3,990 research outputs found
System-adapted correlation energy density functionals from effective pair interactions
We present and discuss some ideas concerning an ``average-pair-density
functional theory'', in which the ground-state energy of a many-electron system
is rewritten as a functional of the spherically and system-averaged pair
density. These ideas are further clarified with simple physical examples. We
then show that the proposed formalism can be combined with density functional
theory to build system-adapted correlation energy functionals. A simple
approximation for the unknown effective electron-electron interaction that
enters in this combined approach is described, and results for the He series
and for the uniform electron gas are briefly reviewed.Comment: to appear in Phil. Mag. as part of Conference proceedings for the
"Electron Correlations and Materials Properties", Kos Greece, July 5-9, 200
On Some Open Problems in Many-Electron Theory
Mel Levy and Elliott Lieb are two of the most prominent researchers who have
dedicated their efforts to the investigation of fundamental questions in
many-electron theory. Their results have not only revolutionized the
theoretical approach of the field, but, directly or indirectly, allowed for a
quantum jump in the computational treatment of realistic systems as well. For
this reason, at the conclusion of our book where the subject is treated across
different disciplines, we have asked Mel Levy and Elliott Lieb to provide us
with some open problems, which they believe will be a worth challenge for the
future also in the perspective of a synergy among the various disciplines.Comment: "Epilogue" chapter in "Many-Electron Approaches in Physics, Chemistry
and Mathematics: A Multidisciplinary View", Volker Bach and Luigi Delle Site
Eds. pages 411-416; Book Series: Mathematical Physics Studies, Springer
International Publishing Switzerland, 2014. The original title has been
modified in order to clarify the subject of the chapter out of the context of
the boo
Implication of the overlap representation for modelling generalized parton distributions
Based on a field theoretically inspired model of light-cone wave functions,
we derive valence-like generalized parton distributions and their double
distributions from the wave function overlap in the parton number conserved
s-channel. The parton number changing contributions in the t-channel are
restored from duality. In our construction constraints of positivity and
polynomiality are simultaneously satisfied and it also implies a model
dependent relation between generalized parton distributions and transverse
momentum dependent parton distribution functions. The model predicts that the
t-behavior of resulting hadronic amplitudes depends on the Bjorken variable
x_Bj. We also propose an improved ansatz for double distributions that embeds
this property.Comment: 15 pages, 8 eps figure
Exact exchange-correlation potential of a ionic Hubbard model with a free surface
We use Lanczos exact diagonalization to compute the exact
exchange-correlation (xc) potential of a Hubbard chain with large binding
energy ("the bulk") followed by a chain with zero binding energy ("the
vacuum"). Several results of density functional theory in the continuum
(sometimes controversial) are verified in the lattice. In particular we show
explicitly that the fundamental gap is given by the gap in the Kohn-Sham
spectrum plus a contribution due to the jump of the xc-potential when a
particle is added. The presence of a staggered potential and a nearest-neighbor
interaction V allows to simulate a ionic solid. We show that in the ionic
regime in the small hopping amplitude limit the xc-contribution to the gap
equals V, while in the Mott regime it is determined by the Hubbard U
interaction. In addition we show that correlations generates a new potential
barrier at the surface
Optimized intermolecular potential for nitriles based on Anisotropic United Atoms model
An extension of the Anisotropic United Atoms intermolecular potential model is proposed for nitriles. The electrostatic part of the intermolecular potential is calculated using atomic charges obtained by a simple Mulliken population analysis. The repulsion-dispersion interaction parameters for methyl and methylene groups are taken from transferable AUA4 literature parameters [Ungerer et al., J. Chem. Phys., 2000, 112, 5499]. Non-bonding Lennard-Jones intermolecular potential parameters are regressed for the carbon and nitrogen atoms of the nitrile group (âCâĄN) from experimental vapor-liquid equilibrium data of acetonitrile. Gibbs Ensemble Monte Carlo simulations and experimental data agreement is very good for acetonitrile, and better than previous molecular potential proposed by Hloucha et al. [J. Chem. Phys., 2000, 113, 5401]. The transferability of the resulting potential is then successfully tested, without any further readjustment, to predict vapor-liquid phase equilibrium of propionitrile and n-butyronitrile
Pressure dependent electronic properties of MgO polymorphs: A first-principles study of Compton profiles and autocorrelation functions
The first-principles periodic linear combination of atomic orbitals method
within the framework of density functional theory implemented in the CRYSTAL06
code has been applied to explore effect of pressure on the Compton profiles and
autocorrelation functions of MgO. Calculations are performed for the B1, B2,
B3, B4, B8_1 and h-MgO polymorphs of MgO to compute lattice constants and bulk
moduli. The isothermal enthalpy calculations predict that B4 to B8_1, h-MgO to
B8_1, B3 to B2, B4 to B2 and h-MgO to B2 transitions take place at 2, 9, 37, 42
and 64 GPa respectively. The high pressure transitions B8_1 to B2 and B1 to B2
are found to occur at 340 and 410 GPa respectively. The pressure dependent
changes are observed largely in the valence electrons Compton profiles whereas
core profiles are almost independent of the pressure in all MgO polymorphs.
Increase in pressure results in broadening of the valence Compton profiles. The
principal maxima in the second derivative of Compton profiles shifts towards
high momentum side in all structures. Reorganization of momentum density in the
B1 to B2 structural phase transition is seen in the first and second
derivatives before and after the transition pressure. Features of the
autocorrelation functions shift towards lower r side with increment in
pressure.Comment: 19 pages, 8 figures, accepted for publication in Journal of Materials
Scienc
Improving the study of proton transfers between amino acid sidechains in solution: choosing appropriate DFT functionals and avoiding hidden pitfalls
We have studied the influence of implicit solvent models, inclusion of explicit water molecules, inclusion of vibrational effects, and density functionals on the quality of the predicted pK a of small amino acid side chain models. We found that the inclusion of vibrational effects and explicit water molecules is crucial to improve the correlation between the computed and the experimental values. In these micro-solvated systems, the best agreement between DFT-computed electronic energies and benchmark values is afforded by BHHLYP and B97-2. However, approaching experimental results requires the addition of more than three explicit water molecules, which generates new problems related to the presence of multiple minima in the potential energy surface. It thus appears that a satisfactory ab initio prediction of amino acid side chain pK a will require methods that sample the configurational space in the presence of large solvation shells, while at the same time computing vibrational contributions to the enthalpy and entropy of the system under study in all points of that surface. Pending development of efficient algorithms for those computations, we strongly suggest that whenever counterintuitive protonation states are found in a computational study (e.g., the presence of a neutral aspartate/neutral histidine dyad instead of a deprotonated aspartate/protonated histidine pair), the reaction profile should be computed under each of the different protonation micro-states by constraining the relevant NâH or OâH bonds, in order to avoid artifacts inherent to the complex nature of the factors contributing to the pK a
Ab initio study of magnetism at the TiO2/LaAlO3 interface
In this paper we study the possible relation between the electronic and
magnetic structure of the TiO2/LaAlO3 interface and the unexpected magnetism
found in undoped TiO2 films grown on LaAlO. We concentrate on the role
played by structural relaxation and interfacial oxygen vacancies.
LaAlO3 has a layered structure along the (001) direction with alternating LaO
and AlO2 planes, with nominal charges of +1 and -1, respectively. As a
consequence of that, an oxygen deficient TiO2 film with anatase structure will
grow preferently on the AlO2 surface layer. We have therefore performed
ab-initio calculations for superlattices with TiO2/AlO2 interfaces with
interfacial oxygen vacancies. Our main results are that vacancies lead to a
change in the valence state of neighbour Ti atoms but not necessarily to a
magnetic solution and that the appearance of magnetism depends also on
structural details, such as second neighbor positions. These results are
obtained using both the LSDA and LSDA+U approximations.Comment: Accepted for publication in Journal of Materials Scienc
- âŠ