The Hamiltonian of the V15_{15} Spin System from first-principles Density-Functional Calculations

We report first-principles all-electron density-functional based studies of the electronic structure, magnetic ordering and anisotropy for the V$_{15}$ molecular magnet. From these calculations, we determine a Heisenberg Hamiltonian with four antiferromagnetic and one {\em ferromagnetic} coupling. We perform direct diagonalization to determine the temperature dependence of the susceptibility. This Hamiltonian reproduces the experimentally observed spin $S$=1/2 ground state and low-lying $S$=3/2 excited state. A small anisotropy term is necessary to account for the temperature independent part of the magnetization curve.Comment: 4 pages in RevTeX format + 2 ps-figures, accepted by PRL Feb. 2001 (previous version was an older version of the paper

Accelerated recent warming and temperature variability over the past eight centuries in the central Asian Altai from blue intensity in tree rings

Funding: National Science Foundation (NSF). Grant Number: 1737788 and NOAA Climate and Global Change Postdoc Fellow Program. Grant Number: NA18NWS4620043B.Warming in Central Asia has been accelerating over the past three decades and is expected to intensify through the end of this century. Here, we develop a summer temperature reconstruction for western Mongolia spanning eight centuries (1269–2004 C.E.) using delta blue intensity measurements from annual rings of Siberian larch. A significant cooling response is observed in the year following major volcanic events and up to five years post-eruption. Observed summer temperatures since the 1990s are the warmest over the past eight centuries, an observation that is also well captured in Coupled Model Intercomparison Project (CMIP5) climate model simulations. Projections for summer temperature relative to observations suggest further warming of between ∼3°C and 6°C by the end of the century (2075–2099 cf. 1950–2004) under the representative concentration pathways 4.5 and 8.5 (RCP4.5 and RCP8.5) emission scenarios. We conclude that projected future warming lies beyond the range of natural climate variability for the past millennium as estimated by our reconstruction.Publisher PDFPeer reviewe

Effect of local Coulomb interactions on the electronic structure and exchange interactions in Mn12 magnetic molecules

We have studied the effect of local Coulomb interactions on the electronic structure of the molecular magnet Mn12-acetate within the LDA+U approach. The account of the on-site repulsion results in a finite energy gap and an integer value of the molecule's magnetic moment, both quantities being in a good agreement with the experimental results. The resulting magnetic moments and charge states of non-equivalent manganese ions agree very well with experiments. The calculated values of the intramolecular exchange parameters depend on the molecule's spin configuration, differing by 25-30% between the ferrimagnetic ground state and the completely ferromagnetic configurations. The values of the ground-state exchange coupling parameters are in reasonable agreement with the recent data on the magnetization jumps in megagauss magnetic fields. Simple estimates show that the obtained exchange parameters can be applied, at least qualitatively, to the description of the spin excitations in Mn12-acetate.Comment: RevTeX, LaTeX2e, 4 EPS figure

The longevity of broadleaf deciduous trees in Northern Hemisphere temperate forests: insights from tree-ring series

Understanding the factors controlling the expression of longevity in trees is still an outstanding challenge for tree biologists and forest ecologists. We gathered tree-ring data and literature for broadleaf deciduous (BD) temperate trees growing in closed-canopy old-growth (OG) forests in the Northern Hemisphere to explore the role of geographic patterns, climate variability, and growth rates on longevity. Our pan-continental analysis, covering 25 species from 12 genera, showed that 300–400 years can be considered a baseline threshold for maximum tree lifespan in many temperate deciduous forests. Maximum age varies greatly in relation to environmental features, even within the same species. Tree longevity is generally promoted by reduced growth rates across large genetic differences and environmental gradients. We argue that slower growth rates, and the associated smaller size, provide trees with an advantage against biotic and abiotic disturbance agents, supporting the idea that size, not age, is the main constraint to tree longevity. The oldest trees were living most of their life in subordinate canopy conditions and/or within primary forests in cool temperate environments and outside major storm tracks. Very old trees are thus characterized by slow growth and often live in forests with harsh site conditions and infrequent disturbance events that kill much of the trees. Temperature inversely controls the expression of longevity in mesophilous species (Fagus spp.), but its role in Quercus spp. is more complex and warrants further research in disturbance ecology. Biological, ecological, and historical drivers must be considered to understand the constraints imposed to longevity within different forest landscapes

Direct Minimization Generating Electronic States with Proper Occupation Numbers

We carry out the direct minimization of the energy functional proposed by Mauri, Galli and Car to derive the correct self-consistent ground state with fractional occupation numbers for a system degenerating at the Fermi level. As a consequence, this approach enables us to determine the electronic structure of metallic systems to a high degree of accuracy without the aid of level broadening of the Fermi-distribution function. The efficiency of the method is illustrated by calculating the ground-state energy of C$_2$ and Si$_2$ molecules and the W(110) surface to which a tungsten adatom is adsorbed.Comment: 4 pages, 4 figure

Variational Hilbert space truncation approach to quantum Heisenberg antiferromagnets on frustrated clusters

We study the spin-$\frac{1}{2}$ Heisenberg antiferromagnet on a series of finite-size clusters with features inspired by the fullerenes. Frustration due to the presence of pentagonal rings makes such structures challenging in the context of quantum Monte-Carlo methods. We use an exact diagonalization approach combined with a truncation method in which only the most important basis states of the Hilbert space are retained. We describe an efficient variational method for finding an optimal truncation of a given size which minimizes the error in the ground state energy. Ground state energies and spin-spin correlations are obtained for clusters with up to thirty-two sites without the need to restrict the symmetry of the structures. The results are compared to full-space calculations and to unfrustrated structures based on the honeycomb lattice.Comment: 22 pages and 12 Postscript figure

First-principles calculations of the self-trapped exciton in crystalline NaCl

The atomic and electronic structure of the lowest triplet state of the off-center (C2v symmetry) self-trapped exciton (STE) in crystalline NaCl is calculated using the local-spin-density (LSDA) approximation. In addition, the Franck-Condon broadening of the luminescence peak and the a1g -> b3u absorption peak are calculated and compared to experiment. LSDA accurately predicts transition energies if the initial and final states are both localized or delocalized, but 1 eV discrepancies with experiment occur if one state is localized and the other is delocalized.Comment: 4 pages with 4 embeddded figure

A first-principles density-functional calculation of the electronic and vibrational structure of the key melanin monomers

We report first-principles density-functional calculations for hydroquinone (HQ), indolequinone (IQ), and semiquinone (SQ). These molecules are believed to be the basic building blocks of the eumelanins, a class of biomacromolecules with important biological functions (including photoprotection) and with the potential for certain bioengineering applications. We have used the difference of self-consistent fields method to study the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, HL. We show that HL is similar in IQ and SQ, but approximately twice as large in HQ. This may have important implications for our understanding of the observed broadband optical absorption of the eumelanins. The possibility of using this difference in HL to molecularly engineer the electronic properties of eumelanins is discussed. We calculate the infrared and Raman spectra of the three redox forms from first principles. Each of the molecules have significantly different infrared and Raman signatures, and so these spectra could be used in situ to nondestructively identify the monomeric content of macromolecules. It is hoped that this may be a helpful analytical tool in determining the structure of eumelanin macromolecules and hence in helping to determine the structure-property-function relationships that control the behavior of the eumelanins

Centennial-scale reductions in nitrogen availability in temperate forests of the United States

Forests cover 30% of the terrestrial Earth surface and are a major component of the global carbon (C) cycle. Humans have doubled the amount of global reactive nitrogen (N), increasing deposition of N onto forests worldwide. However, other global changes—especially climate change and elevated atmospheric carbon dioxide concentrations—are increasing demand for N, the element limiting primary productivity in temperate forests, which could be reducing N availability. To determine the long-term, integrated effects of global changes on forest N cycling, we measured stable N isotopes in wood, a proxy for N supply relative to demand, on large spatial and temporal scales across the continental U.S.A. Here, we show that forest N availability has generally declined across much of the U.S. since at least 1850 C.E. with cool, wet forests demonstrating the greatest declines. Across sites, recent trajectories of N availability were independent of recent atmospheric N deposition rates, implying a minor role for modern N deposition on the trajectory of N status of North American forests. Our results demonstrate that current trends of global changes are likely to be consistent with forest oligotrophication into theforeseeable future, further constraining forest C fixation and potentially storage