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57 records · Page 4

Spin–vibronic coherence drives singlet–triplet conversion

Design-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism. Here we present coherence spectroscopy experiments that reveal the interplay between the spin, electronic and vibrational degrees of freedom that drive efficient singlet-triplet conversion in four structurally related dinuclear Pt(II) metal-metal-to-ligand charge-transfer (MMLCT) complexes. Photoexcitation activates the formation of a Pt-Pt bond, launching a stretching vibrational wavepacket. The molecular-structure-dependent decoherence and recoherence dynamics of this wavepacket resolve the spin-vibronic mechanism. Further, we find that vectorial motion along the Pt-Pt stretching coordinates tunes the singlet and intermediate-state energy gap irreversibly towards the conical intersection and subsequently drives formation of the lowest stable triplet state in a ratcheting fashion. This work demonstrates the viability of using vibronic coherences as probes to clarify the interplay among spin, electronic and nuclear dynamics in spin-conversion processes, and this could inspire new modular designs to tailor the properties of excited states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled skyrmion ratchet in linear protrusion defects

Using atomistic simulations, we investigate the dynamical behavior of a single skyrmion interacting with an asymmetric linear protrusion array under external ac driving. The linear protrusion array is placed in the xy plane and is composed of magnetic walls near the edge of the nanotrack that have angled linear protrusions into the nanotrack. The structure forms a hard axis for –x direction motion and an easy axis for +x direction motion. When the ac drive is applied along the x direction, the skyrmion moves along the hard direction of the substrate asymmetry in three phases: a pinned phase with localized skyrmion orbits, a constant velocity phase where the orbits become delocalized, and a reentrant pinned phase with larger localized orbits. We measure the dependence of the skyrmion velocity on the frequency and amplitude of the ac drive. All three phases appear for all frequency values simulated here, and in the constant velocity phase the skyrmion velocity depends only on the frequency and not on the amplitude of the ac drive. When ac driving is applied in the y direction, the skyrmion moves along the easy direction of the substrate asymmetry and exhibits the same three phases as for x-direction driving along with a fourth phase which, at high driving frequencies, consists of a series of constant velocity phases, each with different average skyrmion velocities. For low frequencies, the constant velocity phase is lost and the skyrmion speed increases linearly with increasing ac drive amplitude due to a Magnus boost effect. Finally, our findings suggest new ways to create reliable data transport for spintronic devices using skyrmions as information carriers, where the skyrmion direction and speed can be controlled by varying only the ac drive amplitude and frequency.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effects of Control Mode and R-Ratio on the Fatigue Behavior of a Metal Matrix Composite

Composite Because of their high specific stiffness and strength at elevated temperatures, continuously reinforced metal matrix composites (MMC's) are under consideration for a future generation of aeropropulsion systems. Since components in aeropropulsion systems experience substantial cyclic thermal and mechanical loads, the fatigue behavior of MMC's is of great interest. Almost without exception, previous investigations of the fatigue behavior of MMC's have been conducted in a tension-tension, load-controlled mode. This has been due to the fact that available material is typically less than 2.5-mm thick and, therefore, unable to withstand high compressive loads without buckling. Since one possible use of MMC's is in aircraft skins, this type of testing mode may be appropriate. However, unlike aircraft skins, most engine components are thick. In addition, the transient thermal gradients experienced in an aircraft engine will impose tension-compression loading on engine components, requiring designers to understand how the MMC will behave under fully reversed loading conditions. The increased thickness of the MMC may also affect the fatigue life. Traditionally, low-cycle fatigue (LCF) tests on MMC's have been performed in load control. For monolithic alloys, low-cycle fatigue tests are more typically performed in strain control. Two reasons justify this choice: (1) the critical volume from which cracks initiate and grow is generally small and elastically constrained by the larger surrounding volume of material, and (2) load-controlled, low-cycle fatigue tests of monolithics invariably lead to unconstrained ratcheting and localized necking--an undesired material response because the failure mechanism is far more severe than, and unrelated to, the fatigue mechanism being studied. It is unknown if this is the proper approach to composite testing. However, there is a lack of strain-controlled data on which to base any decisions. Consequently, this study addresses the isothermal, LCF behavior of a [0]_32 MMC tested under strain- and load-controlled conditions for both zero-tension and tension-compression loading conditions. These tests were run at 427 C on thick specimens of SiC-reinforced Ti-15-3. For the fully-reversed tests, no difference was observed in the lives between the load- and strain-controlled tests. However, for the zero-tension tests, the strain-controlled tests had longer lives by a factor of 3 in comparison to the load-controlled tests. This was due to the fact that under strain-control the specimens cyclically softened, reducing the cracking potential. In contrast, the load-controlled tests ratcheted toward larger tensile strains leading to an eventual overload of the fibers. Fatigue tests revealed that specimens tested under fully-reversed conditions had lives approximately an order of magnitude longer than for those specimens tested under zero tension. When examined on a strain-range basis, the fully reversed specimens had similar, but still shorter lives than those of the unreinforced matrix material. However, the composite had a strain limitation at short lives because of the limited strain capacity of the brittle ceramic fiber. The composite also suffered at very high lives because of the lack of an apparent fatigue limit in comparison to the unreinforced matrix. The value of adding fibers to the matrix is apparent when the fatigue lives are plotted as a function of stress range. Here, the composite is far superior to the unreinforced matrix because of the additional load-carrying capacity of the fibers.

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