Using short-term postseismic displacements to infer the ambient deformation conditions of the upper mantle

Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophyscial Research 117 (2012): B01409, doi:10.1029/2011JB008562.To interpret short-term postseismic surface displacements in the context of key ambient conditions (e.g., temperature, pressure, background strain rate, water content, creep mechanism), we combined steady state and transient flow into a single constitutive relation that can explain the response of a viscoelastic material to a change in stress. The flow law is then used to investigate mantle deformation beneath the Eastern California Shear Zone following the 1999 M7.1 Hector Mine earthquake. The flow law parameters are determined using finite element models of relaxation processes, constrained by surface displacement time series recorded by 55 continuous GPS stations for 7 years following the earthquake. Results suggest that postseismic flow following the Hector Mine earthquake occurs below a depth of ~50 km and is controlled by dislocation creep of wet olivine. Diffusion creep models can also explain the data, but require a grain size (3.5 mm) that is smaller than the inferred grain size (10–20 mm) based on the mantle conditions at these depths. In addition, laboratory flow laws predict dislocation creep would dominate at the stress/grain size conditions that provide the best fit to diffusion creep models. Model results suggest a transient creep phase that lasts ~1 year and has a viscosity ~10 times lower than subsequent steady state flow, in general agreement with laboratory observations. The postseismic response is best explained as occurring within a relatively hot upper mantle (e.g., 1200–1300°C at 50 km depth) with a long-term background mantle strain rate of 0.1–0.2 μstrain/yr, consistent with the observed surface strain rate. Long-term background shear stresses at the top of the mantle are ~4 MPa, then decrease with depth to a minimum of 0.1–0.2 MPa at 70 km depth before increasing slowly with depth due to the pressure dependence of viscosity. These conditions correspond to a background viscosity of 1021 Pa s within a thin mantle lid that decreases to ~5 × 1019 Pa s within the underlying asthenosphere. This study shows the utility of using short-term postseismic observations to infer long-term mantle conditions that are not readily observable by other means.This work was supported by the National Science Foundation grants EAR-0952234 (A.M.F.), EAR-0810188 (G.H.), and EAR-0854673 (M.D.B.).2012-07-3

Rapid spatiotemporal variations in rift structure during development of the Corinth Rift, central Greece

The Corinth Rift, central Greece, enables analysis of early rift development as it is young (<5Ma) and highly active and its full history is recorded at high resolution by sedimentary systems. A complete compilation of marine geophysical data, complemented by onshore data, is used to develop a high-resolution chronostratigraphy and detailed fault history for the offshore Corinth Rift, integrating interpretations and reconciling previous discrepancies. Rift migration and localization of deformation have been significant within the rift since inception. Over the last circa 2Myr the rift transitioned from a spatially complex rift to a uniform asymmetric rift, but this transition did not occur synchronously along strike. Isochore maps at circa 100kyr intervals illustrate a change in fault polarity within the short interval circa 620-340ka, characterized by progressive transfer of activity from major south dipping faults to north dipping faults and southward migration of discrete depocenters at ~30m/kyr. Since circa 340ka there has been localization and linkage of the dominant north dipping border fault system along the southern rift margin, demonstrated by lateral growth of discrete depocenters at ~40m/kyr. A single central depocenter formed by circa 130ka, indicating full fault linkage. These results indicate that rift localization is progressive (not instantaneous) and can be synchronous once a rift border fault system is established. This study illustrates that development processes within young rifts occur at 100kyr timescales, including rapid changes in rift symmetry and growth and linkage of major rift faults

Advances in Molecular Quantum Chemistry Contained in the Q-Chem 4 Program Package

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube

Software for the frontiers of quantum chemistry:An overview of developments in the Q-Chem 5 package

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange–correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear–electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an “open teamware” model and an increasingly modular design

Extreme drought impacts have been underestimated in grasslands and shrublands globally

Climate change is increasing the frequency and severity of short-term (~1 y) drought events-the most common duration of drought-globally. Yet the impact of this intensification of drought on ecosystem functioning remains poorly resolved. This is due in part to the widely disparate approaches ecologists have employed to study drought, variation in the severity and duration of drought studied, and differences among ecosystems in vegetation, edaphic and climatic attributes that can mediate drought impacts. To overcome these problems and better identify the factors that modulate drought responses, we used a coordinated distributed experiment to quantify the impact of short-term drought on grassland and shrubland ecosystems. With a standardized approach, we imposed ~a single year of drought at 100 sites on six continents. Here we show that loss of a foundational ecosystem function-aboveground net primary production (ANPP)-was 60% greater at sites that experienced statistically extreme drought (1-in-100-y event) vs. those sites where drought was nominal (historically more common) in magnitude (35% vs. 21%, respectively). This reduction in a key carbon cycle process with a single year of extreme drought greatly exceeds previously reported losses for grasslands and shrublands. Our global experiment also revealed high variability in drought response but that relative reductions in ANPP were greater in drier ecosystems and those with fewer plant species. Overall, our results demonstrate with unprecedented rigor that the global impacts of projected increases in drought severity have been significantly underestimated and that drier and less diverse sites are likely to be most vulnerable to extreme drought

Theoretical Investigation of the Oxidative Carbonylation of Toluene to Toluic Acid over Rh(III) and Pd(II), and Theoretical Method Development for the Rapid Identification of ab initio Transition States

The use of theoretical chemistry techniques in the investigation of catalytic reactions has been able to provide strong insights into the inner workings of various chemical mechanisms. In tandem with experimental results, such studies often provide information by computing reaction rates with transition state theory, predicting and/or confirming various spectroscopic experiments, and elucidating the identities and structures of key stable intermediates and short-lived transition states. The present work is concerned with the application of these techniques to the study of the oxidative carbonization of toluene to toluic acid over Rh(III) and Pd(II), as well as the development of theoretical techniques to efficiently find ab initio transition states for use in such studies. Previous work has shown that the oxidative carbonylation of toluene to form toluic acid is possible with Rh(III) and Pd(II) with acetic acid. These reactions are believed to operate via a rate-limiting electrophilic mechanism in which toluene binds to the metal complex and has a C-H bond activated. Previous works have suggested that the active catalyst for the Rh(III) system is Rh(CF3COO)3(CO)2, and Pd(CF3COO)2 for the Pd(II) system, though these were not rigorously confirmed. In this work, we properly identify the Rh(III) species as the active catalyst through a series of ab initio spectroscopic calculations with comparison to experiments. Additionally, an unprecedented interaction between an acetate and carbonyl ligand on the Rh(CF3COO)2(CO)2 catalyst is investigated and found to be the result of an unusual charge balance within the structure. Prior work has shown that using trifluoroacetic acid instead of acetic acid significantly increases the rate of reaction, without investigating further. This work demonstrates that the reaction rate passes through a maximum for intermediate strength acids, which is due to competition between the two sub-steps of the rate-limiting step. Weakly basic anionic ligands increase the positive charge on the metal center and increase the rate of toluene binding while decreasing the ability of the same ligands to accept the activated proton. A similar trend and explanation were found with a model catalyst for the Pd(II) system as the ligands were varied. The second part of this work concerns the development of efficient transition state searching algorithms. The calculation of theoretical rate constants often employs transition state theory, but requires the user to possess the transition state structure. The local search for such a structure requires an extremely good guess, and is most practically obtained with the help of an automated guess generator. The most commonly used algorithms operate by optimizing a chain of molecular images connecting known reactant and product structures into the reaction pathway. One such routine, the Growing String Method (GSM), grows a chain of states inward from the known endpoints while optimizing these points. The original GSM algorithm relies upon cartesian coordinates with cubic splines for adding new structures to the chain, however this often leads to unrealistic images which require many steps to relax into the reaction pathway. By replacing the cartesian coordinate interpolation with Linear Synchronous Transit interpolation, the computational cost of optimizing complex reaction pathways may be cut approximately in half. Additionally, by simplifying the algorithm to focus computational effort on the location of just the transition state rather than the entire reaction pathway, the overall cost may be reduced even further. In this new method, the Freezing String Method, nodes are iteratively added to a growing chain, optimized for several steps, and then frozen in place for the remainder of the execution

Grain-size dynamics beneath mid-ocean ridges : implications for permeability and melt extraction

Grain size is an important control on mantle viscosity and permeability, but is difficult or impossible to measure in situ. We construct a two-dimensional, single phase model for the steady state mean grain size beneath a mid-ocean ridge. The mantle rheology is modeled as a composite of diffusion creep, dislocation creep, dislocation accommodated grain boundary sliding, and a plastic stress limiter. The mean grain size is calculated by the paleowattmeter relationship of Austin and Evans (2007). We investigate the sensitivity of our model to global variations in grain growth exponent, potential temperature, spreading-rate, and mantle hydration. We interpret the mean grain-size field in terms of its permeability to melt transport. The permeability structure due to mean grain size may be approximated as a high permeability region beneath a low permeability region. The transition between high and low permeability regions occurs across a boundary that is steeply inclined toward the ridge axis. We hypothesize that such a permeability structure generated from the variability of the mean grain size may focus melt toward the ridge axis, analogous to Sparks and Parmentier (1991)-type focusing. This focusing may, in turn, constrain the region where signifi- cant melt fractions are observed by seismic or magnetotelluric surveys. This interpretation of melt focusing via the grain size permeability structure is consistent with MT observation of the asthenosphere beneath the East Pacific Rise