quantum tunneling in two single-molecule magnets coupled antiferromagnetically and formed a supramolecule dimer is studied. We obtain step-like magnetization curves by means of the numerically exact solution of the time-dependent Schrődinger equation. The steps in magnetization curves show the phenomenon of quantum resonant tunneling quantitatively. The effects of the sweeping rate of applied field is discussed. These results obtained from quantum dynamical evolution well agree with the recent experiment[W.Wernsdorfer et al. Nature 416(2002)406].
Spin tunneling in molecular magnets has attracted much attention, however theoretical considerations of this phenomenon up to now have not taken into account the many-spin nature of molecular magnets. We present, to our knowledge, the first successful attempt of a realistic calculation of tunneling splittings for Mn$_{12}$ molecules, thus achieving a quantitatively accurate many-spin description of a real molecular magnet in the energy interval ranging from about 100 K down to 10$^{-12}$ K. Comparison with the results of the standard single-spin model shows that many-spin effects affect the tu…
We propose a method to determine the direction of surface magnetization and local magnetic moments on the atomic scale. The method comprises high resolution scanning tunneling microscope experiments in conjunction with first principles simulations of the tunneling current. The potential of the method is demonstrated on a model system, antiferromagnetic Mn overlayers on W(110). We expect that it will ultimately allow to study the detailed changes of magnetic surface structures in the vicinity of dopants or impurities.
The electronic structure and spin-dependent tunneling in epitaxial Fe/MgO/Fe(001) tunnel junctions are studied using first-principles calculations. For small MgO barrier thickness the minority-spin resonant bands at the two interfaces make a significant contribution to the tunneling conductance for the antiparallel magnetization, whereas these bands are, in practice, mismatched by disorder and/or small applied bias for the parallel magnetization. This explains the experimentally observed decrease in tunneling magnetoresistance (TMR) for thin MgO barriers. We predict that a monolayer of Ag epit…
We study low temperature resonant spin tunneling in molecular magnets induced by a field sweep with account of dipole-dipole interactions. Numerical simulations uncovered formation of self-organized patterns of the magnetization and of the ensuing dipolar field that provide resonant condition inside a finite volume of the crystal. This effect is robust with respect to disorder and should be relevant to the dynamics of the magnetization steps observed in molecular magnets.
Thin van der Waals (vdW) layered magnetic materials disclose the possibility to realize vdW heterostructures with new functionalities. Here we report on the realization and investigation of tunneling spin valves based on van der Waals heterostructures consisting of an atomically thin hBN layer acting as tunnel barrier and two exfoliated Fe3GeTe2 crystals acting as ferromagnetic electrodes. Low-temperature anomalous Hall effect measurements show that thin Fe3GeTe2 crystals are metallic ferromagnets with an easy axis perpendicular to the layers, and a very sharp magnetization switching at magnet…
We predict the occurrence of metastable skyrmionic spin structures such as antiskyrmions and higher-order skyrmions in ultra-thin transition-metal films at surfaces using Monte Carlo simulations based on a spin Hamiltonian parametrized from density functional theory calculations. We show that such spin structures will appear with a similar contrast in spin-polarized scanning tunneling microscopy (SP-STM) images. Both skyrmions and antiskyrmions display a circular shape for out-of-plane magnetized tips and a two-lobe butterfly contrast for in-plane tips. An unambiguous distinction can be achiev…
Density-functional calculations are used to clarify the role of an ultrathin LiF layer on Al electrodes used in molecular electronics. The LiF layer creates a sharp density of states (DOS), as in a scanning-tunneling microscope (STM) tip. The sharp DOS, coupled with the DOS of the molecule leads to negative differential resistance (NDR). Electron transfer between oriented molecules occurs via resonant tunneling. The I-V characteristic for a thin-film of tris (8-hydroxyquinoline)- aluminum (AlQ) molecules, oriented using electric-field poling, and sandwiched between two Al/LiF electrodes is in …
We show that the conductance $G$ of molecular tunnel junctions wherein the charge transport is dominated by a single energy level can be expressed in closed analytic form which is exact and valid at arbitrary temperature $T$ and model parameter values. On this basis, we show that the single-step tunneling mechanism is compatible with a continuous thermal transition from a weakly $T$-dependent $G$ at low $T$ (Sommerfeld regime) to a nearly exponential $1/T$-dependent $G$ at high $T$ (Arrhenius-like regime). We predict that this Sommerfeld-Arrhenius transition can be observed in real molecular j…
We have combined scanning tunneling microscopy with inelastic electron tunneling spectroscopy (IETS) and density functional theory (DFT) to study a tetracyanoethylene monolayer on Ag(100). Images show that the molecules arrange in locally ordered patterns with three non-equivalent, but undeterminable, adsorption sites. While scanning tunneling spectroscopy only shows subtle variations of the local electronic structure at the three different positions, we find that vibrational modes are very sensitive to the local atomic environment. IETS detects sizeable mode frequency shifts of the molecules …
A microscopic model of the molecular magnet V15 is used to study mechanisms for the adiabatic change of the magnetization in time-dependent magnetic fields. Effects of the Dzyaloshinskii-Moriya interaction, the most plausible source for the energy-level repulsions that lead to adiabatic changes of the magnetization, are studied in detail. We find that the energy-level repulsions that result from this interaction exhibit a strong dependence on the direction of the applied field. We also discuss the role of magnetic anisotropy in the molecule Mn12 -acetate.
We develop a series of propensity rules for interpreting Inelastic Electron Tunneling (IET) spectra of single-molecule transport junctions. IETS has no selection rules, such as those seen in optical, infrared and Raman spectra, because IETS features arise not from the field-dipole interaction characterizing these other spectroscopies, but from vibronic modification of the electronic levels. Expansion of the Landauer-Imry formula in Taylor series in molecular normal coordinates gives a convenient, accurate perturbation-type formula for calculating both frequency and intensity of the IETS spectr…
We present a theory of tunneling and resonant transitions in one-dimensional molecular systems which is based on Green's function theory of electron sub-barrier scattering off the structural units (or functional groups) of a molecular chain. We show that the many-electron effects are of paramount importance in electron transport and they are effectively treated using a formalism of sub-barrier scattering operators. The method which calculates the total scattering amplitude of the bridge molecule not only predicts the enhancement of the amplitude of tunneling transitions in course of tunneling …
Dissipative spin-tunneling transitions at biased resonances in molecular magnets such as Mn-12 Ac are controlled by the dipolar field that can bring the system on and off resonance. It is shown that this leads to spin relaxation in form of propagating fronts of tunneling, with the dipolar field adjusting self-consistently to provide a zero bias within the front core. There are two regimes of the front propagation: laminar and non-laminar with discontinuous magnetization and dipolar field. In the laminar regime the speed of the front can exceed that of the magnetic deflagration, if the transver…
Tunneling magnetoresistance (TMR) in a vertical manganite junction was investigated by low-temperature scanning laser microscopy (LTSLM) allowing to determine the local relative magnetization M orientation of the two electrodes as a function of magnitude and orientation of the external magnetic field H. Sweeping the field amplitude at fixed orientation revealed magnetic domain nucleation and propagation in the junction electrodes. For the high-resistance state an almost single-domain antiparallel magnetization configuration was achieved, while in the low-resistance state the junction remained …
We have studied the bound states of the extra electron in a molecular wire, corresponding to the physical situation of the electron tunneling through the wire. Based on formalism of the scattering operator that accounts for many-electron interactions we have shown that the energy spectrum of the bound states of the extra electron in a linear chain of three-dimensional scattering centers substantially deviates for spectrum of independent single-electron states of Bloch electrons in a system described by a single-electron effective potential. In particular, in the case of elemental wire consisti…
Effects of coupling between a molecular exciton and a surface plasmon (exciton-plasmon coupling) on the luminescence properties of the molecule and the surface plasmons are investigated using the nonequilibrium Green's function method. Molecular absorption and enhancement by molecular electronic and vibrational modes (molecular modes) lead to dip and peak structures in the luminescence spectra of the surface plasmons. These structures will correspond to the peak and dip structures observed in a recent experiment. We found that in addition to the molecular dynamics, the re-absorption by the sur…
A model of coherent tunneling, which combines multi-orbital tight-binding approximation with Landauer-Büttiker formalism, is developed and applied to all-semiconductor heterostructures containing (Ga,Mn)As ferromagnetic layers. A comparison of theoretical predictions and experimental results on spin-dependent Zener tunneling, tunneling magnetoresistance (TMR), and anisotropic magnetoresistance (TAMR) is presented. The dependence of spin current on carrier density, magnetization orientation, strain, voltage bias, and spacer thickness is examined theoretically in order to optimize device design …
Interests in two-dimensional transition-metal dichalcogenides have prompted some recent efforts to grow ultrathin layers of these materials epitaxially using molecular-beam epitaxy. However, growths of monolayer and bilayer WSe2, an important member of the transition-metal dichalcogenides family, by the molecular-beam epitaxy method remain uncharted probably because of the difficulty in generating tungsten fluxes from the elemental source. In this work, we present a scanning tunneling microscopy and spectroscopy study of molecular-beam epitaxy-grown WSe2 monolayer and bilayer, showing atomical…
A novel scanning tunneling microscope manipulation scheme for a controlled molecular transport of weakly adsorbed molecules is demonstrated. Single sexiphenyl molecules adsorbed on a Ag(111) surface at 6 K are shot towards single silver-atoms by excitation with the tip. To achieve atomically straight shooting paths, an electron resonator consisting of linear standing wave fronts is constructed. The sexiphenyl manipulation signals reveal a pi-ring flipping as the molecule moves from hcp to fcc site. Abinitio calculations show an incorporation of the Ag atom below the center of a pi-ring.
The nuclear tunneling crossover temperature ($T_c$) of hydrogen transfer reactions in supported molecular-switch architectures can lie close to room temperature. This calls for the inclusion of nuclear quantum effects (NQE) in the calculation of reaction rates even at high temperatures. However, standard computations of NQE relying on parametrized dimensionality-reduced models, quickly become inadequate in these environments. In this letter, we study the paradigmatic molecular switch based on porphycene molecules adsorbed on metallic surfaces with full-dimensional calculations that combine den…
Molecular beam epitaxy is used to grow TiSe2 ultrathin films on graphitized SiC(0001) substrate. TiSe2films proceed via a nearly layer-by-layer growth mode and exhibit two dominant types of defects, identified as Se vacancy and interstitial, respectively. By means of scanning tunneling microscopy, we demonstrate that the well-established charge density waves can survive in single unit-cell (one triple layer) regime, and find a gradual reduction in their correlation length as the density of surface defects in TiSe2 ultrathin films increases. Our findings offer important insights into the nature…
