Towards Understanding Photodegradation Pathways in Lignins:The Role of Intramolecular Hydrogen Bonding in Excited States

The photoinduced dynamics of the lignin building blocks syringol, guaiacol, and phenol were studied using time-resolved ion yield spectroscopy and velocity map ion imaging. Following irradiation of syringol and guaiacol with a broad-band femtosecond ultraviolet laser pulse, a coherent superposition of out-of-plane OH torsion and/or OMe torsion/flapping motions is created in the first excited 1ππ* (S1) state, resulting in a vibrational wavepacket, which is probed by virtue of a dramatic nonplanar → planar geometry change upon photoionization from S1 to the ground state of the cation (D0). Any similar quantum beat pattern is absent in phenol. In syringol, the nonplanar geometry in S1 is pronounced enough to reduce the degree of intramolecular H bonding (between OH and OMe groups), enabling H atom elimination from the OH group. For guaiacol, H bonding is preserved after excitation, despite the nonplanar geometry in S1, and prevents O–H bond fission. This behavior affects the propensities for forming undesired phenoxyl radical sites in these three lignin chromophores and provides important insight into their relative “photostabilities” within the larger biopolymer

The Earth System Grid Federation: Delivering globally accessible petascale data for CMIP5

The fifth Coupled Model Intercomparison Project (CMIP5) will involve the global production and analysis of petabytes of data. The Program for Climate Model Diagnosis and Intercomparison (PCMDI), with responsibility for archival for CMIP5, has established the global “Earth System Grid Federation” (ESGF) of data producers and data archives to support CMIP5. ESGF will provide a set of globally synchronised views of globally distributed data – including some large cache replicants which will be persisted for (at least) decades. Here we describe the archive requirements and key aspects of the resulting architecture. ESGF will stress international networks, as well as the data archives themselves – but significantly less than would have been the case of a centralised archive. Developing and deploying the ESGF has exploited good will and best efforts, but future developments are likely to require more formalised architecture and management

Mid-Infrared Spectroscopy of Uranus from the Spitzer Infrared Spectrometer: 2. Determination of the Mean Composition of the Upper Troposphere and Stratosphere

Mid-infrared spectral observations Uranus acquired with the Infrared Spectrometer (IRS) on the Spitzer Space Telescope are used to determine the abundances of C2H2, C2H6, CH3C2H, C4H2, CO2, and tentatively CH3 on Uranus at the time of the 2007 equinox. For vertically uniform eddy diffusion coefficients in the range 2200-2600 cm2 s-1, photochemical models that reproduce the observed methane emission also predict C2H6 profiles that compare well with emission in the 11.6-12.5 micron wavelength region, where the nu9 band of C2H6 is prominent. Our nominal model with a uniform eddy diffusion coefficient Kzz = 2430 cm2 sec-1 and a CH4 tropopause mole fraction of 1.6x10-5 provides a good fit to other hydrocarbon emission features, such as those of C2H2 and C4H2, but the model profile for CH3C2H must be scaled by a factor of 0.43, suggesting that improvements are needed in the chemical reaction mechanism for C3Hx species. The nominal model is consistent with a CH3D/CH4 ratio of 3.0+-0.2x10-4. From the best-fit scaling of these photochemical-model profiles, we derive column abundances above the 10-mbar level of 4.5+01.1/-0.8 x 10+19 molecule-cm-2 for CH4, 6.2 +- 1.0 x 10+16 molecule-cm-2 for C2H2 (with a value 24% higher from a different longitudinal sampling), 3.1 +- 0.3 x 10+16 molecule-cm-2 for C2H6, 8.6 +- 2.6 x 10+13 molecule-cm-2 for CH3C2H, 1.8 +- 0.3 x 10+13 molecule-cm-2 for C4H2, and 1.7 +- 0.4 x 10+13 molecule-cm-2 for CO2 on Uranus. Our results have implications with respect to the influx rate of exogenic oxygen species and the production rate of stratospheric hazes on Uranus, as well as the C4H2 vapor pressure over C4H2 ice at low temperatures

Effects of sea-level rise on barrier island groundwater system dynamics – ecohydrological implications

This paper is not subject to U.S. copyright. The definitive version was published in Ecohydrology 7 (2014): 1064–1071, doi:10.1002/eco.1442.We used a numerical model to investigate how a barrier island groundwater system responds to increases of up to 60 cm in sea level. We found that a sea-level rise of 20 cm leads to substantial changes in the depth of the water table and the extent and depth of saltwater intrusion, which are key determinants in the establishment, distribution and succession of vegetation assemblages and habitat suitability in barrier islands ecosystems. In our simulations, increases in water-table height in areas with a shallow depth to water (or thin vadose zone) resulted in extensive groundwater inundation of land surface and a thinning of the underlying freshwater lens. We demonstrated the interdependence of the groundwater response to island morphology by evaluating changes at three sites. This interdependence can have a profound effect on ecosystem composition in these fragile coastal landscapes under long-term changing climatic conditions.We used a numerical model to investigate how a barrier island groundwater system responds to increases of up to 60 cm in sea level. We found that a sea-level rise of 20 cm leads to substantial changes in the depth of the water table and the extent and depth of saltwater intrusion, which are key determinants in the establishment, distribution and succession of vegetation assemblages and habitat suitability in barrier islands ecosystems. In our simulations, increases in water-table height in areas with a shallow depth to water (or thin vadose zone) resulted in extensive groundwater inundation of land surface and a thinning of the underlying freshwater lens. We demonstrated the interdependence of the groundwater response to island morphology by evaluating changes at three sites. This interdependence can have a profound effect on ecosystem composition in these fragile coastal landscapes under long-term changing climatic conditions. Published 2013. This article is a U.S. Government work and is in the public domain in the USA

Layered architecture for quantum computing

We develop a layered quantum computer architecture, which is a systematic framework for tackling the individual challenges of developing a quantum computer while constructing a cohesive device design. We discuss many of the prominent techniques for implementing circuit-model quantum computing and introduce several new methods, with an emphasis on employing surface code quantum error correction. In doing so, we propose a new quantum computer architecture based on optical control of quantum dots. The timescales of physical hardware operations and logical, error-corrected quantum gates differ by several orders of magnitude. By dividing functionality into layers, we can design and analyze subsystems independently, demonstrating the value of our layered architectural approach. Using this concrete hardware platform, we provide resource analysis for executing fault-tolerant quantum algorithms for integer factoring and quantum simulation, finding that the quantum dot architecture we study could solve such problems on the timescale of days.Comment: 27 pages, 20 figure

A Global Repository for Planet-Sized Experiments and Observations

Working across U.S. federal agencies, international agencies, and multiple worldwide data centers, and spanning seven international network organizations, the Earth System Grid Federation (ESGF) allows users to access, analyze, and visualize data using a globally federated collection of networks, computers, and software. Its architecture employs a system of geographically distributed peer nodes that are independently administered yet united by common federation protocols and application programming interfaces (APIs). The full ESGF infrastructure has now been adopted by multiple Earth science projects and allows access to petabytes of geophysical data, including the Coupled Model Intercomparison Project (CMIP)—output used by the Intergovernmental Panel on Climate Change assessment reports. Data served by ESGF not only include model output (i.e., CMIP simulation runs) but also include observational data from satellites and instruments, reanalyses, and generated images. Metadata summarize basic information about the data for fast and easy data discovery.This work was supported by the U.S. Department of Energy Office of Science/Office of Biological and Environmental Research under Contract DE-AC52-07NA27344 at Lawrence Livermore National Laboratory. VB is supported by the Cooperative Institute for Climate Science, Princeton University, under Award NA08OAR4320752 from the National Oceanic and Atmospheric Administration, U.S. Department of Commerce. Part of this work was undertaken with the assistance of resources from the National Computational Infrastructure (NCI), which is supported by the Australian Government. Part of this activity was performed on behalf of the Jet Propulsion Laboratory, California Institute of Technology, under a contract with NASA. Part of this activity was performed on behalf of the Goddard Space Flight Center, under a contract with NASA. This work was supported by ANR Convergence project (Grant Agreement ANR-13-MONU-0008). This work was supported by FP7 IS-ENES2 project (Grant Agreement 312979)

BB Intermeson Potentials in the Quark Model

In this paper we derive quark model results for scattering amplitudes and equivalent low energy potentials for heavy meson pairs, in which each meson contains a heavy quark. This "BB" system is an attractive theoretical laboratory for the study of the nuclear force between color singlets; the hadronic system is relatively simple, and there are lattice gauge theory (LGT) results for V_BB(r) which may be compared to phenomenological models. We find that the quark model potential (after lattice smearing) has qualitative similarities to the LGT potential in the two B*B* channels in which direct comparison is possible, although there is evidence of a difference in length scales. The quark model prediction of equal magnitude but opposite sign for I=0 and I=1 potentials also appears similar to LGT results at intermediate r. There may however be a discrepancy between the LGT and quark model I=1 BB potentials. A numerical study of the two-meson Schrodinger equations in the (bqbar)(bqbar) and (cqbar)(cqbar) sectors with the quark model potentials finds a single "molecule", in the I=0 BB* sector. Binding in other channels might occur if the quark model forces are augmented by pion exchange.Comment: 30 pages, 5 figures, revtex and epsfig. Submitted to Phys. Rev.