92 research outputs found
Range-separated density-functional theory with random phase approximation: detailed formalism and illustrative applications
Using Green-function many-body theory, we present the details of a formally
exact adiabatic-connection fluctuation-dissipation density-functional theory
based on range separation, which was sketched in Toulouse, Gerber, Jansen,
Savin and Angyan, Phys. Rev. Lett. 102, 096404 (2009). Range-separated
density-functional theory approaches combining short-range density functional
approximations with long-range random phase approximations (RPA) are then
obtained as well-identified approximations on the long-range Green-function
self-energy. Range-separated RPA-type schemes with or without long-range
Hartree-Fock exchange response kernel are assessed on rare-gas and
alkaline-earth dimers, and compared to range-separated second-order
perturbation theory and range-separated coupled-cluster theory.Comment: 15 pages, 3 figures, 2 table
Geometric Measure of Indistinguishability for Groups of Identical Particles
The concept of p-orthogonality (1=< p =< n) between n-particle states is
introduced. It generalizes common orthogonality, which is equivalent to
n-orthogonality, and strong orthogonality between fermionic states, which is
equivalent to 1-orthogonality. Within the class of non p-orthogonal states a
finer measure of non p-orthogonality is provided by Araki's angles between
p-internal spaces. The p-orthogonality concept is a geometric measure of
indistinguishability that is independent of the representation chosen for the
quantum states. It induces a new hierarchy of approximations for group function
methods. The simplifications that occur in the calculation of matrix elements
between p-orthogonal group functions are presented
Van der Waals forces in density functional theory: perturbational long-range electron interaction corrections
Long-range exchange and correlation effects, responsible for the failure of
currently used approximate density functionals in describing van der Waals
forces, are taken into account explicitly after a separation of the
electron-electron interaction in the Hamiltonian into short- and long-range
components. We propose a "range-separated hybrid" functional based on a local
density approximation for the short-range exchange-correlation energy, combined
with a long-range exact exchange energy. Long-range correlation effects are
added by a second-order perturbational treatment. The resulting scheme is
general and is particularly well-adapted to describe van der Waals complexes,
like rare gas dimers.Comment: 8 pages, 1 figure, submitted to Phys. Rev.
Assessing the Performance of Recent Density Functionals for Bulk Solids
We assess the performance of recent density functionals for the
exchange-correlation energy of a nonmolecular solid, by applying accurate
calculations with the GAUSSIAN, BAND, and VASP codes to a test set of 24 solid
metals and non-metals. The functionals tested are the modified
Perdew-Burke-Ernzerhof generalized gradient approximation (PBEsol GGA), the
second-order GGA (SOGGA), and the Armiento-Mattsson 2005 (AM05) GGA. For
completeness, we also test more-standard functionals: the local density
approximation, the original PBE GGA, and the Tao-Perdew-Staroverov-Scuseria
(TPSS) meta-GGA. We find that the recent density functionals for solids reach a
high accuracy for bulk properties (lattice constant and bulk modulus). For the
cohesive energy, PBE is better than PBEsol overall, as expected, but PBEsol is
actually better for the alkali metals and alkali halides. For fair comparison
of calculated and experimental results, we consider the zero-point phonon and
finite-temperature effects ignored by many workers. We show how Gaussian basis
sets and inaccurate experimental reference data may affect the rating of the
quality of the functionals. The results show that PBEsol and AM05 perform
somewhat differently from each other for alkali metal, alkaline earth metal and
alkali halide crystals (where the maximum value of the reduced density gradient
is about 2), but perform very similarly for most of the other solids (where it
is often about 1). Our explanation for this is consistent with the importance
of exchange-correlation nonlocality in regions of core-valence overlap.Comment: 32 pages, single pdf fil
Random-phase approximation and its applications in computational chemistry and materials science
The random-phase approximation (RPA) as an approach for computing the
electronic correlation energy is reviewed. After a brief account of its basic
concept and historical development, the paper is devoted to the theoretical
formulations of RPA, and its applications to realistic systems. With several
illustrating applications, we discuss the implications of RPA for computational
chemistry and materials science. The computational cost of RPA is also
addressed which is critical for its widespread use in future applications. In
addition, current correction schemes going beyond RPA and directions of further
development will be discussed.Comment: 25 pages, 11 figures, published online in J. Mater. Sci. (2012
Polymorphic Signature of the Anti-inflammatory Activity of 2,2′- {[1,2-Phenylenebis(methylene)]bis(sulfanediyl)}bis(4,6- dimethylnicotinonitrile)
Weak noncovalent interactions are the basic forces in crystal engineering. Polymorphism in flexible molecules is very common, leading to the development of the crystals of same organic compounds with different medicinal and material properties. Crystallization of 2,2′- {[1,2-phenylenebis(methylene)]bis(sulfanediyl)}bis(4,6-dimethylnicotinonitrile)
by evaporation at room temperature from ethyl acetate and hexane and from methanol and ethyl acetate gave stable polymorphs 4a and 4b, respectively, while in acetic acid, it gave metastable polymorph 4c. The polymorphic behavior of the compound has been visualized through singlecrystal X-ray and Hirshfeld analysis. These polymorphs are
tested for anti-inflammatory activity via the complete Freund’s adjuvant-induced rat paw model, and compounds have exhibited moderate activities. Studies of docking in the catalytic site of cyclooxygenase-2 were used to identify potential anti-inflammatory lead compounds. These results suggest that the supramolecular aggregate structure, which is formed in solution, influences the solid state structure and the biological activity obtained upon crystallization
van der Waals Interactions in Material Modelling
Van der Waals (vdW) interactions stem from electronic zero-point fluctuations and are often critical for the correct description of structure, stability, and response properties of molecules and materials, including biomolecules, nanomaterials, and material interfaces. Here, we give a conceptual as well as mathematical overview of the current state of modeling vdW interactions,focusing in particular on the consequences of different approximations for practical applications. We present a systematic classification of approximate first-principles models based on the adiabatic-connection fluctuation-dissipation theorem, namely the nonlocal density functionals, interatomic methods, and methods based on the random-phase approximation. The applicability of these methods to different types of materials and material properties is discussed in connection with availability of theoretical and experimental benchmarks. We conclude with a roadmap of the open problems that remain to be solved to construct a universal, efficient, and accurate vdW model for realistic material modeling
Fragment-Localized Kohn−Sham Orbitals via a Singles Configuration-Interaction Procedure and Application to Local Properties and Intermolecular Energy Decomposition Analysis
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