10,323 research outputs found
Embedded density functional theory for covalently bonded and strongly interacting subsystems
Embedded density functional theory (e-DFT) is used to describe the electronic structure of strongly interacting molecular subsystems. We present a general implementation of the Exact Embedding (EE) method [J. Chem. Phys. 133, 084103 (2010)] to calculate the large contributions of the nonadditive kinetic potential (NAKP) in such applications. Potential energy curves are computed for the dissociation of Li^+–Be, CH_3–CF_3, and hydrogen-bonded water clusters, and e-DFT results obtained using the EE method are compared with those obtained using approximate kinetic energy functionals. In all cases, the EE method preserves excellent agreement with reference Kohn–Sham calculations, whereas the approximate functionals lead to qualitative failures in the calculated energies and equilibrium structures. We also demonstrate an accurate pairwise approximation to the NAKP that allows for efficient parallelization of the EE method in large systems; benchmark calculations on molecular crystals reveal ideal, size-independent scaling of wall-clock time with increasing system size
Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes
Density functional theory (DFT) embedding provides a formally exact framework
for interfacing correlated wave-function theory (WFT) methods with lower-level
descriptions of electronic structure. Here, we report techniques to improve the
accuracy and stability of WFT-in-DFT embedding calculations. In particular, we
develop spin-dependent embedding potentials in both restricted and unrestricted
orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and
we develop an orbital-occupation-freezing technique to improve the convergence
of optimized effective potential (OEP) calculations that arise in the
evaluation of the embedding potential. The new techniques are demonstrated in
applications to the van-der-Waals-bound ethylene-propylene dimer and to the
hexaaquairon(II) transition-metal cation. Calculation of the dissociation curve
for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces
full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating
errors in the dispersion interactions due to conventional exchange-correlation
(XC) functionals while simultaneously avoiding errors due to subsystem
partitioning across covalent bonds. Application of WFT-in-DFT embedding to the
calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II)
cation reveals that the majority of the dependence on the DFT XC functional can
be eliminated by treating only the single transition-metal atom at the WFT
level; furthermore, these calculations demonstrate the substantial effects of
open-shell contributions to the embedding potential, and they suggest that
restricted open-shell WFT-in-DFT embedding provides better accuracy than
unrestricted open-shell WFT-in-DFT embedding due to the removal of spin
contamination.Comment: 11 pages, 5 figures, 2 table
The Structural Sources of Socioeconomic Inequalities in Health: A Cross-National Perspective
This article investigates how macro-level structures condition the sources of socioeconomic inequalities in health. Drawing on multiple social science disciplines, the authors develop theoretically grounded propositions about how different types of welfare states, varieties of capitalism, and social structures give rise to cross-national variations in the sources of health inequalities. They consider how these macro-level structures affect the distribution of five key resources important to health, estimate the relative contribution that each resource makes to health inequalities, and compare those contributions in 21 developed democracies. Moving beyond a current literature focused on welfare states, the authors show how different types of political economies and social structures also condition the health gradient. This research carries implications for policy and suggests agendas for further investigation into the relationship between macro-level structures and inequalities in health
The Radial Orbit Instability in Collisionless N-Body Simulations
Using a suite of self-gravitating, collisionless N-body models, we
systematically explore a parameter space relevant to the onset and behavior of
the radial orbit instability (ROI), whose strength is measured by the systemic
axis ratios of the models. We show that a combination of two initial
conditions, namely the velocity anisotropy and the virial ratio, determines
whether a system will undergo ROI and exactly how triaxial the system will
become. A third initial condition, the radial shape of the density profile,
plays a smaller, but noticeable role. Regarding the dynamical development of
the ROI, the instability a) begins after systems collapse to their most compact
configuration and b) evolves fastest when a majority of the particles have
radially anisotropic orbits while there is a lack of centrally-concentrated
isotropic orbits. We argue that this is further evidence that self-reinforcing
torques are the key to the onset of the ROI. Our findings support the idea that
a separate orbit instability plays a role in halting the ROI.Comment: accepted for publication in ApJ. 9 figures in emulateapj styl
Stirring N-body systems: Universality of end states
We study the evolution of the phase-space of collisionless N-body systems
under repeated stirrings or perturbations. We find convergence towards a
limited solution group, in accordance with Hansen 2010, that is independent of
the initial system and environmental conditions, paying particular attention to
the assumed gravitational paradigm (Newtonian and MOND). We examine the effects
of changes to the perturbation scheme and in doing so identify a large group of
perturbations featuring radial orbit instability (ROI) which always lead to
convergence. The attractor is thus found to be a robust and reproducible effect
under a variety of circumstances
Density functional theory embedding for correlated wavefunctions: Improved methods for open-shell systems and transition metal complexes
Density functional theory (DFT) embedding provides a formally exact framework for interfacing correlated wave-function theory (WFT) methods with lower-level descriptions of electronic structure. Here, we report techniques to improve the accuracy and stability of WFT-in-DFT embedding calculations. In particular, we develop spin-dependent embedding potentials in both restricted and unrestricted orbital formulations to enable WFT-in-DFT embedding for open-shell systems, and develop an orbital-occupation-freezing technique to improve the convergence of optimized effective potential calculations that arise in the evaluation of the embedding potential. The new techniques are demonstrated in applications to the van-der-Waals-bound ethylene-propylene dimer and to the hexa-aquairon(II) transition-metal cation. Calculation of the dissociation curve for the ethylene-propylene dimer reveals that WFT-in-DFT embedding reproduces full CCSD(T) energies to within 0.1 kcal/mol at all distances, eliminating errors in the dispersion interactions due to conventional exchange-correlation (XC) functionals while simultaneously avoiding errors due to subsystem partitioning across covalent bonds. Application of WFT-in-DFT embedding to the calculation of the low-spin/high-spin splitting energy in the hexaaquairon(II) cation reveals that the majority of the dependence on the DFT XC functional can be eliminated by treating only the single transition-metal atom at the WFT level; furthermore, these calculations demonstrate the substantial effects of open-shell contributions to the embedding potential, and they suggest that restricted open-shell WFT-in-DFT embedding provides better accuracy than unrestricted open-shell WFT-in-DFT embedding due to the removal of spin contamination
Accurate basis set truncation for wavefunction embedding
Density functional theory (DFT) provides a formally exact framework for performing embedded subsystem electronic structure calculations, including DFT-in-DFT and wavefunction theory-in-DFT descriptions. In the interest of efficiency, it is desirable to truncate the atomic orbital basis set in which the subsystem calculation is performed, thus avoiding high-order scaling with respect to the size of the MO virtual space. In this study, we extend a recently introduced projection-based embedding method [F. R. Manby, M. Stella, J. D. Goodpaster, and T. F. Miller III, J. Chem. Theory Comput. 8, 2564 (2012)]10.1021/ct300544e to allow for the systematic and accurate truncation of the embedded subsystem basis set. The approach is applied to both covalently and non-covalently bound test cases, including water clusters and polypeptide chains, and it is demonstrated that errors associated with basis set truncation are controllable to well within chemical accuracy. Furthermore, we show that this approach allows for switching between accurate projection-based embedding and DFT embedding with approximate kinetic energy (KE) functionals; in this sense, the approach provides a means of systematically improving upon the use of approximate KE functionals in DFT embedding
Variation of receptor status in cancer of the breast.
One hundred and nineteen patients with breast cancer had 2 or more lesions removed for oestrogen (REc) or progesterone receptor (RPc) assay, either synchronously (on 38 occasions) or after an interval (on 91 occasions). In all but 7 both receptors were assayed for each lesion. The assays did not agree on the presence or absence of REc alone, RPc alone or the combination of both receptors in 11, 13 and 16% respectively of the synchronous samples, compared with 23, 30 and 43% of the asynchronous samples. The differences between the synchronous and asynchronous samples were significant for the combined receptors (P = 0.007) but not for REc (P = 0.176) or RPc alone (P = 0.077). Variation between asynchronous biopsies was greater when the earlier lesion contained RPc (18/37 disagreed) than when it did not (8/50) disagreed, P = 0.0023). This was not true for oestrogen receptor. In those remaining receptor positive there was only a weak correlation between the first and second values (Spearman rank correlation coefficient, rho = 0.39 for REc, P less than 0.02, and 0.45 for RPc, 0.05 less than P less than 0.1). Receptor levels and receptor status may change with time. Biopsy is most appropriate at the time when systemic treatment is proposed
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