50,545 research outputs found
Relative Entropy: Free Energy Associated with Equilibrium Fluctuations and Nonequilibrium Deviations
Using a one-dimensional macromolecule in aqueous solution as an illustration,
we demonstrate that the relative entropy from information theory, , has a natural role in the energetics of equilibrium and
nonequilibrium conformational fluctuations of the single molecule. It is
identified as the free energy difference associated with a fluctuating density
in equilibrium, and is associated with the distribution deviate from the
equilibrium in nonequilibrium relaxation. This result can be generalized to any
other isothermal macromolecular systems using the mathematical theories of
large deviations and Markov processes, and at the same time provides the
well-known mathematical results with an interesting physical interpretations.Comment: 5 page
Group VIII Coordination Chemistry of a Pincer-Type Bis(8-quinolinyl)amido Ligand
This paper provides an entry point to the coordination chemistry of the group VIII chemistry of the bis(8-quinolinyl)amine (BQA) ligand. In this context, mono- and disubstituted BQA complexes of iron, ruthenium, and osmium are described. For example, the low-spin bis-ligated Fe(III) complex [Fe(BQA)2][BPh4] has been prepared via amine addition to FeCl3 in the presence of a base and NaBPh4. Complexes featuring a single BQA ligand are more readily prepared for Ru and Os. Auxiliary ligands featuring a single BQA ligand, along with two other L-type donor ligands, allow for a variety of ligand types to occupy a sixth coordination site. Representative examples include the halide and pseudohalide complexes trans-(BQA)MX(PPh3)2 (M = Ru, Os; X = Cl, Br, N3, OTf), as well as the hydride and alkyl complexes trans-(BQA)RuH(PMe3)2 and trans-(BQA)RuMe(PMe3)2. Electrochemical studies are discussed that help to contextualize the BQA ligand with respect to its neutral counterpart 2,2β²,2β²β²-terpyridine (terpy) in terms of electron-releasing character. Bidentate ligands have been explored in conjunction with the BQA ligand. Thus, the bidentate, monoanionic aryl(8-quinolinyl)amido ligand 3,5-(CF3)2-(C6H3)QA has been installed onto the (BQA)Ru platform to provide (BQA)Ru(3,5-(CF3)2-(C6H3)QA)(PPh3). A bis(phosphino)borate ligand stabilizes the five-coordinate complex [Ph2B(CH2PPh2)2]Ru(BQA). Finally, access to dinitrogen complexes of the types [(BQA)Ru(N2)(PPh3)2][PF6], [(BQA)Ru(N2)(PMe3)2][PF6], and [(BQA)Os(N2)(PPh3)2][PF6] is provided by exposure of the sixth coordination site under a N2 atmosphere
Linear mixed models with endogenous covariates: modeling sequential treatment effects with application to a mobile health study
Mobile health is a rapidly developing field in which behavioral treatments
are delivered to individuals via wearables or smartphones to facilitate
health-related behavior change. Micro-randomized trials (MRT) are an
experimental design for developing mobile health interventions. In an MRT the
treatments are randomized numerous times for each individual over course of the
trial. Along with assessing treatment effects, behavioral scientists aim to
understand between-person heterogeneity in the treatment effect. A natural
approach is the familiar linear mixed model. However, directly applying linear
mixed models is problematic because potential moderators of the treatment
effect are frequently endogenous---that is, may depend on prior treatment. We
discuss model interpretation and biases that arise in the absence of additional
assumptions when endogenous covariates are included in a linear mixed model. In
particular, when there are endogenous covariates, the coefficients no longer
have the customary marginal interpretation. However, these coefficients still
have a conditional-on-the-random-effect interpretation. We provide an
additional assumption that, if true, allows scientists to use standard software
to fit linear mixed model with endogenous covariates, and person-specific
predictions of effects can be provided. As an illustration, we assess the
effect of activity suggestion in the HeartSteps MRT and analyze the
between-person treatment effect heterogeneity
Field Induced Positional Shift of Bloch Electrons and its Dynamical Implications
We derive the field correction to the Berry curvature of Bloch electrons,
which can be traced back to a positional shift due to the interband mixing
induced by external electromagnetic fields. The resulting semiclassical
dynamics is accurate to second order in the fields, in the same form as before,
provided that the wave packet energy is derived up to the same order. As
applications, we discuss the orbital magnetoelectric polarizability and predict
nonlinear anomalous Hall effects
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Rethinking Secure Precoding via Interference Exploitation: A Smart Eavesdropper Perspective
Based on the concept of constructive interference (CI), multiuser
interference (MUI) has recently been shown to be beneficial for communication
secrecy. A few CI-based secure precoding algorithms have been proposed that use
both the channel state information (CSI) and knowledge of the instantaneous
transmit symbols. In this paper, we examine the CI-based secure precoding
problem with a focus on smart eavesdroppers that exploit statistical
information gleaned from the precoded data for symbol detection. Moreover, the
impact of correlation between the main and eavesdropper channels is taken into
account. We first modify an existing CI-based preocding scheme to better
utilize the destructive impact of the interference. Then, we point out the
drawback of both the existing and the new modified CI-based precoders when
faced with a smart eavesdropper. To address this deficiency, we provide a
general principle for precoder design and then give two specific design
examples. Finally, the scenario where the eavesdropper's CSI is unavailable is
studied. Numerical results show that although our modified CI-based precoder
can achieve a better energy-secrecy trade-off than the existing approach, both
have a limited secrecy benefit. On the contrary, the precoders developed using
the new CI-design principle can achieve a much improved trade-off and
significantly degrade the eavesdropper's performance
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