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Mechanochemical reaction pathways are conventionally obtained from force-displaced stationary points on the potential energy surface of the reaction. This work tests a postulate that the steepest-descent pathway (SDP) from the transition state to reactants can be reasonably accurately used instead to investigate mechanochemical reaction kinetics. This method is much simpler because the SDP and the associated reactant and transition-state structures can be obtained relatively routinely. Experiment and theory are compared for the normal-stress-induced decomposition of methyl thiolate species on Cu(100). The mechanochemical reaction rate was calculated by compressing the initial- and transition-state structures by a stiff copper counter-slab to obtain the plots of energy versus slab displacement for both structures. The reaction rate was also measured experimentally under compression using a nanomechanochemical reactor comprising an atomic-force-microscopy (AFM) instrument tip compressing a methyl thiolate overlayer on Cu(100) (the same system for which the calculations were carried out). The rate was measured from the indent created on a defect-free region of the methyl thiolate overlayer, which also enabled the contact area to be measured. Knowing the force applied by the AFM tip yields the reaction rate as a function of the contact stress. The result agrees well with the theoretical prediction withoutmore »the use of adjustable parameters. This confirms that the postulate is correct and will facilitate the calculation of the rates of more complex mechanochemical reactions. An advantage of this approach, in addition to the results agreeing with the experiment, is that it provides insights into the effects that control mechanochemical reactivity that will assist in the targeted design of new mechanochemical syntheses.« less

Recent website fingerprinting attacks have been shown to achieve very high performance against traffic through Tor. These attacks allow an adversary to deduce the website a Tor user has visited by simply eavesdropping on the encrypted communication. This has consequently motivated the development of many defense strategies that obfuscate traffic through the addition of dummy packets and/or delays. The efficacy and practicality of many of these recent proposals have yet to be scrutinized in detail. In this study, we re-evaluate nine recent defense proposals that claim to provide adequate security with low-overheads using the latest Deep Learning-based attacks. Furthermore, we assess the feasibility of implementing these defenses within the current confines of Tor. To this end, we additionally provide the first on-network implementation of the DynaFlow defense to better assess its real-world utility.

Recent website fingerprinting attacks have been shown to achieve very high performance against traffic through Tor. These attacks allow an adversary to deduce the website a Tor user has visited by simply eavesdropping on the encrypted communication. This has consequently motivated the development of many defense strategies that obfuscate traffic through the addition of dummy packets and/or delays. The efficacy and practicality of many of these recent proposals have yet to be scrutinized in detail. In this study, we re-evaluate nine recent defense proposals that claim to provide adequate security with low-overheads using the latest Deep Learning-based attacks. Furthermore, we assess the feasibility of implementing these defenses within the current confines of Tor. To this end, we additionally provide the first on-network implementation of the DynaFlow defense to better assess its real-world utility.

Website fingerprinting is an attack that uses size and timing characteristics of encrypted downloads to identify targeted websites. Since this can defeat the privacy goals of anonymity networks such as Tor, many algorithms to defend against this attack in Tor have been proposed in the literature. These algorithms typically consist of some combination of the injection of dummy "padding'' packets with the delay of actual packets to disrupt timing patterns. For usability reasons, Tor is intended to provide low latency; as such, many authors focus on padding-only defenses in the belief that they are "zero-delay.'' We demonstrate through Shadow simulations that by increasing queue lengths, padding-only defenses add delay when deployed network-wide, so they should not be considered "zero-delay.'' We further argue that future defenses should also be evaluated using network-wide deployment simulations.

The rates of mechanochemical reactions are generally found to increase exponentially with applied stress. However, a buckling theory analysis of the effect of a normal stress on an adsorbate that is oriented perpendicularly to the surface that reacts by tilting suggests that a critical value of the stress should be required to initiate a mechanochemical reaction. This concept is verified by using density functional theory calculations to simulate the effect of compressing a homologous series of alkyl thiolate species on copper by a hydrogen-terminated copper counter-face. This predicts that a critical stress is indeed needed to initiate methyl thiolate decomposition, which has a perpendicular C–CH 3 bond. In contrast, no critical stress is found for ethyl thiolate with an almost horizontal C–CH 3 bond, while a critical stress is required to isomerize propyl thiolate from a trans to a cis configuration. These predictions are tested by measuring the mechanochemical reaction rates of these alkyl thiolates on a Cu(100) substrate by sliding an atomic force microscope tip over the surface and finding a critical stress of ∼0.43 GPa for methyl thiolate, ∼0.33 GPa for propyl thiolate, but no evidence of a critical stress for ethyl thiolate, in accord with the predictions.more »These results provide insights not only into mechanochemical reaction mechanisms on surfaces, but also on the origin of critical phenomena in stress-induced processes in general. It also suggests novel approaches to designing robust surface films that can resist wear and damage.« less