10,000 publications from this institution
Abstract The application of the eddy covariance flux method to measure fluxes of trace gas and energy between ecosystems and the atmosphere has exploded over the past 25 years. This opinion paper provides a perspective on the contributions and future opportunities of the eddy covariance method. First, the paper discusses the pros and cons of this method relative to other methods used to measure the exchange of trace gases between ecosystems and the atmosphere. Second, it discusses how the use of eddy covariance method has grown and evolved. Today, more than 400 flux measurement sites are operating world‐wide and the duration of the time series exceed a decade at dozens of sites. Networks of tower sites now enable scientists to ask scientific questions related to climatic and ecological gradients, disturbance, changes in land use, and management. The paper ends with discussions on where the field of flux measurement is heading. Topics discussed include role of open access data sharing and data mining, in this new era of big data, and opportunities new sensors that measure a variety of trace gases, like volatile organic carbon compounds, methane and nitrous oxide, and aerosols, may yield.
This Perspective presents the fundamental principles, the elementary reactions, the initial catalytic systems, and the contemporary catalysts that have converted C-H bond functionalization from a curiosity to a reality for synthetic chemists. Many classes of elementary reactions involving transition-metal complexes cleave C-H bonds at typically unreactive positions. These reactions, coupled with a separate or simultaneous functionalization process lead to products containing new C-C, C-N, and C-O bonds. Such reactions were initially studied for the conversion of light alkanes to liquid products, but they have been used (and commercialized in some cases) most often for the synthesis of the more complex structures of natural products, medicinally active compounds, and aromatic materials. Such a change in direction of research in C-H bond functionalization is remarkable because the reactions must occur at an unactivated C-H bond over functional groups that are more reactive than the C-H bond toward classical reagents. The scope of reactions that form C-C bonds or install functionality at an unactivated C-H bond will be presented, and the potential future utility of these reactions will be discussed.
A long-standing limitation of first-principles calculations of substitutional alloy phase diagrams is the difficulty in accounting for lattice vibrations. A survey of the theoretical and experimental literature seeking to quantify the effect of lattice vibrations on phase stability indicates that they can be significant. Typical vibrational entropy differences between phases are of the order of 0.1 to 0.2kB/atom, which is comparable to the typical values of configurational entropy differences in binary alloys (at most 0.693kB/atom). This article presents the basic formalism underlying ab initio phase diagram calculations, along with the generalization required to account for lattice vibrations. The authors review the various techniques allowing the theoretical calculation and the experimental determination of phonon dispersion curves and related thermodynamic quantities, such as vibrational entropy or free energy. A clear picture of the origin of vibrational entropy differences between phases in an alloy system is presented that goes beyond the traditional bond counting and volume change arguments. Vibrational entropy change can be attributed to the changes in chemical bond stiffness associated with the changes in bond length that take place during a phase transformation. This so-called “bond stiffness vs bond length” interpretation both summarizes the key phenomenon driving vibrational entropy changes and provides a practical tool to model them.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Abstract The linear response of a selected arch dam to harmonic upstream, vertical or cross‐stream ground motion is presented for a wide range of the important system parameters characterizing the properties of the dam, foundation rock, impounded water and reservoir boundary materials. Based on these frequency‐response functions, the dam‐foundation rock interaction effects in the dynamic response of arch dams are investigated.
There is an increasing conflict between business incentives to hide models and data as trade secrets, and the societal need for algorithmic transparency. For example, a rightsholder wishing to know whether their copyrighted works have been used during training must convince the model provider to allow a third party to audit the model and data. Finding a mutually agreeable third party is difficult, and the associated costs often make this approach impractical. In this work, we show that it is possible to simultaneously allow model providers to keep their model weights (but not architecture) and data secret while allowing other parties to trustlessly audit model and data properties. We do this by designing a protocol called ZkAudit in which model providers publish cryptographic commitments of datasets and model weights, alongside a zero-knowledge proof (ZKP) certifying that published commitments are derived from training the model. Model providers can then respond to audit requests by privately computing any function F of the dataset (or model) and releasing the output of F alongside another ZKP certifying the correct execution of F. To enable ZkAudit, we develop new methods of computing ZKPs for SGD on modern neural nets for simple recommender systems and image classification models capable of high accuracies on ImageNet. Empirically, we show it is possible to provide trustless audits of DNNs, including copyright, censorship, and counterfactual audits with little to no loss in accuracy.
We consider the problem of service composition in a wide area network, where an end-user can send its packets through intermediate processing points (middleboxes) which can perform a variety of services. Example of such services are filtering, intrusion detection, anonymization, transcoding, and caching. In this paper, we argue that the Internet Indirection Infrastructure (i3)--an overlay network architecture that enables users to locate services and control the path followed by their packets--provides a natural platform for service composition. We discuss the challenges in implementing service compositions on top of i3, and suggest several approaches to address these challenges.
