540 research outputs found
Warming Up Density Functional Theory
Density functional theory (DFT) has become the most popular approach to
electronic structure across disciplines, especially in material and chemical
sciences. Last year, at least 30,000 papers used DFT to make useful predictions
or give insight into an enormous diversity of scientific problems, ranging from
battery development to solar cell efficiency and far beyond. The success of
this field has been driven by usefully accurate approximations based on known
exact conditions and careful testing and validation. In the last decade,
applications of DFT in a new area, warm dense matter, have exploded. DFT is
revolutionizing simulations of warm dense matter including applications in
controlled fusion, planetary interiors, and other areas of high energy density
physics. Over the past decade or so, molecular dynamics calculations driven by
modern density functional theory have played a crucial role in bringing
chemical realism to these applications, often (but not always) with excellent
agreement with experiment. This chapter summarizes recent work from our group
on density functional theory at non-zero temperatures, which we call thermal
DFT. We explain the relevance of this work in the context of warm dense matter,
and the importance of quantum chemistry to this regime. We illustrate many
basic concepts on a simple model system, the asymmetric Hubbard dimer
Controlling the yield and structure of carbon nanofibers grown on a nickel/activated carbon catalyst
Carbon nanofibers (CNFs) were grown via the chemical vapor deposition of C2H4 on an activated carbon (AC)-supported Ni catalyst. The texture of the CNF/AC composites can be tuned by varying the growth temperature and by treatment in reducing atmosphere prior to C2H4/H2 exposure. The Ni-catalyzed gasification of the AC support increases the microporosity of the composite and shown to be dominant throughout the composite synthesis especially during reduction, subsequent treatment in reducing atmosphere, and CNF growth at low temperatures. N2 isotherm and scanning electron microscope were used to characterize the texture and morphology of the composites. Subsequent treatment in reducing atmosphere were shown to increase the Ni catalyst activity to grow CNFs. High resolution transmission electron microscope however did not reveal any microstructural difference for Ni catalyst with and without the subsequent reduction treatment. We propose in this paper that the carbon dissolutions during treatment of the catalyst might have an implication on the CNF growth
Correlation energies of inhomogeneous many-electron systems
We generalize the uniform-gas correlation energy formalism of Singwi, Tosi,
Land and Sjolander to the case of an arbitrary inhomogeneous many-particle
system. For jellium slabs of finite thickness with a self-consistent LDA
groundstate Kohn-Sham potential as input, our numerical results for the
correlation energy agree well with diffusion Monte Carlo results. For a helium
atom we also obtain a good correlation energy.Comment: 4 pages,1 figur
Symmetry breaking and the random-phase approximation in small quantum dots
The random-phase approximation has been used to compute the properties of
parabolic two-dimensional quantum dots beyond the mean-field approximation.
Special emphasis is put on the ground state correlation energy, the symmetry
restoration and the role of the spurious modes within the random-phase
approximation. A systematics with the Coulombic interaction strength is
presented for the 2-electron dot, while for the 6- and 12-electron dots
selected cases are discussed. The validity of the random-phase approximation is
assessed by comparison with available exact results.Comment: 9 pages, 4 embedded + 6 gif Figs. Published versio
Synthesis and reductive chemistry of bimetallic and trimetallic rare-earth metallocene hydrides with (C5H4SiMe3)1â ligands
The reductive chemistry of [Cp\u272Ln(ÎŒâH)(THF)x]y [Ln = Y, Dy, Tb; Cp\u27 = (C5H4SiMe3)1â; x = 2, 0 and y = 2, 3] was examined to determine if these hydrides would be viable precursors for 4fn5d1 Ln2+ ions that could form 5d1-5d1 metalâmetal bonded complexes. The hydrides were prepared by reaction of the chlorides, [Cp\u272Ln(ÎŒâCl)]2, 1-Ln, with allylmagnesium chloride to form the allyl complexes, [Cp\u272Y(η3âC3H5)(THF)], 2-Ln, which were hydrogenolyzed. The solvent-free reaction of solid 2-Ln with 60 psi of H2 gas in a Fischer-Porter apparatus produced, in the Y case, the trimetallic species, [Cp\u272Y(ÎŒâH)]3, 3-Y, and in the Dy and Tb cases, the bimetallic complexes [Cp\u272Ln(ÎŒâH)(THF)]2, 4-Ln (Ln = Dy, Tb). The latter complexes could be converted to 3-Dy and 3-Tb by heating under vacuum. Isopiestic data indicate that 3-Y solvates to 4-Y in THF. Reductions of 4-Y, 4-Dy, and 4-Tb with KC8 in the presence of a chelate such as 2.2.2-cryptand or 18-crown-6 all gave reaction products with intense dark colors characteristic of Ln2+ ions. In the yttrium case, with either chelating agent, the dark green product gives a rhombic EPR spectrum (g1 = 2.01, g2 = 1.99, g3 = 1.98, A = 24.1 G) at 77 K. However, the only crystallographically-characterizable products obtainable from these solutions were Ln3+polyhydride anion complexes of composition, [K(chelate)]{[Cp\u272Ln(ÎŒâH)]3(ÎŒâH)}
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
Global hybrids from the semiclassical atom theory satisfying the local density linear response
We propose global hybrid approximations of the exchange-correlation (XC)
energy functional which reproduce well the modified fourth-order gradient
expansion of the exchange energy in the semiclassical limit of many-electron
neutral atoms and recover the full local density approximation (LDA) linear
response. These XC functionals represent the hybrid versions of the APBE
functional [Phys. Rev. Lett. 106, 186406, (2011)] yet employing an additional
correlation functional which uses the localization concept of the correlation
energy density to improve the compatibility with the Hartree-Fock exchange as
well as the coupling-constant-resolved XC potential energy. Broad energetical
and structural testings, including thermochemistry and geometry, transition
metal complexes, non-covalent interactions, gold clusters and small
gold-molecule interfaces, as well as an analysis of the hybrid parameters, show
that our construction is quite robust. In particular, our testing shows that
the resulting hybrid, including 20\% of Hartree-Fock exchange and named hAPBE,
performs remarkably well for a broad palette of systems and properties, being
generally better than popular hybrids (PBE0 and B3LYP). Semi-empirical
dispersion corrections are also provided.Comment: 12 pages, 4 figure
Excitation energies from time-dependent density-functional theory beyond the adiabatic approximation
doi:10.1063/1.1756865Time-dependent density-functional theory in the adiabatic approximation has been very successful for calculating excitation energies in molecular systems. This paper studies nonadiabatic effects for excitation energies, using the current-density functional of Vignale and Kohn [Phys. Rev. Lett. 77, 2037 (1996)]. We derive a general analytic expression for nonadiabatic corrections to excitation energies of finite systems and calculate singlet sâs and sâp excitations of closed-shell atoms. The approach works well for sâs excitations, giving a small improvement over the adiabatic local-density approximation, but tends to overcorrect sâp excitations. We find that the observed problems with the nonadiabatic correction have two main sources: (1) the currents associated with the sâp excitations are highly nonuniform and, in particular, change direction between atomic shells, (2) the so-called exchange-correlation kernels of the homogeneous electron gas, fxcL and fxcT, are incompletely known, in particular in the high-density atomic core regions.C.A.U. acknowledges support by the donors of the Petroleum Research Fund, administered by the ACS, and by the University of Missouri Research Board. K.B. was supported by DOE under Grant No. DE-FG02-01ER45928
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