Explicitly correlated plane waves: Accelerating convergence in periodic wavefunction expansions

We present an investigation into the use of an explicitly correlated plane wave basis for periodic wavefunction expansions at the level of second-order M{\o}ller-Plesset perturbation theory (MP2). The convergence of the electronic correlation energy with respect to the one-electron basis set is investigated and compared to conventional MP2 theory in a finite homogeneous electron gas model. In addition to the widely used Slater-type geminal correlation factor, we also derive and investigate a novel correlation factor that we term Yukawa-Coulomb. The Yukawa-Coulomb correlation factor is motivated by analytic results for two electrons in a box and allows for a further improved convergence of the correlation energies with respect to the employed basis set. We find the combination of the infinitely delocalized plane waves and local short-ranged geminals provides a complementary, and rapidly convergent basis for the description of periodic wavefunctions. We hope that this approach will expand the scope of discrete wavefunction expansions in periodic systems.Comment: 15 pages, 13 figure

X-ray Absorption Fine Structure in Embedded Atoms

Oscillatory structure is found in the atomic background absorption in x-ray-absorption fine structure (XAFS). This atomic-XAFS or AXAFS arises from scattering within an embedded atom, and is analogous to the Ramsauer-Townsend effect. Calculations and measurements confirm the existence of AXAFS and show that it can dominate contributions such as multi-electron excitations. The structure is sensitive to chemical effects and thus provides a new probe of bonding and exchange effects on the scattering potential.Comment: 4 pages plus 2 postscript figures, REVTEX 3.

Observation of blue-shifted ultralong-range Cs2_{2} Rydberg molecules

We observe ultralong-range blue-shifted Cs$_{2}$ molecular states near $ns_{1/2}$ Rydberg states in an optical dipole trap, where $31\leq n\leq34$. The accidental near degeneracy of $(n-4)l$ and $ns$ Rydberg states for $l>2$ in Cs, due to the small fractional $ns$ quantum defect, leads to non-adiabatic coupling among these states, producing potential wells above the $ns$ thresholds. Two important consequences of admixing high angular momentum states with $ns$ states are the formation of large permanent dipole moments, $\sim 15-100\,$Debye, and accessibility of these states via two-photon association. The observed states are in excellent agreement with theory. Both projections of the total angular momentum on the internuclear axis are visible in the experiment

Is U3Ni3Sn4 best described as near a quantum critical point?

Although most known non-Fermi liquid (NFL) materials are structurally or chemically disordered, the role of this disorder remains unclear. In particular, very few systems have been discovered that may be stoichiometric and well ordered. To test whether U3Ni3Sn4 belongs in this latter class, we present measurements of the x-ray absorption fine structure (XAFS) of polycrystalline and single-crystal U3Ni3Sn4 samples that are consistent with no measurable local structural disorder. We also present temperature-dependent specific heat data in applied magnetic fields as high as 8 T that show features that are inconsistent with the antiferromagnetic Griffiths' phase model, but do support the conclusion that a Fermi liquid/NFL crossover temperature increases with applied field. These results are inconsistent with theoretical explanations that require strong disorder effects, but do support the view that U3Ni3Sn4 is a stoichiometric, ordered material that exhibits NFL behavior, and is best described as being near an antiferromagnetic quantum critical point.Comment: 9 pages, 8 figures, in press with PR

Spectroscopic accuracy directly from quantum chemistry: application to ground and excited states of beryllium dimer

We combine explicit correlation via the canonical transcorrelation approach with the density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods to compute a near-exact beryllium dimer curve, {\it without} the use of composite methods. In particular, our direct density matrix renormalization group calculations produce a well-depth of $D_e$=931.2 cm$^{-1}$ which agrees very well with recent experimentally derived estimates $D_e$=929.7$\pm 2$~cm$^{-1}$ [Science, 324, 1548 (2009)] and $D_e$=934.6~cm$^{-1}$ [Science, 326, 1382 (2009)]], as well the best composite theoretical estimates, $D_e$=938$\pm 15$~cm$^{-1}$ [J. Phys. Chem. A, 111, 12822 (2007)] and $D_e$=935.1$\pm 10$~cm$^{-1}$ [Phys. Chem. Chem. Phys., 13, 20311 (2011)]. Our results suggest possible inaccuracies in the functional form of the potential used at shorter bond lengths to fit the experimental data [Science, 324, 1548 (2009)]. With the density matrix renormalization group we also compute near-exact vertical excitation energies at the equilibrium geometry. These provide non-trivial benchmarks for quantum chemical methods for excited states, and illustrate the surprisingly large error that remains for 1$^1\Sigma^-_g$ state with approximate multi-reference configuration interaction and equation-of-motion coupled cluster methods. Overall, we demonstrate that explicitly correlated density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods allow us to fully converge to the basis set and correlation limit of the non-relativistic Schr\"odinger equation in small molecules

Quantifying structural damage from self-irradiation in a plutonium superconductor

The 18.5 K superconductor PuCoGa5 has many unusual properties, including those due to damage induced by self-irradiation. The superconducting transition temperature decreases sharply with time, suggesting a radiation-induced Frenkel defect concentration much larger than predicted by current radiation damage theories. Extended x-ray absorption fine-structure measurements demonstrate that while the local crystal structure in fresh material is well ordered, aged material is disordered much more strongly than expected from simple defects, consistent with strong disorder throughout the damage cascade region. These data highlight the potential impact of local lattice distortions relative to defects on the properties of irradiated materials and underscore the need for more atomic-resolution structural comparisons between radiation damage experiments and theory.Comment: 7 pages, 5 figures, to be published in PR

Molecular clouds in the centers of galaxies: Constraints from HCN and CO-13 line emission

We have searched for HCN J=1-0 line emission in the centers of 12 galaxies and have detected it in 10 of them. We have obtained complementary data on J=1-0 and 2-1 transitions of CO-12 and CO-13 in these systems. The ratio of integrated intensities, I(CO 1-0)/I(HCN 1-0) = 25 +/- 11 for this sample. We find that HCN emission of this strength can be produced under conditions of subthermal excitation. In combination with the line ratios in CO and CO-13, HCN puts constraints on the mean conditions of molecular clouds and on the mix of cloud types within the projected beam