Variational finite-difference representation of the kinetic energy operator

A potential disadvantage of real-space-grid electronic structure methods is the lack of a variational principle and the concomitant increase of total energy with grid refinement. We show that the origin of this feature is the systematic underestimation of the kinetic energy by the finite difference representation of the Laplacian operator. We present an alternative representation that provides a rigorous upper bound estimate of the true kinetic energy and we illustrate its properties with a harmonic oscillator potential. For a more realistic application, we study the convergence of the total energy of bulk silicon using a real-space-grid density-functional code and employing both the conventional and the alternative representations of the kinetic energy operator.Comment: 3 pages, 3 figures, 1 table. To appear in Phys. Rev. B. Contribution for the 10th anniversary of the eprint serve

Free energy and vibrational entropy difference between ordered and disordered Ni3Al

We have calculated free energy and vibrational entropy differences in Ni3Al between its equilibrium ordered structure and a disordered fcc solid solution. The free energy and entropy differences were calculated using the method of adiabatic switching in a molecular-dynamics formalism. The path chosen for the free-energy calculations directly connects the disordered with the ordered state. The atomic interactions are described by embedded-atom-method potentials. We find that the vibrational entropy difference increases with temperature from 0.14kB/atom at 300 K to 0.22kB/atom at 1200 K. We have calculated the density of states (DOS) of the disordered phase from the Fourier transform of the velocity-velocity autocorrelation function. The disordered DOS looks more like a broadened version of the ordered DOS. Analysis of the partial density of states shows that the Al atoms vibrations are most affected by the compositional disorder. The phonon partial spectral intensities along the 〈100〉 direction show that the vibrational spectrum of the disordered phase contains intensities at optical mode frequencies of the ordered alloy. We find that the volume difference between the ordered and disordered phases plays the most crucial role in the magnitude of the vibrational entropy difference. If the lattice constant of the two phases is set to the same value, the vibrational entropy difference decreases to zero

Dual-Topology Hamiltonian-Replica-Exchange Overlap Histogramming Method to Calculate Relative Free Energy Difference in Rough Energy Landscape

A novel overlap histogramming method based on Dual-Topology Hamiltonian-Replica-Exchange simulation technique is presented to efficiently calculate relative free energy difference in rough energy landscape, in which multiple conformers coexist and are separated by large energy barriers. The proposed method is based on the realization that both DT-HERM exchange efficiency and confidence of free energy determination in overlap histogramming method depend on the same criteria: neighboring states' energy derivative distribution overlap. In this paper, we demonstrate this new methodology by calculating free energy difference between amino acids: Leucine and Asparagine, which is an identified chanllenging system for free energy simulations.Comment: 14 pages with 4 figure

The Okamoto-Nolen-Schiffer anomaly without rho-omega mixing

We examine the effect of isospin-violating meson-nucleon coupling constants and of $\pi$-$\eta$ mixing on the binding-energy differences of mirror nuclei in a model that possesses no contribution from $\rho$-$\omega$ mixing. The ${}^{3}$He-${}^{3}$H binding-energy difference is computed in a nonrelativistic approach using a realistic wave function. We find the ${}^{3}$He-${}^{3}$H binding-energy difference very sensitive to the short-distance behavior of the nucleon-nucleon potential. We conclude that for the typically hard Bonn form factors such models can not account for the observed binding-energy difference in the three-nucleon system. For the medium-mass region (A=15--41) the binding-energy differences of mirror nuclei are computed using a relativistic mean-field approximation to the Walecka model. We obtain large binding-energy differences---of the order of several hundred keV---arising from the pseudoscalar sector. Two effects are primarily responsible for this new finding: a) the inclusion of isospin breaking in the pion-nucleon coupling constant, and b) the in-medium enhancement of the small components of the bound-state wave functions. We look for off-shell ambiguities in these results and find them to be large.Comment: 19 LaTeX pages and 2 postscript figures. Revisions/additions: Manuscript now includes a treatment of the binding-energy difference in the three-nucleon system as well as a study of possible off-shell ambiguities in the binding-energy differences of (A=15-41) mirror nucle