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Structural features and magnetic behaviour of TbPc2 thin films sublimated on LSMO and on cobalt surfaces have been investigated by synchrotron-based XNLD and XMCD techniques. Different orientation of the molecules is observed for the two substrates. No significant magnetic interaction with the ferromagnetic substrates is detected. [ABSTRACT FROM AUTHOR]

Electronic devices have been ever-shrinking toward atomic dimensions and have reached operation frequencies in the GHz range, thereby outperforming most conventional test equipment, such as vector network analyzers (VNA). Here the capabilities of a VNA on the atomic scale in a scanning tunneling microscope are implemented. Nonlinearities present in the voltage-current characteristic of atoms and nanostructures for phase-resolved microwave spectroscopy with unprecedented spatial resolution at GHz frequencies are exploited. The amplitude and phase response up to 9.3 GHz is determined, which permits accurate de-embedding of the transmission line and application of distortion-corrected waveforms in the tunnel junction itself. This enables quantitative characterization of the complex-valued admittance of individual magnetic iron atoms which show a lowpass response with a magnetic-field-tunable cutoff frequency., (© 2024 The Authors. Small Methods published by Wiley‐VCH GmbH.)

The decoration of technologically relevant surfaces, such as metal oxides, with Single-Molecule Magnets (SMMs) constitutes a persistent challenge for the integration of these molecular systems into novel technologies and, in particular, for the development of spintronic and quantum devices. We used UHV thermal sublimation to deposit tetrairon(III) propeller-shaped SMMs (Fe 4 ) as a single layer on a TiO 2 ultrathin film grown on Cu(001). The properties of the molecular deposit were studied using a multi-technique approach based on standard topographic and spectroscopic measurements, which demonstrated that molecules remain largely intact upon deposition. Ultralow temperature X-ray Absorption Spectroscopy (XAS) with linearly and circularly polarized light was further employed to evaluate both the molecular organization and the magnetic properties of the Fe 4 monolayer. X-ray Natural Linear Dichroism (XNLD) and X-ray Magnetic Circular Dichroism (XMCD) showed that molecules in a monolayer display a preferential orientation and an open magnetic hysteresis with pronounced quantum tunnelling steps up to 900 mK. However, unexpected extra features in the XAS and XMCD spectra disclosed a minority fraction of altered molecules, suggesting that the TiO 2 film may be chemically non-innocent. The observed persistence of SMM behaviour on a metal oxide thin film opens new possibilities for the development of SMM-based hybrid systems.

Charge density waves are wave-like modulations of a material's electron density that display collective amplitude and phase dynamics. The interaction with atomic impurities induces strong spatial heterogeneity of the charge-ordered phase. Direct real-space observation of phase excitation dynamics of such defect-induced charge modulation is absent. Here, by utilizing terahertz pump-probe spectroscopy in a scanning tunnelling microscope, we measure the ultrafast collective dynamics of the charge density wave in the transition metal dichalcogenide 2H-NbSe 2 with atomic spatial resolution. The tip-enhanced electric field of the terahertz pulses excites oscillations of the charge density wave that vary in magnitude and frequency on the scale of individual atomic impurities. Overlapping phase excitations originating from the randomly distributed atomic defects in the surface create this spatially structured response of the charge density wave. This ability to observe collective charge order dynamics with local probes makes it possible to study the dynamics of correlated materials at the intrinsic length scale of their underlying interactions., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2024.)

Conformational changes play a key role in the biological function of many proteins, thereby sustaining a multitude of processes essential to life. Thus, the imaging of the conformational space of proteins exhibiting such conformational changes is of great interest. Low-energy electron holography (LEEH) in combination with native electrospray ion beam deposition (ES-IBD) has recently been demonstrated to be capable of exploring the conformational space of conformationally highly variable proteins on the single-molecule level. While the previously studied conformations were induced by changes in environment, it is of relevance to assess the performance of this imaging method when applied to protein conformations inherently tied to a function-related conformational change. We show that LEEH imaging can distinguish different conformations of transferrin, the major iron transport protein in many organisms, by resolving a nanometer-scale cleft in the structure of the iron-free molecule (apo-transferrin) resulting from the conformational change associated with the iron binding/release process. This, along with a statistical analysis of the data, which evidences a degree of flexibility of the molecules, indicates that LEEH is a viable technique for imaging function-related conformational changes in individual proteins., (© 2023. The Author(s).)

Inline low-energy electron holography (LEEH) in conjunction with sample preparation by electrospray ion beam deposition (ES-IBD) has recently emerged as a promising method for the sub-nanometre-scale single-molecule imaging of biomolecules. The single-molecule nature of the LEEH measurement allows for the mapping of the molecules' conformational space and thus for the imaging of structurally variable biomolecules, thereby providing valuable complementary information to well-established biomolecular structure determination methods. Here, after briefly tracing the development of inline LEEH in bioimaging, we present the state-of-the-art of native ES-IBD + LEEH as a method of single-protein imaging, discuss its applications, specifically regarding the imaging of structurally flexible protein systems and the amplitude and phase information encoded in a low-energy electron hologram, and provide an outlook regarding the considerable possibilities for the future advancement of the approach., (© 2023 The Author(s).)

Molecule-surface collisions are known to initiate dynamics that lead to products inaccessible by thermal chemistry. These collision dynamics, however, have mostly been examined on bulk surfaces, leaving vast opportunities unexplored for molecular collisions on nanostructures, especially on those that exhibit mechanical properties radically different from those of their bulk counterparts. Probing energy-dependent dynamics on nanostructures, particularly for large molecules, has been challenging due to their fast time scales and high structural complexity. Here, by examining the dynamics of a protein impinging on a freestanding, single-atom-thick membrane, we discover molecule-on-trampoline dynamics that disperse the collision impact away from the incident protein within a few picoseconds. As a result, our experiments and ab initio calculations show that cytochrome c retains its gas-phase folded structure when it collides onto freestanding single-layer graphene at low energies (∼20 meV/atom). The molecule-on-trampoline dynamics, expected to be operative on many freestanding atomic membranes, enable reliable means to transfer gas-phase macromolecular structures onto freestanding surfaces for their single-molecule imaging, complementing many bioanalytical techniques., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Low-energy electron holography (LEEH) is one of the few techniques capable of imaging large and complex three-dimensional molecules, such as proteins, on the single-molecule level at subnanometer resolution. During the imaging process, the structural information about the object is recorded both in the amplitude and in the phase of the hologram. In low-energy electron holography imaging of proteins, the object's amplitude distribution, which directly reveals molecular size and shape on the single-molecule level, can be retrieved via a one-step reconstruction process. However, such a one-step reconstruction routine cannot directly recover the phase information encoded in the hologram. In order to extract the full information about the imaged molecules, we thus implemented an iterative phase retrieval algorithm and applied it to experimentally acquired low-energy electron holograms, reconstructing the phase shift induced by the protein along with the amplitude data. We show that phase imaging can map the projected atomic density of the molecule given by the number of atoms in the electron path. This directly implies a correlation between reconstructed phase shift and projected mean inner potential of the molecule, and thus a sensitivity to local changes in potential, an interpretation that is further substantiated by the strong phase signatures induced by localized charges.

Stochastic resonance, where noise synchronizes a system's response to an external drive, is a wide-reaching phenomenon found in noisy systems spanning from the dynamics of neurons to the periodicity of ice ages. Quantum tunneling can extend stochastic resonance to the quantum realm. We demonstrate quantum stochastic resonance for magnetic transitions in atoms by inelastic electron tunneling with a scanning tunneling microscope. Stochastic resonance is shown deep in the quantum regime, where spin-state fluctuations are driven by tunneling of the magnetization, and in a semiclassical crossover region, where thermally excited electrons drive transitions between ground and excited states. Inducing synchronization by periodically modulating transition rates provides a general mechanism to determine real-time spin dynamics ranging from milliseconds to picoseconds., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Broadband THz pulses enable ultrafast electronic transport experiments on the nanoscale by coupling THz electric fields into the devices with antennas, asperities, or scanning probe tips. Here, we design a versatile THz source optimized for driving the highly resistive tunnel junction of a scanning tunneling microscope. The source uses optical rectification in lithium niobate to generate arbitrary THz pulse trains with freely adjustable repetition rates between 0.5 and 41 MHz. These induce subpicosecond voltage transients in the tunnel junction with peak amplitudes between 0.1 and 12 V, achieving a conversion efficiency of 0.4 V/(kV/cm) from far-field THz peak electric field strength to peak junction voltage in the STM. Tunnel currents in the quantum limit of less than one electron per THz pulse are readily detected at multi-MHz repetition rates. The ability to tune between high pulse energy and high signal fidelity makes this THz source design effective for exploration of ultrafast and atomic-scale electron dynamics., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Minimizing the invasiveness of scanning tunneling measurements is paramount for observation of the magnetic properties of unperturbed atomic-scale objects. We show that the invasiveness of STM inspection on few-atom spin systems can be drastically reduced by means of a remote detection scheme, which makes use of a sensor spin weakly coupled to the sensed object. By comparing direct and remote measurements we identify the relevant perturbations caused by the local probe. For direct inspection we find that tunneling electrons strongly perturb the investigated object even for currents as low as 3 pA. Electrons injected into the sensor spin induce perturbations with much reduced probability. The sensing scheme uses standard differential conductance measurements, and is decoupled both by its non-local nature, and by dynamic decoupling due to the significantly different time scales at which the sensor and sensed object evolve. The latter makes it possible to effectively remove static interactions between the sensed object and the spin sensor while still allowing the spin sensing. In this way we achieve measurements with a reduction in perturbative effects of up to 100 times relative to direct scanning tunneling measurements, which enables minimally invasive measurements of a few-atom magnet's fragile spin states with STM.

Magnetic materials interfaced with superconductors may reveal new physical phenomena with potential for quantum technologies. The use of molecules as magnetic components has already shown great promise, but the diversity of properties offered by the molecular realm remains largely unexplored. Here we investigate a submonolayer of tetrairon(III) propeller-shaped single molecule magnets deposited on a superconducting lead surface. This material combination reveals a strong influence of the superconductor on the spin dynamics of the single molecule magnet. It is shown that the superconducting transition to the condensate state switches the single molecule magnet from a blocked magnetization state to a resonant quantum tunnelling regime. Our results open perspectives to control single molecule magnetism via superconductors and to use single molecule magnets as local probes of the superconducting state.

Atomic-scale magnetic moments in contact with superconductors host rich physics based on the emergence of Yu-Shiba-Rusinov (YSR) magnetic bound states within the superconducting condensate. Here, we focus on a magnetic bound state induced into Pb nanoislands by individual vanadyl phthalocyanine (VOPc) molecules deposited on the Pb surface. The VOPc molecule is characterized by a spin magnitude of 1/2 arising from a well-isolated singly occupied d xy -orbital and is a promising candidate for a molecular spin qubit with long coherence times. X-ray magnetic circular dichroism (XMCD) measurements show that the molecular spin remains unperturbed even for molecules directly deposited on the Pb surface. Scanning tunneling spectroscopy and density functional theory (DFT) calculations identify two adsorption geometries for this "asymmetric" molecule (i.e., absence of a horizontal symmetry plane): (a) oxygen pointing toward the vacuum with the Pc laying on the Pb, showing negligible spin-superconductor interaction, and (b) oxygen pointing toward the Pb, presenting an efficient interaction with the Pb and promoting a Yu-Shiba-Rusinov bound state. Additionally, we find that in the first case a YSR state can be induced smoothly by exerting mechanical force on the molecules with the scanning tunneling microscope (STM) tip. This allows the interaction strength to be tuned continuously from an isolated molecular spin case, through the quantum critical point (where the bound state energy is zero) and beyond. DFT indicates that a gradual bending of the VO bond relative to the Pc ligand plane promoted by the STM tip can modify the interaction in a continuously tunable manner. The ability to induce a tunable YSR state in the superconductor suggests the possibility of introducing coupled spins on superconductors with switchable interaction.

The alteration of the properties of single-molecule magnets (SMMs) due to the interaction with metallic electrodes is detrimental to their employment in spintronic devices. Conversely, herein we show that the terbium(iii) bis-phthalocyaninato complex, TbPc 2 , maintains its SMM behavior up to 9 K on a graphene/SiC(0001) substrate, making this alternative conductive layer highly promising for molecular spintronic applications.

We present the appearance of negative differential resistance (NDR) in spin-dependent electron transport through a few-atom spin chain. A chain of three antiferromagnetically coupled Fe atoms (Fe trimer) was positioned on a Cu_{2}N/Cu(100) surface and contacted with the spin-polarized tip of a scanning tunneling microscope, thus coupling the Fe trimer to one nonmagnetic and one magnetic lead. Pronounced NDR appears at the low bias of 7 mV, where inelastic electron tunneling dynamically locks the atomic spin in a long-lived excited state. This causes a rapid increase of the magnetoresistance between the spin-polarized tip and Fe trimer and quenches elastic tunneling. By varying the coupling strength between the tip and Fe trimer, we find that in this transport regime the dynamic locking of the Fe trimer competes with magnetic exchange interaction, which statically forces the Fe trimer into its high-magnetoresistance state and removes the NDR.

The ability to sense the magnetic state of individual magnetic nano-objects is a key capability for powerful applications ranging from readout of ultradense magnetic memory to the measurement of spins in complex structures with nanometer precision. Magnetic nano-objects require extremely sensitive sensors and detection methods. We create an atomic spin sensor consisting of three Fe atoms and show that it can detect nanoscale antiferromagnets through minute, surface-mediated magnetic interaction. Coupling, even to an object with no net spin and having vanishing dipolar stray field, modifies the transition matrix element between two spin states of the Fe atom-based spin sensor that changes the sensor's spin relaxation time. The sensor can detect nanoscale antiferromagnets at up to a 3-nm distance and achieves an energy resolution of 10 μeV, surpassing the thermal limit of conventional scanning probe spectroscopy. This scheme permits simultaneous sensing of multiple antiferromagnets with a single-spin sensor integrated onto the surface.

Single-molecule magnets (SMMs) present a promising avenue to develop spintronic technologies. Addressing individual molecules with electrical leads in SMM-based spintronic devices remains a ubiquitous challenge: interactions with metallic electrodes can drastically modify the SMM's properties by charge transfer or through changes in the molecular structure. Here, we probe electrical transport through individual Fe4 SMMs using a scanning tunnelling microscope at 0.5 K. Correlation of topographic and spectroscopic information permits identification of the spin excitation fingerprint of intact Fe4 molecules. Building from this, we find that the exchange coupling strength within the molecule's magnetic core is significantly enhanced. First-principles calculations support the conclusion that this is the result of confinement of the molecule in the two-contact junction formed by the microscope tip and the sample surface.

We demonstrate that Fe4 molecules can be deposited on gold by thermal sublimation in ultra-high vacuum with retention of single molecule magnet behavior. A magnetic hysteresis comparable to that found in bulk samples is indeed observed when a submonolayer film is studied by X-ray magnetic circular dichroism. Scanning tunneling microscopy evidences that Fe4 molecules are assembled in a two-dimensional lattice with short-range hexagonal order and coexist with a smaller contaminant. The presence of intact Fe4 molecules and the retention of their bistable magnetic behavior on the gold surface are supported by density functional theory calculations.

The adsorption of the sterically hindered β-diketonate complex Fe(dpm)3, where Hdpm = dipivaloylmethane, on Au(111) was investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunnelling microscopy (STM). The high volatility of the molecule limited the growth of the film to a few monolayers. While UPS evidenced the presence of the β-diketonate ligands on the surface, the integrity of the molecule on the surface could not be assessed. The low temperature STM images were more informative and at submonolayer coverage they showed the presence of regular domains characterized by a flat morphology and height of ≈0.3 nm. Along with these domains, tetra-lobed features adsorbed on the kinks of the herringbone were also observed. DFT-simulated images of the pristine molecule and its possible decomposition products allowed to assess the partial fragmentation of Fe(dpm)3 upon adsorption on the Au(111) surface. Structural features with intact molecules were only observed for the saturation coverage. An ex situ prepared thick film of the complex was also investigated by X-ray magnetic circular dichroism (XMCD) and features typical of high-spin iron(III) in octahedral environment were observed.

Single-molecule magnets (SMMs) are among the most promising molecular systems for the development of novel molecular electronics based on spin transport. Going beyond investigations focused on physisorbed SMMs, in this work the robust grafting of terbium(III) bis(phthalocyaninato) complexes to a silicon surface from a diluted solution is achieved by rational chemical design yielding the formation of a partially oriented monolayer on the conducting substrate. Here by exploiting the surface sensitivity of X-ray circular magnetic dichroism, we evidence an enhancement of the magnetic bistability of this SMM, in contrast to the dramatic reduction of the magnetic hysteresis that characterizes monolayer deposits evaporated on noble and ferromagnetic metals. Photoelectron spectroscopy investigations and density functional theory analysis suggest a non-innocent role played by the silicon substrate, evidencing the potentiality of this approach for robust integration of bistable magnetic molecules in electronic devices.

A new tetrairon(III) single-molecule magnet with enhanced volatility and processability was obtained by partial fluorination of the ancillary β-diketonato ligands. Fluorinated proligand Hpta = pivaloyltrifluoroacetone was used to assemble the bis(alkoxido)-bridged dimer [Fe2(OEt)2(pta)4] (1) in crystalline form, from which the new tetranuclear complex [Fe4(L)2(pta)6] (2) was synthesized in a one-pot reaction with H3L = 2-hydroxymethyl-2-phenylpropane-1,3-diol, NaOEt, and FeCl3 in a Et2O:EtOH solvent mixture. The structure of compound 2 was inferred from (1)H NMR, mass spectrometry, magnetic measurements, and DFT calculations. Direct current magnetic data are consistent with the expected metal-centered triangular topology for the iron(III) ions, with an antiferromagnetic coupling constant J = 16.20(6) cm(-1) between the central iron and the peripheral ones and consequent stabilization of an S = 5 spin ground state. Alternating current (ac) susceptibility measurements in 0 and 1 kOe static applied fields show the presence of a thermally activated process for magnetic relaxation, with τ0 = 2.3(1) 10(-7) s and U(eff)/kB = 9.9(1) K at zero static field and τ0 = 2.0(2) 10(-7) s and U(eff)/kB = 13.0(2) K at 1 kOe. At a pressure of 10(-7) mbar, compound 2 sublimates at (440 ± 5) K vs (500 ± 10) K for the nonfluorinated variant [Fe4(L)2(dpm)6] (Hdpm = dipivaloylmethane). According to XPS, ToF-SIMS, and ac susceptibility studies, the chemical composition, fragmentation pattern, and slow magnetic relaxation of the pristine material are retained in sublimated samples, suggesting that the molecular structure remains totally unaffected upon vapor-phase processing.

Purpose: To investigate the effects of clinical, sociodemographic, and occupational factors on time to return to work (RTW) during the 2 years after cancer diagnosis and to analyze whether sex differences exist., Patients and Methods: This study was based on a French national cross-sectional survey involving 4,270 cancer survivors. Time to RTW was estimated through the duration of sick leave of 801 cancer survivors younger than 58 years who were employed during the 2-year survey. Multivariate analysis of the RTW after sick leave was performed using a Weibull accelerated failure time model., Results: We found some sex differences in the RTW process. Older men returned to work more slowly than older women (P = .013), whereas married men returned to work much faster than married women (P = .019). Duration dependence was also sex-specific. In men, the time spent on sick leave was independent of the probability of returning to work, whereas in women, this duration dependence was positive (P < .001). For both men and women, clinical factors including chemotherapy, adverse effects, and cancer severity were found to delay RTW (P = .035, P = .001, and P < .001, respectively). Survivors investing most strongly in their personal lives also delayed their RTW (P = .006), as did those with a permanent work contract (P = .042). The factor found to accelerate RTW was a higher educational level (P = .014)., Conclusion: The RTW process 2 years after cancer diagnosis differed between men and women. A better knowledge of this process should help the national implementation of more cost-effective strategies for managing the RTW of cancer survivors.

We present measurements of the magnetic properties of thin film TbPc(2) single-molecule magnets evaporated on a gold substrate and compare them to those in bulk. Zero-field muon spin relaxation measurements were used to determine the molecular spin fluctuation rate of TbPc(2) as a function of temperature. At low temperature, we find that the fluctuations in films are much faster than in bulk and depend strongly on the distance between the molecules and the Au substrate. We measure a molecular spin correlation time that varies between 1.4 μs near the substrate and 6.6 μs far away from it. We attribute this behavior to differences in the packing of the magnetic cores, which change gradually on the scale of ~10-20 nm away from the TbPc(2)/Au interface.

The aim of this study was to describe 2 years cancer survivors' perception of the cancer risk running in their family, and to describe how frequently these survivors recommended cancer screening to their relatives. A national cross-sectional survey was launched by the French Ministry of Health to investigate the living conditions of adult cancer patients 2 years after cancer diagnosis. Among the 13,923 patients identified, 6,957 were eligible to participate in this study and 4460 (64.1%) answered the questionnaire administered by telephone. One participant out of every two (50.8%) reported that they thought their relatives' risk of cancer was greater than that of the relatives of unaffected persons. Higher percentages were recorded among breast and colorectal cancer patients (65 and 65.1%, respectively), and lower percentages among those with lung and hematological cancer (34.9 and 28.4%, respectively). Overall, 61.1% of the participants had already advised relatives to undergo cancer screening and 10.4% planned to do so. Eighty-one percent of the participants with breast cancer and 76.3% of those with colorectal cancer said they had advised relatives to undergo screening. Lower percentages were obtained among patients with urinary tract (41.7%) and hematological malignancies (27.1%). Although patients' perceptions tend to fit the latest data on the frequency of cancer germline mutations, physicians should help their patients to convey more accurate advice to their families. If survivors were better informed, they could play a critical role by conveying relevant and sound risk reduction messages to their relatives.

Objective: To describe patients who reported treatment-induced infertility 2 years after cancer diagnosis and to highlight what factors are related to the patients' lack of information on this topic before starting therapy., Design: Cross-sectional study by telephone interview., Setting: Representative French national sample of survivors 2 years after cancer diagnosis., Patient(s): 282 women (<45 years) and 1137 men (<71 years)., Intervention(s): None., Main Outcome Measure(s): Self-reported treatment-induced infertility, and what information was provided on this issue before starting treatment, including information on systematic sperm cryopreservation., Result(s): Among the participants, 104 women (37%) and 346 men (30%) reported having treatment-induced infertility. Among them, 31 women (30%) and 45 men (13%) reported that they had not been informed about the risk of infertility before they started treatment. Logistic regressions showed that a lack of information was associated with older age and treatment without hormone therapy among women and older age, cancers other than prostate, and a lack of participation in treatment decision-making among men., Conclusion(s): Information about infertility risks and preservation methods should be provided more systematically to all treated patients, irrespective of their age.

This contribution provides an econometric evaluation of the impact of two innovative care programs for elderly persons with dementia (day-care centers and group-living) on the well-being of the primary caregiver of patients. For this evaluation we use data from a survey conducted in six European countries in 1998. The results show that after adjusting for selection bias day-care centers have a positive impact for a specific part of the population. They also reveal a rationing mechanism in the access to group-living.