Jonathan L. DuBois

Path-Integral Monte Carlo Simulation of the Warm Dense Homogeneous Electron Gas

We perform calculations of the 3D finite-temperature homogeneous electron gas in the warm-dense regime (r(s) ≡ (3/4πn)(1/3)a(0)(-1) = 1.0-40.0 and Θ ≡ T/T(F) = 0.0625-8.0) using restricted path-integral Monte Carlo simulations. Precise energies, pair correlation functions, and structure factors are obtained. For all densities, we find a significant discrepancy between the ground state parametrized local density approximation and our results around T(F). These results can be used as a benchmark for developing finite-temperature density functionals, as well as input for orbital-free density function theory formulations.

Measurement-based measure of the size of macroscopic quantum superpositions

Recent experiments claiming formation of quantum superposition states in near macroscopic sys- tems raise the question of how the sizes of general quantum superposition states in an interacting system are to be quantified. We propose here a measure of size for such superposition states that is based on what measurements can be performed to probe and distinguish the different branches of the state. The measure allows comparison of the effective size for superposition states in very different physical systems. It can be applied to a very general class of superposition states and reproduces known results for near-ideal cases. Comparison with a prior measure based on analy- sis of coherence between branches indicates that significantly smaller effective superposition sizes result from our measurement-based measure. Application to a system of interacting bosons in a double-well trapping potential shows that the effective superposition size is strongly dependent on the relative magnitude of the barrier height and interparticle interaction.

Spectral shifts and helium configurations in H4eN–tetracene clusters

Spectral shifts of electronic transitions of tetracene in helium droplets are investigated in a theoretical study of (4)He(N)-tetracene clusters with 1 < or = N < or = 150. Utilizing a pairwise interaction for the S(0) state of tetracene with helium that is extended by semiempirical terms to construct a potential for the S(1) state of tetracene with helium, the spectral shift is calculated from path integral Monte Carlo calculations of the helium equilibrium properties with tetracene in the S(0) and S(1) states at T = 0 and at T = 0.625 K. The calculated spectral shifts are in quantitative agreement with available experimental measurements for small values of N (< or = 8) at T approximately 0.4 K and show qualitative agreement for larger N (10-20). The extrapolated value of the spectral shift in large droplets (N approximately 10(4)) is approximately 90% of the experimentally measured value. We find no evidence of multiple configurations of helium for any cluster size for either the S(0) or S(1) state of tetracene. These results suggest that the observed spectral splitting of electronic transitions of tetracene in large helium droplets is not due to the coexistence of static metastable helium densities, unlike the situation previously analyzed for the phthalocyanine molecule.

Exchange-correlation energy for the three-dimensional homogeneous electron gas at arbitrary temperature

0625]. In doing so, we construct a Pade approximant which collapses to Debye-H´ uckel theory¨inthe high-temperature, low-density limit.Likewise, the zero-temperature limitmatches the numerical results ofground-state quantum Monte Carlo, as well as analytical results in the high-density limit.DOI: 10.1103/PhysRevB.88.081102 PACS number(s): 71

Theoretical Analysis of the Anomalous Spectral Splitting of Tetracene in 4He Droplets

We present a theoretical analysis of the electronic absorption spectra of tetracene in (4)He droplets based on many-body quantum simulations. Using the path integral ground state approach, we calculate one- and two-body reduced density matrices of the most strongly localized He atoms near the molecule surface and use these to investigate the helium ground-state quantum coherence and correlations when tetracene is in its electronic ground and excited states. We identify a trio of quasi-one-dimensional, strongly localized atoms adsorbed along the long axis of the molecule that show some quantum coherence among themselves but far less with the remaining solvating helium. We evaluate the single-particle natural orbitals of the localized He atoms by diagonalization of the one-body density matrix and use these to construct single- and many-particle solvating helium basis states with which the zero-phonon spectral features of the tetracene-(4)He(N) absorption spectrum are then calculated. The absorption spectrum resulting from the three-body density matrix for the strongly bound trio of helium atoms is in very good agreement with the experimental data, accounting quantitatively for the anomalous splitting of the zero-phonon line [Hartmann, M.; Lindinger, A.; Toennies, J. P.; Vilesov, A. F. Chem. Phys. 1998, 239, 139; Krasnokutski, S.; Rouillé, G.; Huisken, F. Chem. Phys. Lett. 2005, 406, 386]. Our results indicate that the combination of strong localization and the quasi-one-dimensional nature of trios of helium atoms adsorbed along the long axis of tetracene leads to a quantum coherent, yet highly correlated ground state for the helium density closest to the molecule. The spectroscopic analysis shows that this feature accounts quantitatively for the anomalous splittings and hitherto unexplained fine structure observed in the absorption spectra of tetracene and suggests that it may be responsible for the corresponding zero-phonon splittings in other quasi-one-dimensional planar aromatic molecules.

Prospects for release-node quantum Monte Carlo

We perform release-node quantum Monte Carlo simulations on the first row diatomic molecules in order to assess how accurately their ground-state energies can be obtained. An analysis of the fermion-boson energy difference is shown to be strongly dependent on the nuclear charge, Z, which in turn determines the growth of variance of the release-node energy. It is possible to use maximum entropy analysis to extrapolate to ground-state energies only for the low Z elements. For the higher Z dimers beyond boron, the error growth is too large to allow accurate data for long enough imaginary times. Within the limit of our statistics we were able to estimate, in atomic units, the ground-state energy of Li(2) (-14.9947(1)), Be(2) (-29.3367(7)), and B(2)(-49.410(2)).

Overcoming the fermion sign problem in homogeneous systems

Explicit treatment of many-body Fermi statistics in path integral Monte Carlo (PIMC) results in exponentially scaling computational cost due to the near cancellation of contributions to observables from even and odd permutations. Through direct analysis of exchange statistics we find that individual exchange probabilities in homogeneous systems are, except for finite size effects, independent of the configuration of other permutations present. For two representative systems, 3-He and the homogeneous electron gas, we show that this allows the entire antisymmetrized density matrix to be generated from a simple model depending on only a few parameters obtainable directly from a standard PIMC simulation. The result is a polynomial scaling algorithm and up to a 10 order of magnitude increase in efficiency in measuring fermionic observables for the systems considered.

Stability of the high-pressure phases of CaTiO 3 perovskite at finite temperatures

The thermodynamic stability of the Pnma structure of CaTiO

Importance of Excitonic Effect in Charge Separation at Quantum-Dot/Organic Interface: First-Principles Many-Body Calculations

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Number-squeezed and fragmented states of strongly interacting bosons in a double well

has been studied using hybrid density functional theory and Gibbs free energy calculations, including anharmonic effects. The use of the screened Heyd-Scuseria-Ernzerhof (HSE06) functional shifts the room temperature transition pressure from perovskite to post-perovskite structure by around 18 GPa, or 37