M\uf6ssbauer spectroscopy of a monolayer of single molecule magnets

The use of single molecule magnets (SMMs) as cornerstone elements in spintronics and quantum computing applications demands that magnetic bistability is retained when molecules are interfaced with solid conducting surfaces. Here, we employ synchrotron M\uf6ssbauer spectroscopy to investigate a monolayer of a tetrairon(III) (Fe4) SMM chemically grafted on a gold substrate. At low temperature and zero magnetic field, we observe the magnetic pattern of the Fe4 molecule, indicating slow spin fluctuations compared to the M\uf6ssbauer timescale. Significant structural deformations of the magnetic core, induced by the interaction with the substrate, as predicted by ab initio molecular dynamics, are also observed. However, the effects of the modifications occurring at the individual iron sites partially compensate each other, so that slow magnetic relaxation is retained on the surface. Interestingly, these deformations escaped detection by conventional synchrotron-based techniques, like X-ray magnetic circular dichroism, thus highlighting the power of synchrotron M\uf6ssbauer spectroscopy for the investigation of hybrid interfaces

Synchrotron M\uf6ssbauer Source technique for in situ measurement of iron-bearing inclusions in natural diamonds

Natural diamonds containing silicate, oxide and sulfide inclusions are a popular focus of investigation as they uniquely provide a window into the conditions of the Earth\u2019s interior at extreme depths. Recent discoveries based on investigations of deep diamonds have considerably improved our knowledge of the Earth\u2019s deep carbon and water cycles and the oxygen fugacity of the Earth\u2019s interior. Super deep diamonds are those that are believed to have formed at depths of at least 300 km and some evidence suggests depths of at least 800 km. A common inclu- sion in these diamonds is ferropericlase, (Mg,Fe2+)O. Ferropericlase is the second most abundant mineral in the lower mantle, constituting up to about 20 mol% of its volume. The Fe3+/Fetot of ferropericlase is a strong func- tion of oxygen fugacity, and provides a measure of the most recent redox conditions under which it equilibrated. Conventional M\uf6ssbauer spectroscopy using a 57Co point source has been used in the past decades to study the Fe3+/Fetot content in inclusions still trapped in their diamond\u2019s host, however its limitations are the low spatial resolution (not below 3c100 \u3bcm2) and the long acquisition time. The Flank method was also proposed, it is fast, it has high spatial resolution (down to 3c20 \u3bcm2) but it measures the bulk value of Fe3+/Fetot since it cannot distinguish between different phases. An ideal method to measure Fe3+/Fetot values of ferropericlase would com- bine (1) the advantage of M\uf6ssbauer spectroscopy to distinguish Fe3+ in different phases and measure inclusions while still in the diamond, with (2) the advantage of the Flank method to conduct rapid measurements with high spatial resolution. The only method that offers the possibility to satisfy all these requirements is the Synchrotron M\uf6ssbauer Source (SMS). We used the SMS for the first time, to study the iron content and iron distribution in ferropericlase inclusion still contained within its diamond host from Juina (Brazil). This definitive non-destructive technique with extremely high spatial resolution ( 3c15 \u3bcm2) enabled measurements in multiple regions of the 150 7 150 \u3bcm2 inclusion to be sampled and showed that while Fe3+/Fetot values in ferropericlase were below the detection limit (0.02) overall, there was a magnetic component whose abundance varied systematically across the inclusion. Hyperfine parameters of the magnetic component are consistent with magnesioferrite, and the absence of superparamagnetism allows the minimum particle size to be estimated as 3c30 nm. Bulk Fe3+/Fetot values are similar to those reported for other ferropericlase inclusions from Juina. Their variation across the inclusion can provide constraints on its history, and ultimate on the deep carbon processes behind diamonds formation and their exhumation from the transition zone and shallow lower mantle regions

First in-situ measurements of Fe3+/Fetot for oxides and silicates included in natural diamonds with Synchrotron M\uf6ssbauer Source

Diamond is the paramount phase to understand the evolution and the physico- chemical condition of the deep portions of the Earth\u2019s mantle, mainly because: (i) it is the stable phase through which carbon is stored in the deep mantle for long geologic time; (ii) it does contain and preserve different types of inclusions (fluid, mineral, etc.); (iii) it is the only material sampling the mantle to depths of 800 km (e.g. Harte, 2010), although the majority of the mined diamonds worldwide derive from shallower depth (150 to 250 km). The study of mineral inclusions trapped in diamonds allows the retrieval of different pieces of information about the Earth\u2019s interior and its active geodynamics, providing important clues on the initiation of subduction processes (Shirey & Richardson, 2011; Smart et al., 2016), tracking the transfer of material through the mantle transition zone (Stachel et al., 2005; Walter et al., 2011), recording the timing of ingress of fluids to the continental lithosphere (e.g. Shirey et al., 2004), preserving carbonatitic fluid that trigger deep mantle melting (e.g. Schrauder & Navon, 1994; Kopylova et al., 2010), providing samples of primordial noble gases (e.g. Ozima & Igarashi, 2000), and capturing the redox state of the mantle (e.g. Rohrbach & Schmidt, 2011). Unfortunately the majority of the techniques used so far to study the mineral inclusions are destructive. It is only in the last decade that the studies on inclusions in diamond have started to use non-destructive techniques, providing new information which would otherwise be lost using earlier destructive techniques. Such an example is the rim fluids around inclusions in diamonds. In this study we present details of the experimental setup on the determination of Fe3+/Fetot ratios of mineral inclusions whilst still within the diamonds by a non-destructive approach using the Synchrotron M\uf6ssbauer Source (SMS; Potapkin et al., 2012) at the Nuclear Resonance beamline SOURCE ID18 (R\ufcffer & Chumakov, 1996), European Synchrotron Radiation Facility (ESRF), Grenoble. The extremely small X-ray spot size (10 7 15 \u3bcm2) is perfectly suited for our purposes as some inclusions are smaller than 30-50 \u3bcm and the Fe3+/Fetot variation over the same inclusion cannot be performed by using standard laboratory radioactive sources because of the larger beam size. The average collection time for thicker inclusions (~ 200 \u3bcm) was 2 hours per spectrum, whilst the smallest inclusion (~ 30 730 730 \u3bcm3) required a collection time of approximately 10-12 hours in order to get a spectrum with nicely distinguishable features and a high signal-to-noise ratio. In general, application to a suite of silicate and oxide inclusions in diamonds produced comparable results with respect to those obtained using conventional M\uf6ssbauer sources (e.g. McCammon et al., 2004)