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Sample records for all-electron quantum monte

  1. Fundamental High-Pressure Calibration from All-Electron Quantum Monte Carlo Calculations

    SciTech Connect

    Esler, K. P.; Cohen, R. E.; Militzer, B.; Kim, Jeongnim; Needs, R. J.; Towler, M. D.

    2010-05-07

    We develop an all-electron quantum Monte Carlo (QMC) method for solids that does not rely on pseudopotentials, and use it to construct a primary ultra-high-pressure calibration based on the equation of state of cubic boron nitride. We compute the static contribution to the free energy with the QMC method and obtain the phonon contribution from density functional theory, yielding a high-accuracy calibration up to 900 GPa usable directly in experiment. We compute the anharmonic Raman frequency shift with QMC simulations as a function of pressure and temperature, allowing optical pressure calibration. In contrast to present experimental approaches, small systematic errors in the theoretical EOS do not increase with pressure, and no extrapolation is needed. This all-electron method is applicable to first-row solids, providing a new reference for ab initio calculations of solids and benchmarks for pseudopotential accuracy.

  2. Broadband all-electronically tunable MEMS terahertz quantum cascade lasers.

    PubMed

    Han, Ningren; de Geofroy, Alexander; Burghoff, David P; Chan, Chun Wang I; Lee, Alan Wei Min; Reno, John L; Hu, Qing

    2014-06-15

    In this work, we demonstrate all-electronically tunable terahertz quantum cascade lasers (THz QCLs) with MEMS tuner structures. A two-stage MEMS tuner device is fabricated by a commercial open-foundry process performed by the company MEMSCAP. This provides an inexpensive, rapid, and reliable approach for MEMS tuner fabrication for THz QCLs with a high-precision alignment scheme. In order to electronically actuate the MEMS tuner device, an open-loop cryogenic piezo nanopositioning stage is integrated with the device chip. Our experimental result shows that at least 240 GHz of single-mode continuous electronic tuning can be achieved in cryogenic environments (∼4  K) without mode hopping. This provides an important step toward realizing turn-key bench-top tunable THz coherent sources for spectroscopic and coherent tomography applications.

  3. Quantum Gibbs ensemble Monte Carlo

    SciTech Connect

    Fantoni, Riccardo; Moroni, Saverio

    2014-09-21

    We present a path integral Monte Carlo method which is the full quantum analogue of the Gibbs ensemble Monte Carlo method of Panagiotopoulos to study the gas-liquid coexistence line of a classical fluid. Unlike previous extensions of Gibbs ensemble Monte Carlo to include quantum effects, our scheme is viable even for systems with strong quantum delocalization in the degenerate regime of temperature. This is demonstrated by an illustrative application to the gas-superfluid transition of {sup 4}He in two dimensions.

  4. MontePython: Implementing Quantum Monte Carlo using Python

    NASA Astrophysics Data System (ADS)

    Nilsen, Jon Kristian

    2007-11-01

    We present a cross-language C++/Python program for simulations of quantum mechanical systems with the use of Quantum Monte Carlo (QMC) methods. We describe a system for which to apply QMC, the algorithms of variational Monte Carlo and diffusion Monte Carlo and we describe how to implement theses methods in pure C++ and C++/Python. Furthermore we check the efficiency of the implementations in serial and parallel cases to show that the overhead using Python can be negligible. Program summaryProgram title: MontePython Catalogue identifier: ADZP_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADZP_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 49 519 No. of bytes in distributed program, including test data, etc.: 114 484 Distribution format: tar.gz Programming language: C++, Python Computer: PC, IBM RS6000/320, HP, ALPHA Operating system: LINUX Has the code been vectorised or parallelized?: Yes, parallelized with MPI Number of processors used: 1-96 RAM: Depends on physical system to be simulated Classification: 7.6; 16.1 Nature of problem: Investigating ab initio quantum mechanical systems, specifically Bose-Einstein condensation in dilute gases of 87Rb Solution method: Quantum Monte Carlo Running time: 225 min with 20 particles (with 4800 walkers moved in 1750 time steps) on 1 AMD Opteron TM Processor 2218 processor; Production run for, e.g., 200 particles takes around 24 hours on 32 such processors.

  5. Interaction picture density matrix quantum Monte Carlo

    SciTech Connect

    Malone, Fionn D. Lee, D. K. K.; Foulkes, W. M. C.; Blunt, N. S.; Shepherd, James J.; Spencer, J. S.

    2015-07-28

    The recently developed density matrix quantum Monte Carlo (DMQMC) algorithm stochastically samples the N-body thermal density matrix and hence provides access to exact properties of many-particle quantum systems at arbitrary temperatures. We demonstrate that moving to the interaction picture provides substantial benefits when applying DMQMC to interacting fermions. In this first study, we focus on a system of much recent interest: the uniform electron gas in the warm dense regime. The basis set incompleteness error at finite temperature is investigated and extrapolated via a simple Monte Carlo sampling procedure. Finally, we provide benchmark calculations for a four-electron system, comparing our results to previous work where possible.

  6. Interaction picture density matrix quantum Monte Carlo.

    PubMed

    Malone, Fionn D; Blunt, N S; Shepherd, James J; Lee, D K K; Spencer, J S; Foulkes, W M C

    2015-07-28

    The recently developed density matrix quantum Monte Carlo (DMQMC) algorithm stochastically samples the N-body thermal density matrix and hence provides access to exact properties of many-particle quantum systems at arbitrary temperatures. We demonstrate that moving to the interaction picture provides substantial benefits when applying DMQMC to interacting fermions. In this first study, we focus on a system of much recent interest: the uniform electron gas in the warm dense regime. The basis set incompleteness error at finite temperature is investigated and extrapolated via a simple Monte Carlo sampling procedure. Finally, we provide benchmark calculations for a four-electron system, comparing our results to previous work where possible.

  7. Quantum Monte Carlo Endstation for Petascale Computing

    SciTech Connect

    David Ceperley

    2011-03-02

    CUDA GPU platform. We restructured the CPU algorithms to express additional parallelism, minimize GPU-CPU communication, and efficiently utilize the GPU memory hierarchy. Using mixed precision on GT200 GPUs and MPI for intercommunication and load balancing, we observe typical full-application speedups of approximately 10x to 15x relative to quad-core Xeon CPUs alone, while reproducing the double-precision CPU results within statistical error. We developed an all-electron quantum Monte Carlo (QMC) method for solids that does not rely on pseudopotentials, and used it to construct a primary ultra-high-pressure calibration based on the equation of state of cubic boron nitride. We computed the static contribution to the free energy with the QMC method and obtained the phonon contribution from density functional theory, yielding a high-accuracy calibration up to 900 GPa usable directly in experiment. We computed the anharmonic Raman frequency shift with QMC simulations as a function of pressure and temperature, allowing optical pressure calibration. In contrast to present experimental approaches, small systematic errors in the theoretical EOS do not increase with pressure, and no extrapolation is needed. This all-electron method is applicable to first-row solids, providing a new reference for ab initio calculations of solids and benchmarks for pseudopotential accuracy. We compared experimental and theoretical results on the momentum distribution and the quasiparticle renormalization factor in sodium. From an x-ray Compton-profile measurement of the valence-electron momentum density, we derived its discontinuity at the Fermi wavevector finding an accurate measure of the renormalization factor that we compared with quantum-Monte-Carlo and G0W0 calculations performed both on crystalline sodium and on the homogeneous electron gas. Our calculated results are in good agreement with the experiment. We have been studying the heat of formation for various Kubas complexes of molecular

  8. Fast quantum Monte Carlo on a GPU

    NASA Astrophysics Data System (ADS)

    Lutsyshyn, Y.

    2015-02-01

    We present a scheme for the parallelization of quantum Monte Carlo method on graphical processing units, focusing on variational Monte Carlo simulation of bosonic systems. We use asynchronous execution schemes with shared memory persistence, and obtain an excellent utilization of the accelerator. The CUDA code is provided along with a package that simulates liquid helium-4. The program was benchmarked on several models of Nvidia GPU, including Fermi GTX560 and M2090, and the Kepler architecture K20 GPU. Special optimization was developed for the Kepler cards, including placement of data structures in the register space of the Kepler GPUs. Kepler-specific optimization is discussed.

  9. Experimental Monte Carlo Quantum Process Certification

    NASA Astrophysics Data System (ADS)

    Steffen, L.; da Silva, M. P.; Fedorov, A.; Baur, M.; Wallraff, A.

    2012-06-01

    Experimental implementations of quantum information processing have now reached a level of sophistication where quantum process tomography is impractical. The number of experimental settings as well as the computational cost of the data postprocessing now translates to days of effort to characterize even experiments with as few as 8 qubits. Recently a more practical approach to determine the fidelity of an experimental quantum process has been proposed, where the experimental data are compared directly with an ideal process using Monte Carlo sampling. Here, we present an experimental implementation of this scheme in a circuit quantum electrodynamics setup to determine the fidelity of 2-qubit gates, such as the CPHASE and the CNOT gate, and 3-qubit gates, such as the Toffoli gate and two sequential CPHASE gates.

  10. Novel Quantum Monte Carlo Approaches for Quantum Liquids

    NASA Astrophysics Data System (ADS)

    Rubenstein, Brenda M.

    Quantum Monte Carlo methods are a powerful suite of techniques for solving the quantum many-body problem. By using random numbers to stochastically sample quantum properties, QMC methods are capable of studying low-temperature quantum systems well beyond the reach of conventional deterministic techniques. QMC techniques have likewise been indispensible tools for augmenting our current knowledge of superfluidity and superconductivity. In this thesis, I present two new quantum Monte Carlo techniques, the Monte Carlo Power Method and Bose-Fermi Auxiliary-Field Quantum Monte Carlo, and apply previously developed Path Integral Monte Carlo methods to explore two new phases of quantum hard spheres and hydrogen. I lay the foundation for a subsequent description of my research by first reviewing the physics of quantum liquids in Chapter One and the mathematics behind Quantum Monte Carlo algorithms in Chapter Two. I then discuss the Monte Carlo Power Method, a stochastic way of computing the first several extremal eigenvalues of a matrix too memory-intensive to be stored and therefore diagonalized. As an illustration of the technique, I demonstrate how it can be used to determine the second eigenvalues of the transition matrices of several popular Monte Carlo algorithms. This information may be used to quantify how rapidly a Monte Carlo algorithm is converging to the equilibrium probability distribution it is sampling. I next present the Bose-Fermi Auxiliary-Field Quantum Monte Carlo algorithm. This algorithm generalizes the well-known Auxiliary-Field Quantum Monte Carlo algorithm for fermions to bosons and Bose-Fermi mixtures. Despite some shortcomings, the Bose-Fermi Auxiliary-Field Quantum Monte Carlo algorithm represents the first exact technique capable of studying Bose-Fermi mixtures of any size in any dimension. In Chapter Six, I describe a new Constant Stress Path Integral Monte Carlo algorithm for the study of quantum mechanical systems under high pressures. While

  11. Interaction picture density matrix quantum Monte Carlo.

    PubMed

    Malone, Fionn D; Blunt, N S; Shepherd, James J; Lee, D K K; Spencer, J S; Foulkes, W M C

    2015-07-28

    The recently developed density matrix quantum Monte Carlo (DMQMC) algorithm stochastically samples the N-body thermal density matrix and hence provides access to exact properties of many-particle quantum systems at arbitrary temperatures. We demonstrate that moving to the interaction picture provides substantial benefits when applying DMQMC to interacting fermions. In this first study, we focus on a system of much recent interest: the uniform electron gas in the warm dense regime. The basis set incompleteness error at finite temperature is investigated and extrapolated via a simple Monte Carlo sampling procedure. Finally, we provide benchmark calculations for a four-electron system, comparing our results to previous work where possible. PMID:26233116

  12. Discovering correlated fermions using quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas K.; Ceperley, David M.

    2016-09-01

    It has become increasingly feasible to use quantum Monte Carlo (QMC) methods to study correlated fermion systems for realistic Hamiltonians. We give a summary of these techniques targeted at researchers in the field of correlated electrons, focusing on the fundamentals, capabilities, and current status of this technique. The QMC methods often offer the highest accuracy solutions available for systems in the continuum, and, since they address the many-body problem directly, the simulations can be analyzed to obtain insight into the nature of correlated quantum behavior.

  13. Discovering correlated fermions using quantum Monte Carlo.

    PubMed

    Wagner, Lucas K; Ceperley, David M

    2016-09-01

    It has become increasingly feasible to use quantum Monte Carlo (QMC) methods to study correlated fermion systems for realistic Hamiltonians. We give a summary of these techniques targeted at researchers in the field of correlated electrons, focusing on the fundamentals, capabilities, and current status of this technique. The QMC methods often offer the highest accuracy solutions available for systems in the continuum, and, since they address the many-body problem directly, the simulations can be analyzed to obtain insight into the nature of correlated quantum behavior. PMID:27518859

  14. Experimental Monte Carlo Quantum Process Certification

    NASA Astrophysics Data System (ADS)

    Steffen, Lars; Fedorov, Arkady; Baur, Matthias; Palmer da Silva, Marcus; Wallraff, Andreas

    2012-02-01

    Experimental implementations of quantum information processing have now reached a state, at which quantum process tomography starts to become impractical, since the number of experimental settings as well as the computational cost of the post processing required to extract the process matrix from the measurements scales exponentially with the number of qubits in the system. In order to determine the fidelity of an implemented process relative to the ideal one, a more practical approach called Monte Carlo quantum process certification was proposed in Ref. [1]. Here we present an experimental implementation of this scheme in a circuit quantum electrodynamics setup. Our system is realized with three superconducting transmon qubits coupled to a coplanar microwave resonator which is used for the joint-readout of the qubit states. We demonstrate an implementation of Monte Carlo quantum process certification and determine the fidelity of different two- and three-qubit gates such as cphase-, cnot-, 2cphase- and Toffoli-gates. The obtained results are compared with the values obtained from conventional process tomography and the errors of the obtained fidelities are determined. [4pt] [1] M. P. da Silva, O. Landon-Cardinal and D. Poulin, arXiv:1104.3835(2011)

  15. Quantum Monte Carlo with known sign structures

    NASA Astrophysics Data System (ADS)

    Nilsson, Johan

    We investigate the merits of different Hubbard-Stratonovich transformations (including fermionic ones) for the description of interacting fermion systems, focusing on the single band Hubbard model as a model system. In particular we revisit an old proposal of Batrouni and Forcrand (PRB 48, 589 1993) for determinant quantum Monte Carlo simulations, in which the signs of all configurations is known beforehand. We will discuss different ways that this knowledge can be used to make more accurate predictions and simulations.

  16. Applications of Maxent to quantum Monte Carlo

    SciTech Connect

    Silver, R.N.; Sivia, D.S.; Gubernatis, J.E. ); Jarrell, M. . Dept. of Physics)

    1990-01-01

    We consider the application of maximum entropy methods to the analysis of data produced by computer simulations. The focus is the calculation of the dynamical properties of quantum many-body systems by Monte Carlo methods, which is termed the Analytical Continuation Problem.'' For the Anderson model of dilute magnetic impurities in metals, we obtain spectral functions and transport coefficients which obey Kondo Universality.'' 24 refs., 7 figs.

  17. Toward Accurate Modelling of Enzymatic Reactions: All Electron Quantum Chemical Analysis combined with QM/MM Calculation of Chorismate Mutase

    SciTech Connect

    Ishida, Toyokazu

    2008-09-17

    To further understand the catalytic role of the protein environment in the enzymatic process, the author has analyzed the reaction mechanism of the Claisen rearrangement of Bacillus subtilis chorismate mutase (BsCM). By introducing a new computational strategy that combines all-electron QM calculations with ab initio QM/MM modelings, it was possible to simulate the molecular interactions between the substrate and the protein environment. The electrostatic nature of the transition state stabilization was characterized by performing all-electron QM calculations based on the fragment molecular orbital technique for the entire enzyme.

  18. Quantum Monte Carlo calculations for light nuclei.

    SciTech Connect

    Wiringa, R. B.

    1998-10-23

    Quantum Monte Carlo calculations of ground and low-lying excited states for nuclei with A {le} 8 are made using a realistic Hamiltonian that fits NN scattering data. Results for more than 40 different (J{pi}, T) states, plus isobaric analogs, are obtained and the known excitation spectra are reproduced reasonably well. Various density and momentum distributions and electromagnetic form factors and moments have also been computed. These are the first microscopic calculations that directly produce nuclear shell structure from realistic NN interactions.

  19. Quantum Monte Carlo of ThO2

    NASA Astrophysics Data System (ADS)

    Hu, Shuming; Mitas, Lubos

    2012-02-01

    Thorium dioxide solid is a unique optical and heat-resistant actinide material with large gap and cohesion. It is a diamagnet, unlike a number of other similar actinide oxides. We investigate the electronic structure of ThO2 using Density Functional Theory (DFT) and quantum Monte Carlo (QMC) methods. We adopt Stuttgart RLC and RSC effective core potentials (pseudopotentials) for the Th atom. In the DFT calculations, some of the properties are verified in all-electron calculations using the FLAPW techniques. Using the fixed-node diffusion Monte Carlo we calculate the ground state and several excited states from which we estimate the cohesion and the band gap. Simulation cells of several sizes are used to estimate/reduce the finite size effects. We compare the QMC results with recent DFT calculations with several types of functionals which include hybrids such as PBE0 and HSE. Insights from QMC calculations give us understanding of the correlations beyond the DFT approaches and pave the way for accurate electronic structure calculations of other actinide materials.

  20. Chemical application of diffusion quantum Monte Carlo

    NASA Technical Reports Server (NTRS)

    Reynolds, P. J.; Lester, W. A., Jr.

    1984-01-01

    The diffusion quantum Monte Carlo (QMC) method gives a stochastic solution to the Schroedinger equation. This approach is receiving increasing attention in chemical applications as a result of its high accuracy. However, reducing statistical uncertainty remains a priority because chemical effects are often obtained as small differences of large numbers. As an example, the single-triplet splitting of the energy of the methylene molecule CH sub 2 is given. The QMC algorithm was implemented on the CYBER 205, first as a direct transcription of the algorithm running on the VAX 11/780, and second by explicitly writing vector code for all loops longer than a crossover length C. The speed of the codes relative to one another as a function of C, and relative to the VAX, are discussed. The computational time dependence obtained versus the number of basis functions is discussed and this is compared with that obtained from traditional quantum chemistry codes and that obtained from traditional computer architectures.

  1. Quantum Monte Carlo methods for nuclear physics

    DOE PAGES

    Carlson, J.; Gandolfi, S.; Pederiva, F.; Pieper, Steven C.; Schiavilla, R.; Schmidt, K. E.; Wiringa, R. B.

    2015-09-09

    Quantum Monte Carlo methods have proved valuable to study the structure and reactions of light nuclei and nucleonic matter starting from realistic nuclear interactions and currents. These ab-initio calculations reproduce many low-lying states, moments, and transitions in light nuclei, and simultaneously predict many properties of light nuclei and neutron matter over a rather wide range of energy and momenta. The nuclear interactions and currents are reviewed along with a description of the continuum quantum Monte Carlo methods used in nuclear physics. These methods are similar to those used in condensed matter and electronic structure but naturally include spin-isospin, tensor, spin-orbit,more » and three-body interactions. A variety of results are presented, including the low-lying spectra of light nuclei, nuclear form factors, and transition matrix elements. Low-energy scattering techniques, studies of the electroweak response of nuclei relevant in electron and neutrino scattering, and the properties of dense nucleonic matter as found in neutron stars are also described. Furthermore, a coherent picture of nuclear structure and dynamics emerges based upon rather simple but realistic interactions and currents.« less

  2. Quantum Monte Carlo methods for nuclear physics

    DOE PAGES

    Carlson, Joseph A.; Gandolfi, Stefano; Pederiva, Francesco; Pieper, Steven C.; Schiavilla, Rocco; Schmidt, K. E,; Wiringa, Robert B.

    2014-10-19

    Quantum Monte Carlo methods have proved very valuable to study the structure and reactions of light nuclei and nucleonic matter starting from realistic nuclear interactions and currents. These ab-initio calculations reproduce many low-lying states, moments and transitions in light nuclei, and simultaneously predict many properties of light nuclei and neutron matter over a rather wide range of energy and momenta. We review the nuclear interactions and currents, and describe the continuum Quantum Monte Carlo methods used in nuclear physics. These methods are similar to those used in condensed matter and electronic structure but naturally include spin-isospin, tensor, spin-orbit, and three-bodymore » interactions. We present a variety of results including the low-lying spectra of light nuclei, nuclear form factors, and transition matrix elements. We also describe low-energy scattering techniques, studies of the electroweak response of nuclei relevant in electron and neutrino scattering, and the properties of dense nucleonic matter as found in neutron stars. A coherent picture of nuclear structure and dynamics emerges based upon rather simple but realistic interactions and currents.« less

  3. Quantum Monte Carlo methods for nuclear physics

    SciTech Connect

    Carlson, J.; Gandolfi, S.; Pederiva, F.; Pieper, Steven C.; Schiavilla, R.; Schmidt, K. E.; Wiringa, R. B.

    2015-09-09

    Quantum Monte Carlo methods have proved valuable to study the structure and reactions of light nuclei and nucleonic matter starting from realistic nuclear interactions and currents. These ab-initio calculations reproduce many low-lying states, moments, and transitions in light nuclei, and simultaneously predict many properties of light nuclei and neutron matter over a rather wide range of energy and momenta. The nuclear interactions and currents are reviewed along with a description of the continuum quantum Monte Carlo methods used in nuclear physics. These methods are similar to those used in condensed matter and electronic structure but naturally include spin-isospin, tensor, spin-orbit, and three-body interactions. A variety of results are presented, including the low-lying spectra of light nuclei, nuclear form factors, and transition matrix elements. Low-energy scattering techniques, studies of the electroweak response of nuclei relevant in electron and neutrino scattering, and the properties of dense nucleonic matter as found in neutron stars are also described. Furthermore, a coherent picture of nuclear structure and dynamics emerges based upon rather simple but realistic interactions and currents.

  4. Quantum Monte Carlo for vibrating molecules

    SciTech Connect

    Brown, W.R. |

    1996-08-01

    Quantum Monte Carlo (QMC) has successfully computed the total electronic energies of atoms and molecules. The main goal of this work is to use correlation function quantum Monte Carlo (CFQMC) to compute the vibrational state energies of molecules given a potential energy surface (PES). In CFQMC, an ensemble of random walkers simulate the diffusion and branching processes of the imaginary-time time dependent Schroedinger equation in order to evaluate the matrix elements. The program QMCVIB was written to perform multi-state VMC and CFQMC calculations and employed for several calculations of the H{sub 2}O and C{sub 3} vibrational states, using 7 PES`s, 3 trial wavefunction forms, two methods of non-linear basis function parameter optimization, and on both serial and parallel computers. In order to construct accurate trial wavefunctions different wavefunctions forms were required for H{sub 2}O and C{sub 3}. In order to construct accurate trial wavefunctions for C{sub 3}, the non-linear parameters were optimized with respect to the sum of the energies of several low-lying vibrational states. In order to stabilize the statistical error estimates for C{sub 3} the Monte Carlo data was collected into blocks. Accurate vibrational state energies were computed using both serial and parallel QMCVIB programs. Comparison of vibrational state energies computed from the three C{sub 3} PES`s suggested that a non-linear equilibrium geometry PES is the most accurate and that discrete potential representations may be used to conveniently determine vibrational state energies.

  5. QWalk: A quantum Monte Carlo program for electronic structure

    SciTech Connect

    Wagner, Lucas K. Bajdich, Michal Mitas, Lubos

    2009-05-20

    We describe QWalk, a new computational package capable of performing quantum Monte Carlo electronic structure calculations for molecules and solids with many electrons. We describe the structure of the program and its implementation of quantum Monte Carlo methods. It is open-source, licensed under the GPL, and available at the web site (http://www.qwalk.org)

  6. Quantum Monte Carlo Endstation for Petascale Computing

    SciTech Connect

    Lubos Mitas

    2011-01-26

    NCSU research group has been focused on accomplising the key goals of this initiative: establishing new generation of quantum Monte Carlo (QMC) computational tools as a part of Endstation petaflop initiative for use at the DOE ORNL computational facilities and for use by computational electronic structure community at large; carrying out high accuracy quantum Monte Carlo demonstration projects in application of these tools to the forefront electronic structure problems in molecular and solid systems; expanding the impact of QMC methods and approaches; explaining and enhancing the impact of these advanced computational approaches. In particular, we have developed quantum Monte Carlo code (QWalk, www.qwalk.org) which was significantly expanded and optimized using funds from this support and at present became an actively used tool in the petascale regime by ORNL researchers and beyond. These developments have been built upon efforts undertaken by the PI's group and collaborators over the period of the last decade. The code was optimized and tested extensively on a number of parallel architectures including petaflop ORNL Jaguar machine. We have developed and redesigned a number of code modules such as evaluation of wave functions and orbitals, calculations of pfaffians and introduction of backflow coordinates together with overall organization of the code and random walker distribution over multicore architectures. We have addressed several bottlenecks such as load balancing and verified efficiency and accuracy of the calculations with the other groups of the Endstation team. The QWalk package contains about 50,000 lines of high quality object-oriented C++ and includes also interfaces to data files from other conventional electronic structure codes such as Gamess, Gaussian, Crystal and others. This grant supported PI for one month during summers, a full-time postdoc and partially three graduate students over the period of the grant duration, it has resulted in 13

  7. Hybrid algorithms in quantum Monte Carlo

    SciTech Connect

    Esler, Kenneth P; Mcminis, Jeremy; Morales, Miguel A; Clark, Bryan K.; Shulenburger, Luke; Ceperley, David M

    2012-01-01

    With advances in algorithms and growing computing powers, quantum Monte Carlo (QMC) methods have become a leading contender for high accuracy calculations for the electronic structure of realistic systems. The performance gain on recent HPC systems is largely driven by increasing parallelism: the number of compute cores of a SMP and the number of SMPs have been going up, as the Top500 list attests. However, the available memory as well as the communication and memory bandwidth per element has not kept pace with the increasing parallelism. This severely limits the applicability of QMC and the problem size it can handle. OpenMP/MPI hybrid programming provides applications with simple but effective solutions to overcome efficiency and scalability bottlenecks on large-scale clusters based on multi/many-core SMPs. We discuss the design and implementation of hybrid methods in QMCPACK and analyze its performance on current HPC platforms characterized by various memory and communication hierarchies.

  8. Quantum Monte Carlo for atoms and molecules

    SciTech Connect

    Barnett, R.N.

    1989-11-01

    The diffusion quantum Monte Carlo with fixed nodes (QMC) approach has been employed in studying energy-eigenstates for 1--4 electron systems. Previous work employing the diffusion QMC technique yielded energies of high quality for H{sub 2}, LiH, Li{sub 2}, and H{sub 2}O. Here, the range of calculations with this new approach has been extended to include additional first-row atoms and molecules. In addition, improvements in the previously computed fixed-node energies of LiH, Li{sub 2}, and H{sub 2}O have been obtained using more accurate trial functions. All computations were performed within, but are not limited to, the Born-Oppenheimer approximation. In our computations, the effects of variation of Monte Carlo parameters on the QMC solution of the Schroedinger equation were studied extensively. These parameters include the time step, renormalization time and nodal structure. These studies have been very useful in determining which choices of such parameters will yield accurate QMC energies most efficiently. Generally, very accurate energies (90--100% of the correlation energy is obtained) have been computed with single-determinant trail functions multiplied by simple correlation functions. Improvements in accuracy should be readily obtained using more complex trial functions.

  9. Quantum Monte Carlo with very large multideterminant wavefunctions.

    PubMed

    Scemama, Anthony; Applencourt, Thomas; Giner, Emmanuel; Caffarel, Michel

    2016-07-01

    An algorithm to compute efficiently the first two derivatives of (very) large multideterminant wavefunctions for quantum Monte Carlo calculations is presented. The calculation of determinants and their derivatives is performed using the Sherman-Morrison formula for updating the inverse Slater matrix. An improved implementation based on the reduction of the number of column substitutions and on a very efficient implementation of the calculation of the scalar products involved is presented. It is emphasized that multideterminant expansions contain in general a large number of identical spin-specific determinants: for typical configuration interaction-type wavefunctions the number of unique spin-specific determinants Ndetσ ( σ=↑,↓) with a non-negligible weight in the expansion is of order O(Ndet). We show that a careful implementation of the calculation of the Ndet -dependent contributions can make this step negligible enough so that in practice the algorithm scales as the total number of unique spin-specific determinants,  Ndet↑+Ndet↓, over a wide range of total number of determinants (here, Ndet up to about one million), thus greatly reducing the total computational cost. Finally, a new truncation scheme for the multideterminant expansion is proposed so that larger expansions can be considered without increasing the computational time. The algorithm is illustrated with all-electron fixed-node diffusion Monte Carlo calculations of the total energy of the chlorine atom. Calculations using a trial wavefunction including about 750,000 determinants with a computational increase of ∼400 compared to a single-determinant calculation are shown to be feasible. © 2016 Wiley Periodicals, Inc.

  10. Quantum Monte Carlo with very large multideterminant wavefunctions.

    PubMed

    Scemama, Anthony; Applencourt, Thomas; Giner, Emmanuel; Caffarel, Michel

    2016-07-01

    An algorithm to compute efficiently the first two derivatives of (very) large multideterminant wavefunctions for quantum Monte Carlo calculations is presented. The calculation of determinants and their derivatives is performed using the Sherman-Morrison formula for updating the inverse Slater matrix. An improved implementation based on the reduction of the number of column substitutions and on a very efficient implementation of the calculation of the scalar products involved is presented. It is emphasized that multideterminant expansions contain in general a large number of identical spin-specific determinants: for typical configuration interaction-type wavefunctions the number of unique spin-specific determinants Ndetσ ( σ=↑,↓) with a non-negligible weight in the expansion is of order O(Ndet). We show that a careful implementation of the calculation of the Ndet -dependent contributions can make this step negligible enough so that in practice the algorithm scales as the total number of unique spin-specific determinants,  Ndet↑+Ndet↓, over a wide range of total number of determinants (here, Ndet up to about one million), thus greatly reducing the total computational cost. Finally, a new truncation scheme for the multideterminant expansion is proposed so that larger expansions can be considered without increasing the computational time. The algorithm is illustrated with all-electron fixed-node diffusion Monte Carlo calculations of the total energy of the chlorine atom. Calculations using a trial wavefunction including about 750,000 determinants with a computational increase of ∼400 compared to a single-determinant calculation are shown to be feasible. © 2016 Wiley Periodicals, Inc. PMID:27302337

  11. Quantum Monte Carlo using a Stochastic Poisson Solver

    SciTech Connect

    Das, D; Martin, R M; Kalos, M H

    2005-05-06

    Quantum Monte Carlo (QMC) is an extremely powerful method to treat many-body systems. Usually quantum Monte Carlo has been applied in cases where the interaction potential has a simple analytic form, like the 1/r Coulomb potential. However, in a complicated environment as in a semiconductor heterostructure, the evaluation of the interaction itself becomes a non-trivial problem. Obtaining the potential from any grid-based finite-difference method, for every walker and every step is unfeasible. We demonstrate an alternative approach of solving the Poisson equation by a classical Monte Carlo within the overall quantum Monte Carlo scheme. We have developed a modified ''Walk On Spheres'' algorithm using Green's function techniques, which can efficiently account for the interaction energy of walker configurations, typical of quantum Monte Carlo algorithms. This stochastically obtained potential can be easily incorporated within popular quantum Monte Carlo techniques like variational Monte Carlo (VMC) or diffusion Monte Carlo (DMC). We demonstrate the validity of this method by studying a simple problem, the polarization of a helium atom in the electric field of an infinite capacitor.

  12. Instantons in Quantum Annealing: Thermally Assisted Tunneling Vs Quantum Monte Carlo Simulations

    NASA Technical Reports Server (NTRS)

    Jiang, Zhang; Smelyanskiy, Vadim N.; Boixo, Sergio; Isakov, Sergei V.; Neven, Hartmut; Mazzola, Guglielmo; Troyer, Matthias

    2015-01-01

    Recent numerical result (arXiv:1512.02206) from Google suggested that the D-Wave quantum annealer may have an asymptotic speed-up than simulated annealing, however, the asymptotic advantage disappears when it is compared to quantum Monte Carlo (a classical algorithm despite its name). We show analytically that the asymptotic scaling of quantum tunneling is exactly the same as the escape rate in quantum Monte Carlo for a class of problems. Thus, the Google result might be explained in our framework. We also found that the transition state in quantum Monte Carlo corresponds to the instanton solution in quantum tunneling problems, which is observed in numerical simulations.

  13. Quantum Monte Carlo : not just for energy levels.

    SciTech Connect

    Nollett, K. M.; Physics

    2007-01-01

    Quantum Monte Carlo and realistic interactions can provide well-motivated vertices and overlaps for DWBA analyses of reactions. Given an interaction in vaccum, there are several computational approaches to nuclear systems, as you have been hearing: No-core shell model with Lee-Suzuki or Bloch-Horowitz for Hamiltonian Coupled clusters with G-matrix interaction Density functional theory, granted an energy functional derived from the interaction Quantum Monte Carlo - Variational Monte Carlo Green's function Monte Carlo. The last two work directly with a bare interaction and bare operators and describe the wave function without expanding in basis functions, so they have rather different sets of advantages and disadvantages from the others. Variational Monte Carlo (VMC) is built on a sophisticated Ansatz for the wave function, built on shell model like structure modified by operator correlations. Green's function Monte Carlo (GFMC) uses an operator method to project the true ground state out of a reasonable guess wave function.

  14. Recent Developments in Quantum Monte Carlo: Methods and Applications

    NASA Astrophysics Data System (ADS)

    Aspuru-Guzik, Alan; Austin, Brian; Domin, Dominik; Galek, Peter T. A.; Handy, Nicholas; Prasad, Rajendra; Salomon-Ferrer, Romelia; Umezawa, Naoto; Lester, William A.

    2007-12-01

    The quantum Monte Carlo method in the diffusion Monte Carlo form has become recognized for its capability of describing the electronic structure of atomic, molecular and condensed matter systems to high accuracy. This talk will briefly outline the method with emphasis on recent developments connected with trial function construction, linear scaling, and applications to selected systems.

  15. Monte Carlo simulation of quantum Zeno effect in the brain

    NASA Astrophysics Data System (ADS)

    Georgiev, Danko

    2015-12-01

    Environmental decoherence appears to be the biggest obstacle for successful construction of quantum mind theories. Nevertheless, the quantum physicist Henry Stapp promoted the view that the mind could utilize quantum Zeno effect to influence brain dynamics and that the efficacy of such mental efforts would not be undermined by environmental decoherence of the brain. To address the physical plausibility of Stapp's claim, we modeled the brain using quantum tunneling of an electron in a multiple-well structure such as the voltage sensor in neuronal ion channels and performed Monte Carlo simulations of quantum Zeno effect exerted by the mind upon the brain in the presence or absence of environmental decoherence. The simulations unambiguously showed that the quantum Zeno effect breaks down for timescales greater than the brain decoherence time. To generalize the Monte Carlo simulation results for any n-level quantum system, we further analyzed the change of brain entropy due to the mind probing actions and proved a theorem according to which local projections cannot decrease the von Neumann entropy of the unconditional brain density matrix. The latter theorem establishes that Stapp's model is physically implausible but leaves a door open for future development of quantum mind theories provided the brain has a decoherence-free subspace.

  16. Reagents for Electrophilic Amination: A Quantum Monte CarloStudy

    SciTech Connect

    Amador-Bedolla, Carlos; Salomon-Ferrer, Romelia; Lester Jr.,William A.; Vazquez-Martinez, Jose A.; Aspuru-Guzik, Alan

    2006-11-01

    Electroamination is an appealing synthetic strategy toconstruct carbon-nitrogen bonds. We explore the use of the quantum MonteCarlo method and a proposed variant of the electron-pair localizationfunction--the electron-pair localization function density--as a measureof the nucleophilicity of nitrogen lone-pairs as a possible screeningprocedure for electrophilic reagents.

  17. Quantum Monte Carlo simulation with a black hole

    NASA Astrophysics Data System (ADS)

    Benić, Sanjin; Yamamoto, Arata

    2016-05-01

    We perform quantum Monte Carlo simulations in the background of a classical black hole. The lattice discretized path integral is numerically calculated in the Schwarzschild metric and in its approximated metric. We study spontaneous symmetry breaking of a real scalar field theory. We observe inhomogeneous symmetry breaking induced by an inhomogeneous gravitational field.

  18. Bayesian methods, maximum entropy, and quantum Monte Carlo

    SciTech Connect

    Gubernatis, J.E.; Silver, R.N. ); Jarrell, M. )

    1991-01-01

    We heuristically discuss the application of the method of maximum entropy to the extraction of dynamical information from imaginary-time, quantum Monte Carlo data. The discussion emphasizes the utility of a Bayesian approach to statistical inference and the importance of statistically well-characterized data. 14 refs.

  19. Chemical accuracy from quantum Monte Carlo for the benzene dimer.

    PubMed

    Azadi, Sam; Cohen, R E

    2015-09-14

    We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of -2.3(4) and -2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is -2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods. PMID:26374029

  20. Chemical accuracy from quantum Monte Carlo for the benzene dimer

    SciTech Connect

    Azadi, Sam; Cohen, R. E.

    2015-09-14

    We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of −2.3(4) and −2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is −2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.

  1. Chemical accuracy from quantum Monte Carlo for the benzene dimer.

    PubMed

    Azadi, Sam; Cohen, R E

    2015-09-14

    We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of -2.3(4) and -2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is -2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.

  2. Simple formalism for efficient derivatives and multi-determinant expansions in quantum Monte Carlo.

    PubMed

    Filippi, Claudia; Assaraf, Roland; Moroni, Saverio

    2016-05-21

    We present a simple and general formalism to compute efficiently the derivatives of a multi-determinant Jastrow-Slater wave function, the local energy, the interatomic forces, and similar quantities needed in quantum Monte Carlo. Through a straightforward manipulation of matrices evaluated on the occupied and virtual orbitals, we obtain an efficiency equivalent to algorithmic differentiation in the computation of the interatomic forces and the optimization of the orbital parameters. Furthermore, for a large multi-determinant expansion, the significant computational gain afforded by a recently introduced table method is here extended to the local value of any one-body operator and to its derivatives, in both all-electron and pseudopotential calculations. PMID:27208934

  3. Quantum Monte Carlo Calculations of Symmetric Nuclear Matter

    SciTech Connect

    Gandolfi, Stefano; Pederiva, Francesco; Fantoni, Stefano; Schmidt, Kevin E.

    2007-03-09

    We present an accurate numerical study of the equation of state of nuclear matter based on realistic nucleon-nucleon interactions by means of auxiliary field diffusion Monte Carlo (AFDMC) calculations. The AFDMC method samples the spin and isospin degrees of freedom allowing for quantum simulations of large nucleonic systems and represents an important step forward towards a quantitative understanding of problems in nuclear structure and astrophysics.

  4. Quantum Monte Carlo calculations of symmetric nuclear matter.

    PubMed

    Gandolfi, Stefano; Pederiva, Francesco; Fantoni, Stefano; Schmidt, Kevin E

    2007-03-01

    We present an accurate numerical study of the equation of state of nuclear matter based on realistic nucleon-nucleon interactions by means of auxiliary field diffusion Monte Carlo (AFDMC) calculations. The AFDMC method samples the spin and isospin degrees of freedom allowing for quantum simulations of large nucleonic systems and represents an important step forward towards a quantitative understanding of problems in nuclear structure and astrophysics.

  5. Valence-bond quantum Monte Carlo algorithms defined on trees.

    PubMed

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update. PMID:25314561

  6. Applying Quantum Monte Carlo to the Electronic Structure Problem

    NASA Astrophysics Data System (ADS)

    Powell, Andrew D.; Dawes, Richard

    2016-06-01

    Two distinct types of Quantum Monte Carlo (QMC) calculations are applied to electronic structure problems such as calculating potential energy curves and producing benchmark values for reaction barriers. First, Variational and Diffusion Monte Carlo (VMC and DMC) methods using a trial wavefunction subject to the fixed node approximation were tested using the CASINO code.[1] Next, Full Configuration Interaction Quantum Monte Carlo (FCIQMC), along with its initiator extension (i-FCIQMC) were tested using the NECI code.[2] FCIQMC seeks the FCI energy for a specific basis set. At a reduced cost, the efficient i-FCIQMC method can be applied to systems in which the standard FCIQMC approach proves to be too costly. Since all of these methods are statistical approaches, uncertainties (error-bars) are introduced for each calculated energy. This study tests the performance of the methods relative to traditional quantum chemistry for some benchmark systems. References: [1] R. J. Needs et al., J. Phys.: Condensed Matter 22, 023201 (2010). [2] G. H. Booth et al., J. Chem. Phys. 131, 054106 (2009).

  7. Valence-bond quantum Monte Carlo algorithms defined on trees.

    PubMed

    Deschner, Andreas; Sørensen, Erik S

    2014-09-01

    We present a class of algorithms for performing valence-bond quantum Monte Carlo of quantum spin models. Valence-bond quantum Monte Carlo is a projective T=0 Monte Carlo method based on sampling of a set of operator strings that can be viewed as forming a treelike structure. The algorithms presented here utilize the notion of a worm that moves up and down this tree and changes the associated operator string. In quite general terms, we derive a set of equations whose solutions correspond to a whole class of algorithms. As specific examples of this class of algorithms, we focus on two cases. The bouncing worm algorithm, for which updates are always accepted by allowing the worm to bounce up and down the tree, and the driven worm algorithm, where a single parameter controls how far up the tree the worm reaches before turning around. The latter algorithm involves only a single bounce where the worm turns from going up the tree to going down. The presence of the control parameter necessitates the introduction of an acceptance probability for the update.

  8. Continuous-time quantum Monte Carlo impurity solvers

    NASA Astrophysics Data System (ADS)

    Gull, Emanuel; Werner, Philipp; Fuchs, Sebastian; Surer, Brigitte; Pruschke, Thomas; Troyer, Matthias

    2011-04-01

    Continuous-time quantum Monte Carlo impurity solvers are algorithms that sample the partition function of an impurity model using diagrammatic Monte Carlo techniques. The present paper describes codes that implement the interaction expansion algorithm originally developed by Rubtsov, Savkin, and Lichtenstein, as well as the hybridization expansion method developed by Werner, Millis, Troyer, et al. These impurity solvers are part of the ALPS-DMFT application package and are accompanied by an implementation of dynamical mean-field self-consistency equations for (single orbital single site) dynamical mean-field problems with arbitrary densities of states. Program summaryProgram title: dmft Catalogue identifier: AEIL_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEIL_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: ALPS LIBRARY LICENSE version 1.1 No. of lines in distributed program, including test data, etc.: 899 806 No. of bytes in distributed program, including test data, etc.: 32 153 916 Distribution format: tar.gz Programming language: C++ Operating system: The ALPS libraries have been tested on the following platforms and compilers: Linux with GNU Compiler Collection (g++ version 3.1 and higher), and Intel C++ Compiler (icc version 7.0 and higher) MacOS X with GNU Compiler (g++ Apple-version 3.1, 3.3 and 4.0) IBM AIX with Visual Age C++ (xlC version 6.0) and GNU (g++ version 3.1 and higher) compilers Compaq Tru64 UNIX with Compq C++ Compiler (cxx) SGI IRIX with MIPSpro C++ Compiler (CC) HP-UX with HP C++ Compiler (aCC) Windows with Cygwin or coLinux platforms and GNU Compiler Collection (g++ version 3.1 and higher) RAM: 10 MB-1 GB Classification: 7.3 External routines: ALPS [1], BLAS/LAPACK, HDF5 Nature of problem: (See [2].) Quantum impurity models describe an atom or molecule embedded in a host material with which it can exchange electrons. They are basic to nanoscience as

  9. Infinite variance in fermion quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Shi, Hao; Zhang, Shiwei

    2016-03-01

    For important classes of many-fermion problems, quantum Monte Carlo (QMC) methods allow exact calculations of ground-state and finite-temperature properties without the sign problem. The list spans condensed matter, nuclear physics, and high-energy physics, including the half-filled repulsive Hubbard model, the spin-balanced atomic Fermi gas, and lattice quantum chromodynamics calculations at zero density with Wilson Fermions, and is growing rapidly as a number of problems have been discovered recently to be free of the sign problem. In these situations, QMC calculations are relied on to provide definitive answers. Their results are instrumental to our ability to understand and compute properties in fundamental models important to multiple subareas in quantum physics. It is shown, however, that the most commonly employed algorithms in such situations have an infinite variance problem. A diverging variance causes the estimated Monte Carlo statistical error bar to be incorrect, which can render the results of the calculation unreliable or meaningless. We discuss how to identify the infinite variance problem. An approach is then proposed to solve the problem. The solution does not require major modifications to standard algorithms, adding a "bridge link" to the imaginary-time path integral. The general idea is applicable to a variety of situations where the infinite variance problem may be present. Illustrative results are presented for the ground state of the Hubbard model at half-filling.

  10. Infinite variance in fermion quantum Monte Carlo calculations.

    PubMed

    Shi, Hao; Zhang, Shiwei

    2016-03-01

    For important classes of many-fermion problems, quantum Monte Carlo (QMC) methods allow exact calculations of ground-state and finite-temperature properties without the sign problem. The list spans condensed matter, nuclear physics, and high-energy physics, including the half-filled repulsive Hubbard model, the spin-balanced atomic Fermi gas, and lattice quantum chromodynamics calculations at zero density with Wilson Fermions, and is growing rapidly as a number of problems have been discovered recently to be free of the sign problem. In these situations, QMC calculations are relied on to provide definitive answers. Their results are instrumental to our ability to understand and compute properties in fundamental models important to multiple subareas in quantum physics. It is shown, however, that the most commonly employed algorithms in such situations have an infinite variance problem. A diverging variance causes the estimated Monte Carlo statistical error bar to be incorrect, which can render the results of the calculation unreliable or meaningless. We discuss how to identify the infinite variance problem. An approach is then proposed to solve the problem. The solution does not require major modifications to standard algorithms, adding a "bridge link" to the imaginary-time path integral. The general idea is applicable to a variety of situations where the infinite variance problem may be present. Illustrative results are presented for the ground state of the Hubbard model at half-filling. PMID:27078480

  11. Minimising biases in full configuration interaction quantum Monte Carlo.

    PubMed

    Vigor, W A; Spencer, J S; Bearpark, M J; Thom, A J W

    2015-03-14

    We show that Full Configuration Interaction Quantum Monte Carlo (FCIQMC) is a Markov chain in its present form. We construct the Markov matrix of FCIQMC for a two determinant system and hence compute the stationary distribution. These solutions are used to quantify the dependence of the population dynamics on the parameters defining the Markov chain. Despite the simplicity of a system with only two determinants, it still reveals a population control bias inherent to the FCIQMC algorithm. We investigate the effect of simulation parameters on the population control bias for the neon atom and suggest simulation setups to, in general, minimise the bias. We show a reweight ing scheme to remove the bias caused by population control commonly used in diffusion Monte Carlo [Umrigar et al., J. Chem. Phys. 99, 2865 (1993)] is effective and recommend its use as a post processing step. PMID:25770522

  12. Quantum Monte Carlo calculations with chiral effective field theory interactions.

    PubMed

    Gezerlis, A; Tews, I; Epelbaum, E; Gandolfi, S; Hebeler, K; Nogga, A; Schwenk, A

    2013-07-19

    We present the first quantum Monte Carlo (QMC) calculations with chiral effective field theory (EFT) interactions. To achieve this, we remove all sources of nonlocality, which hamper the inclusion in QMC calculations, in nuclear forces to next-to-next-to-leading order. We perform auxiliary-field diffusion Monte Carlo (AFDMC) calculations for the neutron matter energy up to saturation density based on local leading-order, next-to-leading order, and next-to-next-to-leading order nucleon-nucleon interactions. Our results exhibit a systematic order-by-order convergence in chiral EFT and provide nonperturbative benchmarks with theoretical uncertainties. For the softer interactions, perturbative calculations are in excellent agreement with the AFDMC results. This work paves the way for QMC calculations with systematic chiral EFT interactions for nuclei and nuclear matter, for testing the perturbativeness of different orders, and allows for matching to lattice QCD results by varying the pion mass.

  13. Monte Carlo sampling from the quantum state space. I

    NASA Astrophysics Data System (ADS)

    Shang, Jiangwei; Seah, Yi-Lin; Khoon Ng, Hui; Nott, David John; Englert, Berthold-Georg

    2015-04-01

    High-quality random samples of quantum states are needed for a variety of tasks in quantum information and quantum computation. Searching the high-dimensional quantum state space for a global maximum of an objective function with many local maxima or evaluating an integral over a region in the quantum state space are but two exemplary applications of many. These tasks can only be performed reliably and efficiently with Monte Carlo methods, which involve good samplings of the parameter space in accordance with the relevant target distribution. We show how the standard strategies of rejection sampling, importance sampling, and Markov-chain sampling can be adapted to this context, where the samples must obey the constraints imposed by the positivity of the statistical operator. For illustration, we generate sample points in the probability space of qubits, qutrits, and qubit pairs, both for tomographically complete and incomplete measurements. We use these samples for various purposes: establish the marginal distribution of the purity; compute the fractional volume of separable two-qubit states; and calculate the size of regions with bounded likelihood.

  14. Correlated wavefunction quantum Monte Carlo approach to solids

    SciTech Connect

    Louie, S.G.

    1992-10-01

    A method for calculating the electronic and structural properties of solids using correlated wavefunctions together with quantum Monte Carlo techniques is described. The approach retains the exact Coulomb interaction between the electrons and employs a many-electron wavefunction of the Jastrow-Slater form. Several examples are given to illustrate the utility of the method. Topics discussed include the cohesive properties of bulk semiconductors, the magnetic-field- induced Wigner crystal in two dimensions, and the magnetic structure of bcc hydrogen. Landau level mixing is shown to be important in determining the transition between the fractional quantum Hall liquid and the Wigner crystal. Information on electron correlations such as the pair correlation functions which are not accessible to one- electron theories is also obtained. 24 refs, 5 figs, 1 tab.

  15. Performance of quantum Monte Carlo for calculating molecular bond lengths

    NASA Astrophysics Data System (ADS)

    Cleland, Deidre M.; Per, Manolo C.

    2016-03-01

    This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF. The most accurate MAD of 3 ± 2 × 10-3 Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10-3 Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries.

  16. A pure-sampling quantum Monte Carlo algorithm

    SciTech Connect

    Ospadov, Egor; Rothstein, Stuart M.

    2015-01-14

    The objective of pure-sampling quantum Monte Carlo is to calculate physical properties that are independent of the importance sampling function being employed in the calculation, save for the mismatch of its nodal hypersurface with that of the exact wave function. To achieve this objective, we report a pure-sampling algorithm that combines features of forward walking methods of pure-sampling and reptation quantum Monte Carlo (RQMC). The new algorithm accurately samples properties from the mixed and pure distributions simultaneously in runs performed at a single set of time-steps, over which extrapolation to zero time-step is performed. In a detailed comparison, we found RQMC to be less efficient. It requires different sets of time-steps to accurately determine the energy and other properties, such as the dipole moment. We implement our algorithm by systematically increasing an algorithmic parameter until the properties converge to statistically equivalent values. As a proof in principle, we calculated the fixed-node energy, static α polarizability, and other one-electron expectation values for the ground-states of LiH and water molecules. These quantities are free from importance sampling bias, population control bias, time-step bias, extrapolation-model bias, and the finite-field approximation. We found excellent agreement with the accepted values for the energy and a variety of other properties for those systems.

  17. A pure-sampling quantum Monte Carlo algorithm

    NASA Astrophysics Data System (ADS)

    Ospadov, Egor; Rothstein, Stuart M.

    2015-01-01

    The objective of pure-sampling quantum Monte Carlo is to calculate physical properties that are independent of the importance sampling function being employed in the calculation, save for the mismatch of its nodal hypersurface with that of the exact wave function. To achieve this objective, we report a pure-sampling algorithm that combines features of forward walking methods of pure-sampling and reptation quantum Monte Carlo (RQMC). The new algorithm accurately samples properties from the mixed and pure distributions simultaneously in runs performed at a single set of time-steps, over which extrapolation to zero time-step is performed. In a detailed comparison, we found RQMC to be less efficient. It requires different sets of time-steps to accurately determine the energy and other properties, such as the dipole moment. We implement our algorithm by systematically increasing an algorithmic parameter until the properties converge to statistically equivalent values. As a proof in principle, we calculated the fixed-node energy, static α polarizability, and other one-electron expectation values for the ground-states of LiH and water molecules. These quantities are free from importance sampling bias, population control bias, time-step bias, extrapolation-model bias, and the finite-field approximation. We found excellent agreement with the accepted values for the energy and a variety of other properties for those systems.

  18. Properties of reactive oxygen species by quantum Monte Carlo

    SciTech Connect

    Zen, Andrea; Trout, Bernhardt L.; Guidoni, Leonardo

    2014-07-07

    The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N{sup 3} − N{sup 4}, where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles.

  19. Properties of reactive oxygen species by quantum Monte Carlo.

    PubMed

    Zen, Andrea; Trout, Bernhardt L; Guidoni, Leonardo

    2014-07-01

    The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N(3) - N(4), where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles. PMID:25005287

  20. Properties of reactive oxygen species by quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Zen, Andrea; Trout, Bernhardt L.; Guidoni, Leonardo

    2014-07-01

    The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N3 - N4, where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles.

  1. Quantum Monte-Carlo Study of Electron Correlation in Heterostructure Quantum Dots

    SciTech Connect

    Mei-Yin Chou

    2006-11-12

    The goal of this project is to study electron correlation in a confined geometry (quantum dots) within the two-dimensional quantum well in the sandwiches of two semiconductor materials. For these systems one is able to tune the electronic properties by controlling the size and the electron number, creating tremendous potential for novel applications. Much effort in this emerging field has been devoted to producing entangled states that are required for quantum information processing. At the same time, new physical phenomena have emerged from these artificial structures. Adding electrons to a quantum dot is more complicated than filling up discrete energy levels due to electron correlation. Therefore, our project is focusing on employing the state-of-the-art quantum Monte Carlo methods to study the electron-electron interaction. A close examination of the breakdown of Hund's rules and electron localization has been conducted in our simulations. The results are summarized in this report.

  2. Interdimensional degeneracies in van der Waals clusters and quantum Monte Carlo computation of rovibrational states.

    PubMed

    Nightingale, M P; Moodley, Mervlyn

    2005-07-01

    Quantum Monte Carlo estimates of the spectrum of rotationally invariant states of noble gas clusters suggest interdimensional degeneracy in N-1 and N+1 spatial dimensions. We derive this property by mapping the Schrodinger eigenvalue problem onto an eigenvalue equation in which D appears as a continuous variable. We discuss implications for quantum Monte Carlo and dimensional scaling methods.

  3. Itinerant scenario for Fe pnictides: Comparison with quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Chubukov, Andrey V.; Xing, Rui-Qi

    2016-04-01

    Recent applications of quantum Monte Carlo (QMC) technique to Fe-based superconductors opened a way to directly verify the applicability of the itinerant scenario for these systems. Fe-based superconductors undergo various instabilities upon lowering temperature (magnetism, superconductivity, nematicity/orbital order), and one can check whether the hierarchy of instabilities obtained within the itinerant approach is the same as in unbiased QMC simulations. In a recent paper [arXiv:1512.08523] the authors considered the simplest two-band model with interaction tailored to favor orbital order. The type of the orbital order found in QMC is different from the one found in earlier itinerant analysis. We report the results of our calculations within the itinerant scenario and argue that they are in perfect agreement with QMC.

  4. Neutron monitor generated data distributions in quantum variational Monte Carlo

    NASA Astrophysics Data System (ADS)

    Kussainov, A. S.; Pya, N.

    2016-08-01

    We have assessed the potential applications of the neutron monitor hardware as random number generator for normal and uniform distributions. The data tables from the acquisition channels with no extreme changes in the signal level were chosen as the retrospective model. The stochastic component was extracted by fitting the raw data with splines and then subtracting the fit. Scaling the extracted data to zero mean and variance of one is sufficient to obtain a stable standard normal random variate. Distributions under consideration pass all available normality tests. Inverse transform sampling is suggested to use as a source of the uniform random numbers. Variational Monte Carlo method for quantum harmonic oscillator was used to test the quality of our random numbers. If the data delivery rate is of importance and the conventional one minute resolution neutron count is insufficient, we could always settle for an efficient seed generator to feed into the faster algorithmic random number generator or create a buffer.

  5. Quantum Monte Carlo Calculations in Solids with Downfolded Hamiltonians

    NASA Astrophysics Data System (ADS)

    Ma, Fengjie; Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2015-06-01

    We present a combination of a downfolding many-body approach with auxiliary-field quantum Monte Carlo (AFQMC) calculations for extended systems. Many-body calculations operate on a simpler Hamiltonian which retains material-specific properties. The Hamiltonian is systematically improvable and allows one to dial, in principle, between the simplest model and the original Hamiltonian. As a by-product, pseudopotential errors are essentially eliminated using frozen orbitals constructed adaptively from the solid environment. The computational cost of the many-body calculation is dramatically reduced without sacrificing accuracy. Excellent accuracy is achieved for a range of solids, including semiconductors, ionic insulators, and metals. We apply the method to calculate the equation of state of cubic BN under ultrahigh pressure, and determine the spin gap in NiO, a challenging prototypical material with strong electron correlation effects.

  6. Quantum Monte Carlo Calculations in Solids with Downfolded Hamiltonians.

    PubMed

    Ma, Fengjie; Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2015-06-01

    We present a combination of a downfolding many-body approach with auxiliary-field quantum Monte Carlo (AFQMC) calculations for extended systems. Many-body calculations operate on a simpler Hamiltonian which retains material-specific properties. The Hamiltonian is systematically improvable and allows one to dial, in principle, between the simplest model and the original Hamiltonian. As a by-product, pseudopotential errors are essentially eliminated using frozen orbitals constructed adaptively from the solid environment. The computational cost of the many-body calculation is dramatically reduced without sacrificing accuracy. Excellent accuracy is achieved for a range of solids, including semiconductors, ionic insulators, and metals. We apply the method to calculate the equation of state of cubic BN under ultrahigh pressure, and determine the spin gap in NiO, a challenging prototypical material with strong electron correlation effects. PMID:26196632

  7. Pseudopotentials for quantum Monte Carlo studies of transition metal oxides

    DOE PAGES

    Krogel, Jaron T.; Santana Palacio, Juan A.; Reboredo, Fernando A.

    2016-02-22

    Quantum Monte Carlo (QMC) calculations of transition metal oxides are partially limited by the availability of high-quality pseudopotentials that are both accurate in QMC and compatible with major plane-wave electronic structure codes. We have generated a set of neon-core pseudopotentials with small cutoff radii for the early transition metal elements Sc to Zn within the local density approximation of density functional theory. The pseudopotentials have been directly tested for accuracy within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (M) atoms and the binding curve of each M-O dimer. We find the ionization potentialsmore » to be accurate to 0.16(1) eV, on average, relative to experiment. The equilibrium bond lengths of the dimers are within 0.5(1)% of experimental values, on average, and the binding energies are also typically accurate to 0.18(3) eV. The level of accuracy we find for atoms and dimers is comparable to what has recently been observed for bulk metals and oxides using the same pseudopotentials. Our QMC pseudopotential results compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.« less

  8. Pseudopotentials for quantum Monte Carlo studies of transition metal oxides

    NASA Astrophysics Data System (ADS)

    Krogel, Jaron T.; Santana, Juan A.; Reboredo, Fernando A.

    2016-02-01

    Quantum Monte Carlo (QMC) calculations of transition metal oxides are partially limited by the availability of high-quality pseudopotentials that are both accurate in QMC and compatible with major plane-wave electronic structure codes. We have generated a set of neon-core pseudopotentials with small cutoff radii for the early transition metal elements Sc to Zn within the local density approximation of density functional theory. The pseudopotentials have been directly tested for accuracy within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (M) atoms and the binding curve of each M-O dimer. We find the ionization potentials to be accurate to 0.16(1) eV, on average, relative to experiment. The equilibrium bond lengths of the dimers are within 0.5(1)% of experimental values, on average, and the binding energies are also typically accurate to 0.18(3) eV. The level of accuracy we find for atoms and dimers is comparable to what has recently been observed for bulk metals and oxides using the same pseudopotentials. Our QMC pseudopotential results also compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.

  9. Correlation effects in quantum spin-Hall insulators: a quantum Monte Carlo study.

    PubMed

    Hohenadler, M; Lang, T C; Assaad, F F

    2011-03-11

    We consider the Kane-Mele model supplemented by a Hubbard U term. The phase diagram is mapped out using projective auxiliary field quantum Monte Carlo simulations. The quantum spin liquid of the Hubbard model is robust against weak spin-orbit interaction, and is not adiabatically connected to the spin-Hall insulating state. Beyond a critical value of U>U(c) both states are unstable toward magnetic ordering. In the quantum spin-Hall state we study the spin, charge, and single-particle dynamics of the helical Luttinger liquid by retaining the Hubbard interaction only on a ribbon edge. The Hubbard interaction greatly suppresses charge currents along the edge and promotes edge magnetism but leaves the single-particle signatures of the helical liquid intact.

  10. Quantum Monte Carlo Algorithms for Diagrammatic Vibrational Structure Calculations

    NASA Astrophysics Data System (ADS)

    Hermes, Matthew; Hirata, So

    2015-06-01

    Convergent hierarchies of theories for calculating many-body vibrational ground and excited-state wave functions, such as Møller-Plesset perturbation theory or coupled cluster theory, tend to rely on matrix-algebraic manipulations of large, high-dimensional arrays of anharmonic force constants, tasks which require large amounts of computer storage space and which are very difficult to implement in a parallel-scalable fashion. On the other hand, existing quantum Monte Carlo (QMC) methods for vibrational wave functions tend to lack robust techniques for obtaining excited-state energies, especially for large systems. By exploiting analytical identities for matrix elements of position operators in a harmonic oscillator basis, we have developed stochastic implementations of the size-extensive vibrational self-consistent field (MC-XVSCF) and size-extensive vibrational Møller-Plesset second-order perturbation (MC-XVMP2) theories which do not require storing the potential energy surface (PES). The programmable equations of MC-XVSCF and MC-XVMP2 take the form of a small number of high-dimensional integrals evaluated using Metropolis Monte Carlo techniques. The associated integrands require independent evaluations of only the value, not the derivatives, of the PES at many points, a task which is trivial to parallelize. However, unlike existing vibrational QMC methods, MC-XVSCF and MC-XVMP2 can calculate anharmonic frequencies directly, rather than as a small difference between two noisy total energies, and do not require user-selected coordinates or nodal surfaces. MC-XVSCF and MC-XVMP2 can also directly sample the PES in a given approximation without analytical or grid-based approximations, enabling us to quantify the errors induced by such approximations.

  11. Quantum Monte Carlo Calculations Applied to Magnetic Molecules

    SciTech Connect

    Engelhardt, Larry

    2006-01-01

    We have calculated the equilibrium thermodynamic properties of Heisenberg spin systems using a quantum Monte Carlo (QMC) method. We have used some of these systems as models to describe recently synthesized magnetic molecules, and-upon comparing the results of these calculations with experimental data-have obtained accurate estimates for the basic parameters of these models. We have also performed calculations for other systems that are of more general interest, being relevant both for existing experimental data and for future experiments. Utilizing the concept of importance sampling, these calculations can be carried out in an arbitrarily large quantum Hilbert space, while still avoiding any approximations that would introduce systematic errors. The only errors are statistical in nature, and as such, their magnitudes are accurately estimated during the course of a simulation. Frustrated spin systems present a major challenge to the QMC method, nevertheless, in many instances progress can be made. In this chapter, the field of magnetic molecules is introduced, paying particular attention to the characteristics that distinguish magnetic molecules from other systems that are studied in condensed matter physics. We briefly outline the typical path by which we learn about magnetic molecules, which requires a close relationship between experiments and theoretical calculations. The typical experiments are introduced here, while the theoretical methods are discussed in the next chapter. Each of these theoretical methods has a considerable limitation, also described in Chapter 2, which together serve to motivate the present work. As is shown throughout the later chapters, the present QMC method is often able to provide useful information where other methods fail. In Chapter 3, the use of Monte Carlo methods in statistical physics is reviewed, building up the fundamental ideas that are necessary in order to understand the method that has been used in this work. With these

  12. Energy density matrix formalism for interacting quantum systems: Quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Krogel, Jaron T.; Kim, Jeongnim; Reboredo, Fernando A.

    2014-07-01

    We develop an energy density matrix that parallels the one-body reduced density matrix (1RDM) for many-body quantum systems. Just as the density matrix gives access to the number density and occupation numbers, the energy density matrix yields the energy density and orbital occupation energies. The eigenvectors of the matrix provide a natural orbital partitioning of the energy density while the eigenvalues comprise a single-particle energy spectrum obeying a total energy sum rule. For mean-field systems the energy density matrix recovers the exact spectrum. When correlation becomes important, the occupation energies resemble quasiparticle energies in some respects. We explore the occupation energy spectrum for the finite 3D homogeneous electron gas in the metallic regime and an isolated oxygen atom with ground-state quantum Monte Carlo techniques implemented in the qmcpack simulation code. The occupation energy spectrum for the homogeneous electron gas can be described by an effective mass below the Fermi level. Above the Fermi level evanescent behavior in the occupation energies is observed in similar fashion to the occupation numbers of the 1RDM. A direct comparison with total energy differences shows a quantitative connection between the occupation energies and electron addition and removal energies for the electron gas. For the oxygen atom, the association between the ground-state occupation energies and particle addition and removal energies becomes only qualitative. The energy density matrix provides an avenue for describing energetics with quantum Monte Carlo methods which have traditionally been limited to total energies.

  13. Quantum Monte Carlo calculations of magnetic couplings in cuprates

    NASA Astrophysics Data System (ADS)

    Foyevtsova, Kateryna; Krogel, Jaron; Kim, Jeongnim; Reboredo, Fernando

    2014-03-01

    Spin excitations are generally believed to play a fundamental role in the mechanism of high temperature superconductivity in cuprates. However, accurate description of the cuprates' magnetic properties and, in particular, calculation of spin exchange couplings have been a long-standing challenge to the electronic structure theory. While the quantum-mechanically more rigorous cluster methods suffer from finite-size effects, the density functional theory approach, on the other hand, is ambiguous due to a rich variety of approximations to the exchange-correlation functional available which often give very different numbers for the spin exchange constants. For example, in some cuprates the theoretically predicted values of the nearest-neighbor superexchange range from 1 eV (local density approximation) to 0.05 eV (periodic unrestricted Hartree Fock) [C. de Graaf et al, PRB 63 014404 (2000)]. We compute spin exchange constants with the fixed-node diffusion Monte Carlo method (FN-DMC). In one-dimensional cuprates, we find that the FN-DMC computed nearest-neighbor spin superexchange is in an excellent agreement with experiment. This both demonstrates that FN-DMC is capable of describing properly the magnetism of strongly correlated oxides as well as positions this technique as the method of choice for theoretical parameterization of spin models. Research supported by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division.

  14. Cohesion energetics of carbon allotropes: Quantum Monte Carlo study

    SciTech Connect

    Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun; Lee, Hoonkyung; Kwon, Yongkyung; Kim, Jeongnim

    2014-03-21

    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp{sup 3}-bonded diamond, sp{sup 2}-bonded graphene, sp–sp{sup 2} hybridized graphynes, and sp-bonded carbyne. The computed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values determined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases systematically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of γ-graphyne, the most energetically stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experimental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally, we conclude that the cohesive energy of a newly proposed graphyne can be accurately estimated with the carbon–carbon bond energies determined from the cohesive energies of graphene and three different graphynes considered here.

  15. Cohesion Energetics of Carbon Allotropes: Quantum Monte Carlo Study

    SciTech Connect

    Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun; Lee, Hoonkyung; Kim, Jeongnim; Kwon, Yongkyung

    2014-01-01

    We have performed quantum Monte Carlo calculations to study the cohesion energetics of carbon allotropes, including sp3-bonded diamond, sp2-bonded graphene, sp-sp2 hybridized graphynes, and sp-bonded carbyne. The comput- ed cohesive energies of diamond and graphene are found to be in excellent agreement with the corresponding values de- termined experimentally for diamond and graphite, respectively, when the zero-point energies, along with the interlayer binding in the case of graphite, are included. We have also found that the cohesive energy of graphyne decreases system- atically as the ratio of sp-bonded carbon atoms increases. The cohesive energy of -graphyne, the most energetically- stable graphyne, turns out to be 6.766(6) eV/atom, which is smaller than that of graphene by 0.698(12) eV/atom. Experi- mental difficulty in synthesizing graphynes could be explained by their significantly smaller cohesive energies. Finally we conclude that the cohesive energy of a newly-proposed two-dimensional carbon network can be accurately estimated with the carbon-carbon bond energies determined from the cohesive energies of graphene and three different graphynes.

  16. Quantum Monte Carlo Simulation of condensed van der Waals Systems

    NASA Astrophysics Data System (ADS)

    Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; Kim, Jeongnim; Anatole von Lilienfeld, O.

    2012-02-01

    Van der Waals forces are as ubiquitous as infamous. While post-Hartree-Fock methods enable accurate estimates of these forces in molecules and clusters, they remain elusive for dealing with many-electron condensed phase systems. We present Quantum Monte Carlo [1,2] results for condensed van der Waals systems. Interatomic many-body contributions to cohesive energies and bulk modulus will be discussed. Numerical evidence is presented for crystals of rare gas atoms, and compared to experiments and methods [3]. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DoE's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.[4pt] [1] J. Kim, K. Esler, J. McMinis and D. Ceperley, SciDAC 2010, J. of Physics: Conference series, Chattanooga, Tennessee, July 11 2011 [0pt] [2] QMCPACK simulation suite, http://qmcpack.cmscc.org (unpublished)[0pt] [3] O. A. von Lillienfeld and A. Tkatchenko, J. Chem. Phys. 132 234109 (2010)

  17. Quantum Monte Carlo study of magnetic impurity in bilayer grephene

    NASA Astrophysics Data System (ADS)

    Sun, J. H.; Hu, F. M.; Tang, H. K.; Lin, Hai-Qing

    2012-02-01

    It is expected to observe many different properties in bilayer graphene when compared with single layer graphene due to the differences in crystal structure. Additionally, bilayer system offers a freedom of inducing a gap in the energy band by applying a shift in the electrochemical potential to two graphene layers. In this work, we study the magnetic properties of an Anderson magnetic adatom in Bernal stacking bilayer graphene and compare the results with those of single layer counterpart. Several different cases such as different adatom position and different potential bias of two layers are studied using the quantum Monte Carlo method. In all the cases, we find that the impurity local magnetic moment can be switched between relatively large and small values by tuning the chemical potential. We apply MaxEnT method to compute impurity spectral density and find its behavior to differ from that of an impurity in a single layer graphene. We also calculate various correlation functions and make comparisons.

  18. Quantum dynamics at finite temperature: Time-dependent quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Christov, Ivan P.

    2016-08-01

    In this work we investigate the ground state and the dissipative quantum dynamics of interacting charged particles in an external potential at finite temperature. The recently devised time-dependent quantum Monte Carlo (TDQMC) method allows a self-consistent treatment of the system of particles together with bath oscillators first for imaginary-time propagation of Schrödinger type of equations where both the system and the bath converge to their finite temperature ground state, and next for real time calculation where the dissipative dynamics is demonstrated. In that context the application of TDQMC appears as promising alternative to the path-integral related techniques where the real time propagation can be a challenge.

  19. Quantum Monte Carlo calculations for point defects in semiconductors

    NASA Astrophysics Data System (ADS)

    Hennig, Richard

    2010-03-01

    Point defects in silicon have been studied extensively for many years. Nevertheless the mechanism for self diffusion in Si is still debated. Direct experimental measurements of the selfdiffusion in silicon are complicated by the lack of suitable isotopes. Formation energies are either obtained from theory or indirectly through the analysis of dopant and metal diffusion experiments. Density functional calculations predict formation energies ranging from 3 to 5 eV depending on the approximations used for the exchange-correlation functional [1]. Analysis of dopant and metal diffusion experiments result in similar broad range of diffusion activation energies of 4.95 [2], 4.68 [3], 2.4 eV [4]. Assuming a migration energy barrier of 0.1-0.3 eV [5], the resulting experimental interstitial formation energies range from 2.1 - 4.9 eV. To answer the question of the formation energy of Si interstitials we resort to a many-body description of the wave functions using quantum Monte Carlo (QMC) techniques. Previous QMC calculations resulted in formation energies for the interstitials of around 5 eV [1,6]. We present a careful analysis of all the controlled and uncontrolled approximations that affect the defect formation energies in variational and diffusion Monte Carlo calculations. We find that more accurate trial wave functions for QMC using improved Jastrow expansions and most importantly a backflow transformation for the electron coordinates significantly improve the wave functions. Using zero-variance extrapolation, we predict interstitial formation energies in good agreement with hybrid DFT functionals [1] and recent GW calculations [7]. [4pt] [1] E. R. Batista, J. Heyd, R. G. Hennig, B. P. Uberuaga, R. L. Martin, G. E. Scuseria, C. J. Umrigar, and J. W. Wilkins. Phys. Rev. B 74, 121102(R) (2006).[0pt] [2] H. Bracht, E. E. Haller, and R. Clark-Phelps, Phys. Rev. Lett. 81, 393 (1998). [0pt] [3] A. Ural, P. B. Griffin, and J. D. Plummer, Phys. Rev. Lett. 83, 3454 (1999). [0pt

  20. Quantum Monte Carlo for electronic structure: Recent developments and applications

    SciTech Connect

    Rodriquez, M. M.S.

    1995-04-01

    Quantum Monte Carlo (QMC) methods have been found to give excellent results when applied to chemical systems. The main goal of the present work is to use QMC to perform electronic structure calculations. In QMC, a Monte Carlo simulation is used to solve the Schroedinger equation, taking advantage of its analogy to a classical diffusion process with branching. In the present work the author focuses on how to extend the usefulness of QMC to more meaningful molecular systems. This study is aimed at questions concerning polyatomic and large atomic number systems. The accuracy of the solution obtained is determined by the accuracy of the trial wave function`s nodal structure. Efforts in the group have given great emphasis to finding optimized wave functions for the QMC calculations. Little work had been done by systematically looking at a family of systems to see how the best wave functions evolve with system size. In this work the author presents a study of trial wave functions for C, CH, C{sub 2}H and C{sub 2}H{sub 2}. The goal is to study how to build wave functions for larger systems by accumulating knowledge from the wave functions of its fragments as well as gaining some knowledge on the usefulness of multi-reference wave functions. In a MC calculation of a heavy atom, for reasonable time steps most moves for core electrons are rejected. For this reason true equilibration is rarely achieved. A method proposed by Batrouni and Reynolds modifies the way the simulation is performed without altering the final steady-state solution. It introduces an acceleration matrix chosen so that all coordinates (i.e., of core and valence electrons) propagate at comparable speeds. A study of the results obtained using their proposed matrix suggests that it may not be the optimum choice. In this work the author has found that the desired mixing of coordinates between core and valence electrons is not achieved when using this matrix. A bibliography of 175 references is included.

  1. Quantum Monte Carlo Studies of Interaction-Induced Localization in Quantum Dots and Wires

    NASA Astrophysics Data System (ADS)

    Devrim Güçlü, A.

    2009-03-01

    We investigate interaction-induced localization of electrons in both quantum dots and inhomogeneous quantum wires using variational and diffusion quantum Monte Carlo methods. Quantum dots and wires are highly tunable systems that enable the study of the physics of strongly correlated electrons. With decreasing electronic density, interactions become stronger and electrons are expected to localize at their classical positions, as in Wigner crystallization in an infinite 2D system. (1) Dots: We show that the addition energy shows a clear progression from features associated with shell structure to those caused by commensurability of a Wigner crystal. This cross-over is, then, a signature of localization; it occurs near rs˜20. For higher values of rs, the configuration symmetry of the quantum dot becomes fully consistent with the classical ground state. (2) Wires: We study an inhomogeneous quasi-one-dimensional system -- a wire with two regions, one at low density and the other high. We find that strong localization occurs in the low density quantum point contact region as the gate potential is increased. The nature of the transition from high to low density depends on the density gradient -- if it is steep, a barrier develops between the two regions, causing Coulomb blockade effects. We find no evidence for ferromagnetic spin polarization for the range of parameters studied. The picture emerging here is in good agreement with the experimental measurements of tunneling between two wires. Collaborators: C. J. Umrigar (Cornell), Hong Jiang (Fritz Haber Institut), Amit Ghosal (IISER Calcutta), and H. U. Baranger (Duke).

  2. Quantum Monte Carlo methods and lithium cluster properties. [Atomic clusters

    SciTech Connect

    Owen, R.K.

    1990-12-01

    Properties of small lithium clusters with sizes ranging from n = 1 to 5 atoms were investigated using quantum Monte Carlo (QMC) methods. Cluster geometries were found from complete active space self consistent field (CASSCF) calculations. A detailed development of the QMC method leading to the variational QMC (V-QMC) and diffusion QMC (D-QMC) methods is shown. The many-body aspect of electron correlation is introduced into the QMC importance sampling electron-electron correlation functions by using density dependent parameters, and are shown to increase the amount of correlation energy obtained in V-QMC calculations. A detailed analysis of D-QMC time-step bias is made and is found to be at least linear with respect to the time-step. The D-QMC calculations determined the lithium cluster ionization potentials to be 0.1982(14) (0.1981), 0.1895(9) (0.1874(4)), 0.1530(34) (0.1599(73)), 0.1664(37) (0.1724(110)), 0.1613(43) (0.1675(110)) Hartrees for lithium clusters n = 1 through 5, respectively; in good agreement with experimental results shown in the brackets. Also, the binding energies per atom was computed to be 0.0177(8) (0.0203(12)), 0.0188(10) (0.0220(21)), 0.0247(8) (0.0310(12)), 0.0253(8) (0.0351(8)) Hartrees for lithium clusters n = 2 through 5, respectively. The lithium cluster one-electron density is shown to have charge concentrations corresponding to nonnuclear attractors. The overall shape of the electronic charge density also bears a remarkable similarity with the anisotropic harmonic oscillator model shape for the given number of valence electrons.

  3. Quantum Monte Carlo methods and lithium cluster properties

    SciTech Connect

    Owen, R.K.

    1990-12-01

    Properties of small lithium clusters with sizes ranging from n = 1 to 5 atoms were investigated using quantum Monte Carlo (QMC) methods. Cluster geometries were found from complete active space self consistent field (CASSCF) calculations. A detailed development of the QMC method leading to the variational QMC (V-QMC) and diffusion QMC (D-QMC) methods is shown. The many-body aspect of electron correlation is introduced into the QMC importance sampling electron-electron correlation functions by using density dependent parameters, and are shown to increase the amount of correlation energy obtained in V-QMC calculations. A detailed analysis of D-QMC time-step bias is made and is found to be at least linear with respect to the time-step. The D-QMC calculations determined the lithium cluster ionization potentials to be 0.1982(14) [0.1981], 0.1895(9) [0.1874(4)], 0.1530(34) [0.1599(73)], 0.1664(37) [0.1724(110)], 0.1613(43) [0.1675(110)] Hartrees for lithium clusters n = 1 through 5, respectively; in good agreement with experimental results shown in the brackets. Also, the binding energies per atom was computed to be 0.0177(8) [0.0203(12)], 0.0188(10) [0.0220(21)], 0.0247(8) [0.0310(12)], 0.0253(8) [0.0351(8)] Hartrees for lithium clusters n = 2 through 5, respectively. The lithium cluster one-electron density is shown to have charge concentrations corresponding to nonnuclear attractors. The overall shape of the electronic charge density also bears a remarkable similarity with the anisotropic harmonic oscillator model shape for the given number of valence electrons.

  4. Quantum Monte Carlo Methods for First Principles Simulation of Liquid Water

    ERIC Educational Resources Information Center

    Gergely, John Robert

    2009-01-01

    Obtaining an accurate microscopic description of water structure and dynamics is of great interest to molecular biology researchers and in the physics and quantum chemistry simulation communities. This dissertation describes efforts to apply quantum Monte Carlo methods to this problem with the goal of making progress toward a fully "ab initio"…

  5. An algorithm for nonrelativistic quantum-mechanical finite-nuclear-mass variational calculations of nitrogen atom in L = 0, M = 0 states using all-electrons explicitly correlated Gaussian basis functions

    SciTech Connect

    Sharkey, Keeper L.; Adamowicz, Ludwik

    2014-05-07

    An algorithm for quantum-mechanical nonrelativistic variational calculations of L = 0 and M = 0 states of atoms with an arbitrary number of s electrons and with three p electrons have been implemented and tested in the calculations of the ground {sup 4}S state of the nitrogen atom. The spatial part of the wave function is expanded in terms of all-electrons explicitly correlated Gaussian functions with the appropriate pre-exponential Cartesian angular factors for states with the L = 0 and M = 0 symmetry. The algorithm includes formulas for calculating the Hamiltonian and overlap matrix elements, as well as formulas for calculating the analytic energy gradient determined with respect to the Gaussian exponential parameters. The gradient is used in the variational optimization of these parameters. The Hamiltonian used in the approach is obtained by rigorously separating the center-of-mass motion from the laboratory-frame all-particle Hamiltonian, and thus it explicitly depends on the finite mass of the nucleus. With that, the mass effect on the total ground-state energy is determined.

  6. Communication: Excited states, dynamic correlation functions and spectral properties from full configuration interaction quantum Monte Carlo.

    PubMed

    Booth, George H; Chan, Garnet Kin-Lic

    2012-11-21

    In this communication, we propose a method for obtaining isolated excited states within the full configuration interaction quantum Monte Carlo framework. This method allows for stable sampling with respect to collapse to lower energy states and requires no uncontrolled approximations. In contrast with most previous methods to extract excited state information from quantum Monte Carlo methods, this results from a modification to the underlying propagator, and does not require explicit orthogonalization, analytic continuation, transient estimators, or restriction of the Hilbert space via a trial wavefunction. Furthermore, we show that the propagator can directly yield frequency-domain correlation functions and spectral functions such as the density of states which are difficult to obtain within a traditional quantum Monte Carlo framework. We demonstrate this approach with pilot applications to the neon atom and beryllium dimer.

  7. Algorithmic differentiation and the calculation of forces by quantum Monte Carlo.

    PubMed

    Sorella, Sandro; Capriotti, Luca

    2010-12-21

    We describe an efficient algorithm to compute forces in quantum Monte Carlo using adjoint algorithmic differentiation. This allows us to apply the space warp coordinate transformation in differential form, and compute all the 3M force components of a system with M atoms with a computational effort comparable with the one to obtain the total energy. Few examples illustrating the method for an electronic system containing several water molecules are presented. With the present technique, the calculation of finite-temperature thermodynamic properties of materials with quantum Monte Carlo will be feasible in the near future.

  8. Renyi entanglement entropy of interacting fermions calculated using the continuous-time quantum Monte Carlo method.

    PubMed

    Wang, Lei; Troyer, Matthias

    2014-09-12

    We present a new algorithm for calculating the Renyi entanglement entropy of interacting fermions using the continuous-time quantum Monte Carlo method. The algorithm only samples the interaction correction of the entanglement entropy, which by design ensures the efficient calculation of weakly interacting systems. Combined with Monte Carlo reweighting, the algorithm also performs well for systems with strong interactions. We demonstrate the potential of this method by studying the quantum entanglement signatures of the charge-density-wave transition of interacting fermions on a square lattice.

  9. Systematic study of finite-size effects in quantum Monte Carlo calculations of real metallic systems

    SciTech Connect

    Azadi, Sam Foulkes, W. M. C.

    2015-09-14

    We present a systematic and comprehensive study of finite-size effects in diffusion quantum Monte Carlo calculations of metals. Several previously introduced schemes for correcting finite-size errors are compared for accuracy and efficiency, and practical improvements are introduced. In particular, we test a simple but efficient method of finite-size correction based on an accurate combination of twist averaging and density functional theory. Our diffusion quantum Monte Carlo results for lithium and aluminum, as examples of metallic systems, demonstrate excellent agreement between all of the approaches considered.

  10. Spin-orbit interactions in electronic structure quantum Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Melton, Cody A.; Zhu, Minyi; Guo, Shi; Ambrosetti, Alberto; Pederiva, Francesco; Mitas, Lubos

    2016-04-01

    We develop generalization of the fixed-phase diffusion Monte Carlo method for Hamiltonians which explicitly depends on particle spins such as for spin-orbit interactions. The method is formulated in a zero-variance manner and is similar to the treatment of nonlocal operators in commonly used static-spin calculations. Tests on atomic and molecular systems show that it is very accurate, on par with the fixed-node method. This opens electronic structure quantum Monte Carlo methods to a vast research area of quantum phenomena in which spin-related interactions play an important role.

  11. An introduction to applied quantum mechanics in the Wigner Monte Carlo formalism

    NASA Astrophysics Data System (ADS)

    Sellier, J. M.; Nedjalkov, M.; Dimov, I.

    2015-05-01

    The Wigner formulation of quantum mechanics is a very intuitive approach which allows the comprehension and prediction of quantum mechanical phenomena in terms of quasi-distribution functions. In this review, our aim is to provide a detailed introduction to this theory along with a Monte Carlo method for the simulation of time-dependent quantum systems evolving in a phase-space. This work consists of three main parts. First, we introduce the Wigner formalism, then we discuss in detail the Wigner Monte Carlo method and, finally, we present practical applications. In particular, the Wigner model is first derived from the Schrödinger equation. Then a generalization of the formalism due to Moyal is provided, which allows to recover important mathematical properties of the model. Next, the Wigner equation is further generalized to the case of many-body quantum systems. Finally, a physical interpretation of the negative part of a quasi-distribution function is suggested. In the second part, the Wigner Monte Carlo method, based on the concept of signed (virtual) particles, is introduced in detail for the single-body problem. Two extensions of the Wigner Monte Carlo method to quantum many-body problems are introduced, in the frameworks of time-dependent density functional theory and ab-initio methods. Finally, in the third and last part of this paper, applications to single- and many-body problems are performed in the context of quantum physics and quantum chemistry, specifically focusing on the hydrogen, lithium and boron atoms, the H2 molecule and a system of two identical Fermions. We conclude this work with a discussion on the still unexplored directions the Wigner Monte Carlo method could take in the next future.

  12. Quantum Monte Carlo Simulations of Adulteration Effect on Bond Alternating Spin=1/2 Chain

    NASA Astrophysics Data System (ADS)

    Zhang, Peng; Xu, Zhaoxin; Ying, Heping; Dai, Jianhui; Crompton, Peter

    The S=1/2 Heisenberg chain with bond alternation and randomness of antiferromagnetic (AFM) and ferromagnetic (FM) interactions is investigated by quantum Monte Carlo simulations of loop/cluster algorithm. Our results have shown interesting finite temperature magnetic properties of this model. The relevance of our study to former investigation results is discussed.

  13. Monte-Carlo Quantum Chemistry of Biogene Amines. Laser and Neutron Capture Effects

    SciTech Connect

    Glushkov, A. V.; Malinovskaya, S. V.; Khetselius, O. Yu.; Loboda, A. V.

    2009-03-09

    Monte-Carlo quantum calculation of the cluster consisting of the serotonine ST (histamine HM) molecules and 100 molecules of water is carried out. It is found that the zwitterion appears as expected to be strongly favoured with respect to neutral molecule. The perspective possibilities of laser and neutron capture action on different biomolecules are indicated.

  14. Monte-Carlo Quantum Chemistry of Biogene Amines. Laser and Neutron Capture Effects

    NASA Astrophysics Data System (ADS)

    Glushkov, A. V.; Malinovskaya, S. V.; Khetselius, O. Yu.; Loboda, A. V.

    2009-03-01

    Monte-Carlo quantum calculation of the cluster consisting of the serotonine ST (histamine HM) molecules and 100 molecules of water is carried out. It is found that the zwitterion appears as expected to be strongly favoured with respect to neutral molecule. The perspective possibilities of laser and neutron capture action on different biomolecules are indicated.

  15. Path-integral Monte Carlo study of asymmetric quantum quadrupolar rotors with fourth-order propagators

    NASA Astrophysics Data System (ADS)

    Park, Sungjin; Shin, Hyeondeok; Kwon, Yongkyung

    2012-08-01

    The recently-proposed fourth-order propagator based on the multi-product expansion has been applied to path-integral Monte Carlo calculations for asymmetric quantum quadruploar rotors fixed at face-centered cubic lattice sites. The rotors are observed to undergo an orientational orderdisorder phase transition at a low temperature when the electric quadrupole-quadrupole interaction is strong enough. At intermediate interaction strength, a further decrease of temperature after the first transition to the ordered phase results in a reentrant transition back to the disordered phase. The theoretical phase diagram of these asymmetric rotors determined by using fourth-order path-integral Monte Carlo calculations is found to be in good quantitative agreement with the experimental one for solid hydrogen deuteride. This leads us to conclude that the fourth-order propagator can be effectively implemented for an accurate path-integral Monte Carlo calculation of a quantum many-body system with rotational degrees of freedom.

  16. Communication: Variation after response in quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Neuscamman, Eric

    2016-08-01

    We present a new method for modeling electronically excited states that overcomes a key failing of linear response theory by allowing the underlying ground state ansatz to relax in the presence of an excitation. The method is variational, has a cost similar to ground state variational Monte Carlo, and admits both open and periodic boundary conditions. We present preliminary numerical results showing that, when paired with the Jastrow antisymmetric geminal power ansatz, the variation-after-response formalism delivers accuracies for valence and charge transfer single excitations on par with equation of motion coupled cluster, while surpassing coupled cluster's accuracy for excitations with significant doubly excited character.

  17. Quantum Monte Carlo Simulation of Overpressurized Liquid {sup 4}He

    SciTech Connect

    Vranjes, L.; Boronat, J.; Casulleras, J.; Cazorla, C.

    2005-09-30

    A diffusion Monte Carlo simulation of superfluid {sup 4}He at zero temperature and pressures up to 275 bar is presented. Increasing the pressure beyond freezing ({approx}25 bar), the liquid enters the overpressurized phase in a metastable state. In this regime, we report results of the equation of state and the pressure dependence of the static structure factor, the condensate fraction, and the excited-state energy corresponding to the roton. Along this large pressure range, both the condensate fraction and the roton energy decrease but do not become zero. The roton energies obtained are compared with recent experimental data in the overpressurized regime.

  18. Communication: Variation after response in quantum Monte Carlo.

    PubMed

    Neuscamman, Eric

    2016-08-28

    We present a new method for modeling electronically excited states that overcomes a key failing of linear response theory by allowing the underlying ground state ansatz to relax in the presence of an excitation. The method is variational, has a cost similar to ground state variational Monte Carlo, and admits both open and periodic boundary conditions. We present preliminary numerical results showing that, when paired with the Jastrow antisymmetric geminal power ansatz, the variation-after-response formalism delivers accuracies for valence and charge transfer single excitations on par with equation of motion coupled cluster, while surpassing coupled cluster's accuracy for excitations with significant doubly excited character.

  19. Communication: Variation after response in quantum Monte Carlo.

    PubMed

    Neuscamman, Eric

    2016-08-28

    We present a new method for modeling electronically excited states that overcomes a key failing of linear response theory by allowing the underlying ground state ansatz to relax in the presence of an excitation. The method is variational, has a cost similar to ground state variational Monte Carlo, and admits both open and periodic boundary conditions. We present preliminary numerical results showing that, when paired with the Jastrow antisymmetric geminal power ansatz, the variation-after-response formalism delivers accuracies for valence and charge transfer single excitations on par with equation of motion coupled cluster, while surpassing coupled cluster's accuracy for excitations with significant doubly excited character. PMID:27586897

  20. Krylov-Projected Quantum Monte Carlo Method.

    PubMed

    Blunt, N S; Alavi, Ali; Booth, George H

    2015-07-31

    We present an approach to the calculation of arbitrary spectral, thermal, and excited state properties within the full configuration interaction quzantum Monte Carlo framework. This is achieved via an unbiased projection of the Hamiltonian eigenvalue problem into a space of stochastically sampled Krylov vectors, thus, enabling the calculation of real-frequency spectral and thermal properties and avoiding explicit analytic continuation. We use this approach to calculate temperature-dependent properties and one- and two-body spectral functions for various Hubbard models, as well as isolated excited states in ab initio systems. PMID:26274406

  1. Quantum Monte Carlo simulation of spin-polarized H

    SciTech Connect

    Markic, L. Vranjes; Boronat, J.; Casulleras, J.

    2007-02-01

    The ground-state properties of spin polarized hydrogen H{down_arrow} are obtained by means of diffusion Monte Carlo calculations. Using the most accurate to date ab initio H{down_arrow}-H{down_arrow} interatomic potential we have studied its gas phase, from the very dilute regime until densities above its freezing point. At very small densities, the equation of state of the gas is very well described in terms of the gas parameter {rho}a{sup 3}, with a the s-wave scattering length. The solid phase has also been studied up to high pressures. The gas-solid phase transition occurs at a pressure of 173 bar, a much higher value than suggested by previous approximate descriptions.

  2. Practical Schemes for Accurate Forces in Quantum Monte Carlo.

    PubMed

    Moroni, S; Saccani, S; Filippi, C

    2014-11-11

    While the computation of interatomic forces has become a well-established practice within variational Monte Carlo (VMC), the use of the more accurate Fixed-Node Diffusion Monte Carlo (DMC) method is still largely limited to the computation of total energies on structures obtained at a lower level of theory. Algorithms to compute exact DMC forces have been proposed in the past, and one such scheme is also put forward in this work, but remain rather impractical due to their high computational cost. As a practical route to DMC forces, we therefore revisit here an approximate method, originally developed in the context of correlated sampling and named here the Variational Drift-Diffusion (VD) approach. We thoroughly investigate its accuracy by checking the consistency between the approximate VD force and the derivative of the DMC potential energy surface for the SiH and C2 molecules and employ a wide range of wave functions optimized in VMC to assess its robustness against the choice of trial function. We find that, for all but the poorest wave function, the discrepancy between force and energy is very small over all interatomic distances, affecting the equilibrium bond length obtained with the VD forces by less than 0.004 au. Furthermore, when the VMC forces are approximate due to the use of a partially optimized wave function, the DMC forces have smaller errors and always lead to an equilibrium distance in better agreement with the experimental value. We also show that the cost of computing the VD forces is only slightly larger than the cost of calculating the DMC energy. Therefore, the VD approximation represents a robust and efficient approach to compute accurate DMC forces, superior to the VMC counterparts.

  3. Random Number Generation for Petascale Quantum Monte Carlo

    SciTech Connect

    Ashok Srinivasan

    2010-03-16

    The quality of random number generators can affect the results of Monte Carlo computations, especially when a large number of random numbers are consumed. Furthermore, correlations present between different random number streams in a parallel computation can further affect the results. The SPRNG software, which the author had developed earlier, has pseudo-random number generators (PRNGs) capable of producing large numbers of streams with large periods. However, they had been empirically tested on only thousand streams earlier. In the work summarized here, we tested the SPRNG generators with over a hundred thousand streams, involving over 10^14 random numbers per test, on some tests. We also tested the popular Mersenne Twister. We believe that these are the largest tests of PRNGs, both in terms of the numbers of streams tested and the number of random numbers tested. We observed defects in some of these generators, including the Mersenne Twister, while a few generators appeared to perform well. We also corrected an error in the implementation of one of the SPRNG generators.

  4. Quantum Monte Carlo studies of relativistic effects in light nuclei

    SciTech Connect

    J. L. Forest; V. R. Pandharipande; A. Arriaga

    1998-05-01

    Relativistic Hamiltonians are defined as the sum of relativistic one-body kinetic energy, two- and three-body potentials and their boost corrections. In this work the authors use the variational Monte Carlo method to study two kinds of relativistic effects in the binding energy of {sup 3}H and {sup 4}He. The first is due to the nonlocalities in the relativistic kinetic energy and relativistic one-pion exchange potential (OPEP), and the second is from boost interaction. The OPEP contribution is reduced by about 15% by the relativistic nonlocality, which may also have significant effects on pion exchange currents. However, almost all of this reduction is canceled by changes in the kinetic energy and other interaction terms, and the total effect of the nonlocalities on the binding energy is very small. The boost interactions, on the other hand, give repulsive contributions of 0.4 (1.9) MeV in {sup 3}H ({sup 4}He) and account for 37% of the phenomenological part of the three-nucleon interaction needed in the nonrelativistic Hamiltonians.

  5. Unbiased reduced density matrices and electronic properties from full configuration interaction quantum Monte Carlo

    SciTech Connect

    Overy, Catherine; Blunt, N. S.; Shepherd, James J.; Booth, George H.; Cleland, Deidre; Alavi, Ali

    2014-12-28

    Properties that are necessarily formulated within pure (symmetric) expectation values are difficult to calculate for projector quantum Monte Carlo approaches, but are critical in order to compute many of the important observable properties of electronic systems. Here, we investigate an approach for the sampling of unbiased reduced density matrices within the full configuration interaction quantum Monte Carlo dynamic, which requires only small computational overheads. This is achieved via an independent replica population of walkers in the dynamic, sampled alongside the original population. The resulting reduced density matrices are free from systematic error (beyond those present via constraints on the dynamic itself) and can be used to compute a variety of expectation values and properties, with rapid convergence to an exact limit. A quasi-variational energy estimate derived from these density matrices is proposed as an accurate alternative to the projected estimator for multiconfigurational wavefunctions, while its variational property could potentially lend itself to accurate extrapolation approaches in larger systems.

  6. Global-View Coefficients: A Data Management Solution for Parallel Quantum Monte Carlo Applications

    SciTech Connect

    Niu, Qingpeng; Dinan, James

    2013-01-01

    Quantum Monte Carlo (QMC) applications perform simulation with respect to an initial state of the quantum mechanical system, which is often captured by using a cubic B-spline basis. This representation is stored as a read-only table of coefficients, and accesses to the table are generated at random as part of the Monte Carlo simulation. Current QMC applications, such as QWalk and QMCPACK, replicate this table at every process or node, which limits scalability because increasing the number of processors does not enable larger systems to be run. We present a partitioned global address space (PGAS) approach to transparently managing this data using Global Arrays in a manner that allows the memory of multiple nodes to be aggregated. We develop an automated data management system that significantly reduces communication overheads, enabling new capabilities for QMC codes. Experimental results with QWalk and QMCPACK demonstrate the effectiveness of the data management system.

  7. Communication: Fixed-node errors in quantum Monte Carlo: Interplay of electron density and node nonlinearities

    SciTech Connect

    Rasch, Kevin M.; Hu, Shuming; Mitas, Lubos

    2014-01-28

    We elucidate the origin of large differences (two-fold or more) in the fixed-node errors between the first- vs second-row systems for single-configuration trial wave functions in quantum Monte Carlo calculations. This significant difference in the valence fixed-node biases is studied across a set of atoms, molecules, and also Si, C solid crystals. We show that the key features which affect the fixed-node errors are the differences in electron density and the degree of node nonlinearity. The findings reveal how the accuracy of the quantum Monte Carlo varies across a variety of systems, provide new perspectives on the origins of the fixed-node biases in calculations of molecular and condensed systems, and carry implications for pseudopotential constructions for heavy elements.

  8. Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Azadi, Sam; Cohen, R. E.

    2016-08-01

    We studied the low-pressure (0-10 GPa) phase diagram of crystalline benzene using quantum Monte Carlo and density functional theory (DFT) methods. We performed diffusion quantum Monte Carlo (DMC) calculations to obtain accurate static phase diagrams as benchmarks for modern van der Waals density functionals. Using density functional perturbation theory, we computed the phonon contributions to the free energies. Our DFT enthalpy-pressure phase diagrams indicate that the Pbca and P21/c structures are the most stable phases within the studied pressure range. The DMC Gibbs free-energy calculations predict that the room temperature Pbca to P21/c phase transition occurs at 2.1(1) GPa. This prediction is consistent with available experimental results at room temperature. Our DMC calculations give 50.6 ± 0.5 kJ/mol for crystalline benzene lattice energy.

  9. Majorana Positivity and the Fermion Sign Problem of Quantum Monte Carlo Simulations

    NASA Astrophysics Data System (ADS)

    Wei, Z. C.; Wu, Congjun; Li, Yi; Zhang, Shiwei; Xiang, T.

    2016-06-01

    The sign problem is a major obstacle in quantum Monte Carlo simulations for many-body fermion systems. We examine this problem with a new perspective based on the Majorana reflection positivity and Majorana Kramers positivity. Two sufficient conditions are proven for the absence of the fermion sign problem. Our proof provides a unified description for all the interacting lattice fermion models previously known to be free of the sign problem based on the auxiliary field quantum Monte Carlo method. It also allows us to identify a number of new sign-problem-free interacting fermion models including, but not limited to, lattice fermion models with repulsive interactions but without particle-hole symmetry, and interacting topological insulators with spin-flip terms.

  10. Majorana Positivity and the Fermion Sign Problem of Quantum Monte Carlo Simulations.

    PubMed

    Wei, Z C; Wu, Congjun; Li, Yi; Zhang, Shiwei; Xiang, T

    2016-06-24

    The sign problem is a major obstacle in quantum Monte Carlo simulations for many-body fermion systems. We examine this problem with a new perspective based on the Majorana reflection positivity and Majorana Kramers positivity. Two sufficient conditions are proven for the absence of the fermion sign problem. Our proof provides a unified description for all the interacting lattice fermion models previously known to be free of the sign problem based on the auxiliary field quantum Monte Carlo method. It also allows us to identify a number of new sign-problem-free interacting fermion models including, but not limited to, lattice fermion models with repulsive interactions but without particle-hole symmetry, and interacting topological insulators with spin-flip terms. PMID:27391709

  11. Communication: Toward an improved control of the fixed-node error in quantum Monte Carlo: The case of the water molecule.

    PubMed

    Caffarel, Michel; Applencourt, Thomas; Giner, Emmanuel; Scemama, Anthony

    2016-04-21

    All-electron Fixed-node DiffusionMonte Carlo calculations for the nonrelativistic ground-state energy of the water molecule at equilibrium geometry are presented. The determinantal part of the trial wavefunction is obtained from a selected Configuration Interaction calculation[Configuration Interaction using a Perturbative Selection done Iteratively (CIPSI) method] including up to about 1.4 × 10(6) of determinants. Calculations are made using the cc-pCVnZ family of basis sets, with n = 2 to 5. In contrast with most quantum Monte Carlo works no re-optimization of the determinantal part in presence of a Jastrow is performed. For the largest cc-pCV5Z basis set the lowest upper bound for the ground-state energy reported so far of -76.437 44(18) is obtained. The fixed-node energy is found to decrease regularly as a function of the cardinal numbern and the Complete Basis Set limit associated with exact nodes is easily extracted. The resulting energy of -76.438 94(12) - in perfect agreement with the best experimentally derived value - is the most accurate theoretical estimate reported so far. We emphasize that employing selected configuration interactionnodes of increasing quality in a given family of basis sets may represent a simple, deterministic, reproducible, and systematic way of controlling the fixed-node error in diffusionMonte Carlo.

  12. Flat-histogram methods in quantum Monte Carlo simulations: Application to the t-J model

    NASA Astrophysics Data System (ADS)

    Diamantis, Nikolaos G.; Manousakis, Efstratios

    2016-09-01

    We discuss that flat-histogram techniques can be appropriately applied in the sampling of quantum Monte Carlo simulation in order to improve the statistical quality of the results at long imaginary time or low excitation energy. Typical imaginary-time correlation functions calculated in quantum Monte Carlo are subject to exponentially growing errors as the range of imaginary time grows and this smears the information on the low energy excitations. We show that we can extract the low energy physics by modifying the Monte Carlo sampling technique to one in which configurations which contribute to making the histogram of certain quantities flat are promoted. We apply the diagrammatic Monte Carlo (diag-MC) method to the motion of a single hole in the t-J model and we show that the implementation of flat-histogram techniques allows us to calculate the Green's function in a wide range of imaginary-time. In addition, we show that applying the flat-histogram technique alleviates the “sign”-problem associated with the simulation of the single-hole Green's function at long imaginary time.

  13. TRIQS/CTHYB: A continuous-time quantum Monte Carlo hybridisation expansion solver for quantum impurity problems

    NASA Astrophysics Data System (ADS)

    Seth, Priyanka; Krivenko, Igor; Ferrero, Michel; Parcollet, Olivier

    2016-03-01

    We present TRIQS/CTHYB, a state-of-the art open-source implementation of the continuous-time hybridisation expansion quantum impurity solver of the TRIQS package. This code is mainly designed to be used with the TRIQS library in order to solve the self-consistent quantum impurity problem in a multi-orbital dynamical mean field theory approach to strongly-correlated electrons, in particular in the context of realistic electronic structure calculations. It is implemented in C++ for efficiency and is provided with a high-level Python interface. The code ships with a new partitioning algorithm that divides the local Hilbert space without any user knowledge of the symmetries and quantum numbers of the Hamiltonian. Furthermore, we implement higher-order configuration moves and show that such moves are necessary to ensure ergodicity of the Monte Carlo in common Hamiltonians even without symmetry-breaking.

  14. Introducing QMC/MMpol: Quantum Monte Carlo in Polarizable Force Fields for Excited States.

    PubMed

    Guareschi, Riccardo; Zulfikri, Habiburrahman; Daday, Csaba; Floris, Franca Maria; Amovilli, Claudio; Mennucci, Benedetta; Filippi, Claudia

    2016-04-12

    We present for the first time a quantum mechanics/molecular mechanics scheme which combines quantum Monte Carlo with the reaction field of classical polarizable dipoles (QMC/MMpol). In our approach, the optimal dipoles are self-consistently generated at the variational Monte Carlo level and then used to include environmental effects in diffusion Monte Carlo. We investigate the performance of this hybrid model in describing the vertical excitation energies of prototypical small molecules solvated in water, namely, methylenecyclopropene and s-trans acrolein. Two polarization regimes are explored where either the dipoles are optimized with respect to the ground-state solute density (polGS) or different sets of dipoles are separately brought to equilibrium with the states involved in the electronic transition (polSS). By comparing with reference supermolecular calculations where both solute and solvent are treated quantum mechanically, we find that the inclusion of the response of the environment to the excitation of the solute leads to superior results than the use of a frozen environment (point charges or polGS), in particular, when the solute-solvent coupling is dominated by electrostatic effects which are well recovered in the polSS condition. QMC/MMpol represents therefore a robust scheme to treat important environmental effects beyond static point charges, combining the accuracy of QMC with the simplicity of a classical approach. PMID:26959751

  15. Entanglement and the fermion sign problem in auxiliary field quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Broecker, Peter; Trebst, Simon

    2016-08-01

    Quantum Monte Carlo simulations of fermions are hampered by the notorious sign problem whose most striking manifestation is an exponential growth of sampling errors with the number of particles. With the sign problem known to be an NP-hard problem and any generic solution thus highly elusive, the Monte Carlo sampling of interacting many-fermion systems is commonly thought to be restricted to a small class of model systems for which a sign-free basis has been identified. Here we demonstrate that entanglement measures, in particular the so-called Rényi entropies, can intrinsically exhibit a certain robustness against the sign problem in auxiliary-field quantum Monte Carlo approaches and possibly allow for the identification of global ground-state properties via their scaling behavior even in the presence of a strong sign problem. We corroborate these findings via numerical simulations of fermionic quantum phase transitions of spinless fermions on the honeycomb lattice at and below half filling.

  16. Quantum Monte Carlo algorithms for electronic structure at the petascale; the endstation project

    SciTech Connect

    Esler, Kenneth P; Kim, Jeongnim; Ceperley, David M; Purwanto, Wirawan; Walter, Eric J; Krakauer, Henry; Zhang, Shiwei; Kent, Paul R; Hennig, Richard G; Bajdich, Michal; Kolorenc, Jindrich; Mitas, Lubos; Srinivasan, Ashok

    2008-01-01

    Over the past two decades, continuum quantum Monte Carlo (QMC) has proved to be an invaluable tool for predicting of the properties of matter from fundamental principles. By solving the Schroedinger equation through a stochastic projection, it achieves the greatest accuracy and reliability of methods available for physical systems containing more than a few quantum particles. QMC enjoys scaling favorable to quantum chemical methods, with a computational effort which grows with the second or third power of system size. This accuracy and scalability has enabled scientific discovery across a broad spectrum of disciplines. The current methods perform very efficiently at the terascale. The quantum Monte Carlo Endstation project is a collaborative effort among researchers in the field to develop a new generation of algorithms, and their efficient implementations, which will take advantage of the upcoming petaflop architectures. Some aspects of these developments are discussed here. These tools will expand the accuracy, efficiency and range of QMC applicability and enable us to tackle challenges which are currently out of reach. The methods will be applied to several important problems including electronic and structural properties of water, transition metal oxides, nanosystems and ultracold atoms.

  17. Quantum Monte Carlo algorithms for electronic structure at the petascale; the endstation project.

    SciTech Connect

    Kim, J; Ceperley, D M; Purwanto, W; Walter, E J; Krakauer, H; Zhang, S W; Kent, P.R. C; Hennig, R G; Umrigar, C; Bajdich, M; Kolorenc, J; Mitas, L; Srinivasan, A

    2008-10-01

    Over the past two decades, continuum quantum Monte Carlo (QMC) has proved to be an invaluable tool for predicting of the properties of matter from fundamental principles. By solving the Schrodinger equation through a stochastic projection, it achieves the greatest accuracy and reliability of methods available for physical systems containing more than a few quantum particles. QMC enjoys scaling favorable to quantum chemical methods, with a computational effort which grows with the second or third power of system size. This accuracy and scalability has enabled scientific discovery across a broad spectrum of disciplines. The current methods perform very efficiently at the terascale. The quantum Monte Carlo Endstation project is a collaborative effort among researchers in the field to develop a new generation of algorithms, and their efficient implementations, which will take advantage of the upcoming petaflop architectures. Some aspects of these developments are discussed here. These tools will expand the accuracy, efficiency and range of QMC applicability and enable us to tackle challenges which are currently out of reach. The methods will be applied to several important problems including electronic and structural properties of water, transition metal oxides, nanosystems and ultracold atoms.

  18. Hybrid quantum-classical Monte Carlo study of a molecule-based magnet

    NASA Astrophysics Data System (ADS)

    Henelius, P.; Fishman, R. S.

    2008-12-01

    Using a Monte Carlo (MC) method, we study an effective model for the Fe(II)Fe(III) bimetallic oxalates. Within a hybrid quantum-classical MC algorithm, the Heisenberg S=2 and S'=5/2 spins on the Fe(II) and Fe(III) sites are updated using a quantum MC loop while the Ising-type orbital angular momenta on the Fe(II) sites are updated using a single-spin classical MC flip. The effective field acting on the orbital angular momenta depends on the quantum state of the system. We find that the mean-field phase diagram for the model is surprisingly robust with respect to fluctuations. In particular, the region displaying two compensation points shifts and shrinks but remains finite.

  19. Ising nematic quantum critical point in a metal: a Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Lederer, Samuel

    The Ising nematic quantum critical point (QCP) associated with the zero temperature transition from a symmetric to a nematic metal is an exemplar of metallic quantum criticality. We have carried out a minus sign-free quantum Monte Carlo study of this QCP for a two dimensional lattice model with sizes up to 24 × 24 sites. The system remains non-superconducting down to the lowest accessible temperatures. The results exhibit critical scaling behavior over the accessible ranges of temperature, (imaginary) time, and distance. This scaling behavior has remarkable similarities with recently measured properties of the Fe-based superconductors proximate to their putative nematic QCP. With Yoni Schattner, Steven A. Kivelson, and Erez Berg.

  20. Torsional diffusion Monte Carlo: A method for quantum simulations of proteins

    NASA Astrophysics Data System (ADS)

    Clary, David C.

    2001-06-01

    The quantum diffusion Monte Carlo (DMC) method is extended to the treatment of coupled torsional motions in proteins. A general algorithm and computer program has been developed by interfacing this torsional-DMC method with all-atom force-fields for proteins. The method gives the zero-point energy and atomic coordinates averaged over the coupled torsional motions in the quantum ground state of the protein. Application of the new algorithm is made to the proteins gelsolin (356 atoms and 142 torsions) and gp41-HIV (1101 atoms and 452 torsions). The results indicate that quantum-dynamical effects are important for the energies and geometries of typical proteins such as these.

  1. Sign-problem-free quantum Monte Carlo of the onset of antiferromagnetism in metals.

    PubMed

    Berg, Erez; Metlitski, Max A; Sachdev, Subir

    2012-12-21

    The quantum theory of antiferromagnetism in metals is necessary for our understanding of numerous intermetallic compounds of widespread interest. In these systems, a quantum critical point emerges as external parameters (such as chemical doping) are varied. Because of the strong coupling nature of this critical point and the "sign problem" plaguing numerical quantum Monte Carlo (QMC) methods, its theoretical understanding is still incomplete. Here, we show that the universal low-energy theory for the onset of antiferromagnetism in a metal can be realized in lattice models, which are free from the sign problem and hence can be simulated efficiently with QMC. Our simulations show Fermi surface reconstruction and unconventional spin-singlet superconductivity across the critical point. PMID:23258893

  2. Sign Learning Kink-based (SiLK) Quantum Monte Carlo for molecular systems

    NASA Astrophysics Data System (ADS)

    Ma, Xiaoyao; Hall, Randall W.; Löffler, Frank; Kowalski, Karol; Bhaskaran-Nair, Kiran; Jarrell, Mark; Moreno, Juana

    2016-01-01

    The Sign Learning Kink (SiLK) based Quantum Monte Carlo (QMC) method is used to calculate the ab initio ground state energies for multiple geometries of the H2O, N2, and F2 molecules. The method is based on Feynman's path integral formulation of quantum mechanics and has two stages. The first stage is called the learning stage and reduces the well-known QMC minus sign problem by optimizing the linear combinations of Slater determinants which are used in the second stage, a conventional QMC simulation. The method is tested using different vector spaces and compared to the results of other quantum chemical methods and to exact diagonalization. Our findings demonstrate that the SiLK method is accurate and reduces or eliminates the minus sign problem.

  3. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  4. The accuracy of diffusion quantum Monte Carlo simulations in the determination of molecular equilibrium structures

    NASA Astrophysics Data System (ADS)

    Lu, Shih-I.

    2004-12-01

    For a test set of 17 first-row small molecules, the equilibrium structures are calculated with Ornstein-Uhlenbeck diffusion quantum Monte Carlo simulations guiding by trial wave functions constructed from floating spherical Gaussian orbitals and spherical Gaussian geminals. To measure performance of the Monte Carlo calculations, the mean deviation, the mean absolute deviation, the maximum absolute deviation, and the standard deviation of Monte Carlo calculated equilibrium structures with respect to empirical equilibrium structures are given. This approach is found to yield results having a uniformly high quality, being consistent with empirical equilibrium structures and surpassing calculated values from the coupled cluster model with single, double, and noniterative triple excitations [CCSD(T)] with the basis sets of cc-pCVQZ and cc-pVQZ. The nonrelativistic equilibrium atomization energies are also presented to assess performance of the calculated methods. The mean absolute deviations regarding experimental atomization energy are 0.16 and 0.21 kcal/mol for the Monte Carlo and CCSD(T)/cc-pCV(56)Z calculations, respectively.

  5. Quantum Monte-Carlo simulation of spin-one antiferromagnets with single-ion anisotropy

    NASA Astrophysics Data System (ADS)

    Kato, Yasuyuki; Wierschem, Keola; Nishida, Yusuke; Batista, Cristian; Sengupta, Pinaki

    2013-03-01

    We study a spin-one Heisenberg model with uniaxial single-ion anisotropy, D, and Zeeman coupling to a magnetic field, B, parallel to the symmetry axis. We compute the (D / J , B / J) quantum phase diagram for square and simple cubic lattices by combining analytical and Quantum Monte Carlo approaches, and find a transition between XY-antiferromagnetic and ferronematic phases that spontaneously break the U(1) symmetry of the model. In the language of bosonic gases, this is a transition between a Bose-Einstein condensate (BEC) of single bosons and a BEC of pairs. For the efficient simulation of ferronematic phase, we developed and implemented a new multi-discontinuity algorithm based on the directed-loop algorithm. The ordinary quantum Monte-Carlo methods fall into freezing problems when we apply them to this system at large D / J and finite B / J ~ 1 . The new method does not suffer from the freezing problems. This research used resources of the NERSCC (DOE Contract No. DE-AC02-05CH11231). Work at LANL was performed under the auspices of a J. Robert Oppenheimer Fellowship and the U.S. DOE contract No. DE-AC52-06NA25396 through the LDRD program.

  6. Geometrically Constructed Markov Chain Monte Carlo Study of Quantum Spin-phonon Complex Systems

    NASA Astrophysics Data System (ADS)

    Suwa, Hidemaro

    2013-03-01

    We have developed novel Monte Carlo methods for precisely calculating quantum spin-boson models and investigated the critical phenomena of the spin-Peierls systems. Three significant methods are presented. The first is a new optimization algorithm of the Markov chain transition kernel based on the geometric weight allocation. This algorithm, for the first time, satisfies the total balance generally without imposing the detailed balance and always minimizes the average rejection rate, being better than the Metropolis algorithm. The second is the extension of the worm (directed-loop) algorithm to non-conserved particles, which cannot be treated efficiently by the conventional methods. The third is the combination with the level spectroscopy. Proposing a new gap estimator, we are successful in eliminating the systematic error of the conventional moment method. Then we have elucidated the phase diagram and the universality class of the one-dimensional XXZ spin-Peierls system. The criticality is totally consistent with the J1 -J2 model, an effective model in the antiadiabatic limit. Through this research, we have succeeded in investigating the critical phenomena of the effectively frustrated quantum spin system by the quantum Monte Carlo method without the negative sign. JSPS Postdoctoral Fellow for Research Abroad

  7. Electron density of states of Fe-based superconductors: Quantum trajectory Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Kashurnikov, V. A.; Krasavin, A. V.; Zhumagulov, Ya. V.

    2016-03-01

    The spectral and total electron densities of states in two-dimensional FeAs clusters, which simulate iron-based superconductors, have been calculated using the generalized quantum Monte Carlo algorithm within the full two-orbital model. Spectra have been reconstructed by solving the integral equation relating the Matsubara Green's function and spectral density by the method combining the gradient descent and Monte Carlo algorithms. The calculations have been performed for clusters with dimensions up to 10 × 10 FeAs cells. The profiles of the Fermi surface for the entire Brillouin zone have been presented in the quasiparticle approximation. Data for the total density of states near the Fermi level have been obtained. The effect of the interaction parameter, size of the cluster, and temperature on the spectrum of excitations has been studied.

  8. Diffusion quantum Monte Carlo study of martensitic phase transition energetics: The case of phosphorene

    NASA Astrophysics Data System (ADS)

    Reeves, Kyle G.; Yao, Yi; Kanai, Yosuke

    2016-09-01

    Recent technical advances in dealing with finite-size errors make quantum Monte Carlo methods quite appealing for treating extended systems in electronic structure calculations, especially when commonly used density functional theory (DFT) methods might not be satisfactory. We present a theoretical study of martensitic phase transition energetics of a two-dimensional phosphorene by employing diffusion Monte Carlo (DMC) approach. The DMC calculation supports DFT prediction of having a rather diffusive barrier that is characterized by having two transition states, in addition to confirming that the so-called black and blue phases of phosphorene are essentially degenerate. At the same time, the DFT calculations do not provide the quantitative accuracy in describing the energy changes for the martensitic phase transition even when hybrid exchange-correlation functional is employed. We also discuss how mechanical strain influences the stabilities of the two phases of phosphorene.

  9. Feature Article: Understanding strongly correlated many-body systems with quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Lavalle, Catia; Rigol, Marcos; Muramatsu, Alejandro

    2005-08-01

    The cover picture of the current issue, taken from the Feature Article [1], depicts the evolution of local density (a) and its quantum fluctuations (b) in trapped fermions on one-dimensional optical lattices. As the number of fermions in the trap is increased, figure (a) shows the formation of a Mott-insulating plateau (local density equal to one) whereas the quantum fluctuations - see figure (b) - are strongly suppressed, but nonzero. For a larger number of fermions new insulating plateaus appear (this time with local density equal to two), but no density fluctuations. Regions with non-constant density are metallic and exhibit large quantum fluctuations of the density.The first author Catia Lavalle is a Postdoc at the University of Stuttgart. She works in the field of strongly correlated quantum systems by means of Quantum Monte Carlo methods (QMC). While working on her PhD thesis at the University of Stuttgart, she developed a new QMC technique that allows to study dynamical properties of the t-J model.

  10. Quantum Monte Carlo simulation of a two-dimensional Bose gas

    SciTech Connect

    Pilati, S.; Boronat, J.; Casulleras, J.; Giorgini, S.

    2005-02-01

    The equation of state of a homogeneous two-dimensional Bose gas is calculated using quantum Monte Carlo methods. The low-density universal behavior is investigated using different interatomic model potentials, both finite ranged and strictly repulsive and zero ranged, supporting a bound state. The condensate fraction and the pair distribution function are calculated as a function of the gas parameter, ranging from the dilute to the strongly correlated regime. In the case of the zero-range pseudopotential we discuss the stability of the gaslike state for large values of the two-dimensional scattering length, and we calculate the critical density where the system becomes unstable against cluster formation.

  11. Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo

    SciTech Connect

    Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.

    2014-10-01

    We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, a finding in stark contrast to DAC data.

  12. Monte Carlo sampling of Wigner functions and surface hopping quantum dynamics

    NASA Astrophysics Data System (ADS)

    Kube, Susanna; Lasser, Caroline; Weber, Marcus

    2009-04-01

    The article addresses the achievable accuracy for a Monte Carlo sampling of Wigner functions in combination with a surface hopping algorithm for non-adiabatic quantum dynamics. The approximation of Wigner functions is realized by an adaption of the Metropolis algorithm for real-valued functions with disconnected support. The integration, which is necessary for computing values of the Wigner function, uses importance sampling with a Gaussian weight function. The numerical experiments agree with theoretical considerations and show an error of 2-3%.

  13. Quantum Monte Carlo study of dipolar lattice bosons in the presence of random diagonal disorder

    NASA Astrophysics Data System (ADS)

    Zhang, Chao; Safavi-Naini, Arghavan; Capogrosso-Sansone, Barbara

    2015-05-01

    We report the results of our study of dipolar bosons in a two dimensional optical lattice in the presence of random diagonal disorders using Path Integral Quantum Monte Carlo simulations. We study the phase diagram at half filling which features three phases: superfluid, checkerboard solid and bose glass. We observe that, in contrast to the standard Bose-Hubbard model in presence of diagonal disorder, superfluidity is destroyed at considerable lower disorder strengths in favor of the Bose glass phase. Additionally we find that as the disorder strength increases, larger dipolar interaction is required in order to stabilize a checkerboard solid.

  14. A Monte Carlo-quantum mechanics study of a solvatochromic π* probe.

    PubMed

    Domínguez, Moisés; Rezende, Marcos Caroli

    2016-09-01

    The solvation and the solvatochromic behavior of 5-(dimethylamino)-5'-nitro-2,2'-bithiophene 1, the basis of a π* scale of solvent polarities, was investigated theoretically in toluene, dichloromethane, methanol and formamide with a Monte Carlo and quantum mechanics (QM/MM) iterative approach. The calculated transition energies of the solvatochromic band of 1, obtained as averages of statistically uncorrelated configurations, including the solute and explicit solvent molecules of the first solvation layer, besides showing good agreement with the experimental transitions, reproduced very well the positive solvatochromism of this probe in various solvents.

  15. Pair correlation functions of FeAs-based superconductors: Quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Kashurnikov, V. A.; Krasavin, A. V.

    2015-01-01

    The new generalized quantum continuous time world line Monte Carlo algorithm was developed to calculate pair correlation functions for two-dimensional FeAs-clusters modeling of iron-based superconductors within the framework of the two-orbital model. The analysis of pair correlations depending on the cluster size, temperature, interaction, and the type of symmetry of the order parameter is carried out. The data obtained for clusters with sizes up to 1 0x1 0 FeAs-cells favor the possibility of an effective charge carrier's attraction that is corresponding the A1g-symmetry, at some parameters of interaction.

  16. Monte Carlo studies of supersymmetric matrix quantum mechanics with sixteen supercharges at finite temperature.

    PubMed

    Anagnostopoulos, Konstantinos N; Hanada, Masanori; Nishimura, Jun; Takeuchi, Shingo

    2008-01-18

    We present the first Monte Carlo results for supersymmetric matrix quantum mechanics with 16 supercharges at finite temperature. The recently proposed nonlattice simulation enables us to include the effects of fermionic matrices in a transparent and reliable manner. The internal energy nicely interpolates the weak coupling behavior obtained by the high temperature expansion, and the strong coupling behavior predicted from the dual black-hole geometry. The Polyakov line asymptotes at low temperature to a characteristic behavior for a deconfined theory, suggesting the absence of a phase transition. These results provide highly nontrivial evidence for the gauge-gravity duality. PMID:18232852

  17. A study of potential energy curves from the model space quantum Monte Carlo method

    SciTech Connect

    Ohtsuka, Yuhki; Ten-no, Seiichiro

    2015-12-07

    We report on the first application of the model space quantum Monte Carlo (MSQMC) to potential energy curves (PECs) for the excited states of C{sub 2}, N{sub 2}, and O{sub 2} to validate the applicability of the method. A parallel MSQMC code is implemented with the initiator approximation to enable efficient sampling. The PECs of MSQMC for various excited and ionized states are compared with those from the Rydberg-Klein-Rees and full configuration interaction methods. The results indicate the usefulness of MSQMC for precise PECs in a wide range obviating problems concerning quasi-degeneracy.

  18. Role of collisional broadening in Monte Carlo simulations of terahertz quantum cascade lasers

    SciTech Connect

    Matyas, Alpar; Lugli, Paolo; Jirauschek, Christian

    2013-01-07

    Using a generalized version of Fermi's golden rule, collisional broadening is self-consistently implemented into ensemble Monte Carlo carrier transport simulations, and its effect on the transport and optical properties of terahertz quantum cascade lasers is investigated. The inclusion of broadening yields improved agreement with the experiment, without a significant increase of the numerical load. Specifically, this effect is crucial for a correct modeling at low biases. In the lasing regime, broadening can lead to significantly reduced optical gain and output power, affecting the obtained current-voltage characteristics.

  19. Chiral 2N and 3N interactions and quantum Monte Carlo applications

    NASA Astrophysics Data System (ADS)

    Gezerlis, Alexandros

    2016-07-01

    Chiral Effective Field Theory (EFT) two- and three-nucleon forces are now widely employed. Since they were originally formulated in momentum space, these interactions were non-local, making them inaccessible to Quantum Monte Carlo (QMC) methods. We have recently derived a local version of chiral EFT nucleon-nucleon and three-nucleon interactions, which we also used in QMC calculations for neutron matter and light nuclei. In this contribution I go over the basics of local chiral EFT and then summarize recent results.

  20. Fermion sign problem in imaginary-time projection continuum quantum Monte Carlo with local interaction.

    PubMed

    Calcavecchia, Francesco; Holzmann, Markus

    2016-04-01

    We use the shadow wave function formalism as a convenient model to study the fermion sign problem affecting all projector quantum Monte Carlo methods in continuum space. We demonstrate that the efficiency of imaginary-time projection algorithms decays exponentially with increasing number of particles and/or imaginary-time propagation. Moreover, we derive an analytical expression that connects the localization of the system with the magnitude of the sign problem, illustrating this behavior through numerical results. Finally, we discuss the computational complexity of the fermion sign problem and methods for alleviating its severity. PMID:27176442

  1. Theory of finite size effects for electronic quantum Monte Carlo calculations of liquids and solids

    NASA Astrophysics Data System (ADS)

    Holzmann, Markus; Clay, Raymond C.; Morales, Miguel A.; Tubman, Norm M.; Ceperley, David M.; Pierleoni, Carlo

    2016-07-01

    Concentrating on zero temperature quantum Monte Carlo calculations of electronic systems, we give a general description of the theory of finite size extrapolations of energies to the thermodynamic limit based on one- and two-body correlation functions. We introduce effective procedures, such as using the potential and wave function split up into long and short range functions to simplify the method, and we discuss how to treat backflow wave functions. Then we explicitly test the accuracy of our method to correct finite size errors on example hydrogen and helium many-body systems and show that the finite size bias can be drastically reduced for even small systems.

  2. A Monte Carlo-quantum mechanics study of a solvatochromic π* probe.

    PubMed

    Domínguez, Moisés; Rezende, Marcos Caroli

    2016-09-01

    The solvation and the solvatochromic behavior of 5-(dimethylamino)-5'-nitro-2,2'-bithiophene 1, the basis of a π* scale of solvent polarities, was investigated theoretically in toluene, dichloromethane, methanol and formamide with a Monte Carlo and quantum mechanics (QM/MM) iterative approach. The calculated transition energies of the solvatochromic band of 1, obtained as averages of statistically uncorrelated configurations, including the solute and explicit solvent molecules of the first solvation layer, besides showing good agreement with the experimental transitions, reproduced very well the positive solvatochromism of this probe in various solvents. PMID:27553303

  3. Neutron matter with Quantum Monte Carlo: chiral 3N forces and static response

    DOE PAGES

    Buraczynski, M.; Gandolfi, S.; Gezerlis, A.; Schwenk, A.; Tews, I.

    2016-03-01

    Neutron matter is related to the physics of neutron stars and that of neutron-rich nuclei. Moreover, Quantum Monte Carlo (QMC) methods offer a unique way of solving the many-body problem non-perturbatively, providing feedback on features of nuclear interactions and addressing scenarios that are inaccessible to other approaches. Our contribution goes over two recent accomplishments in the theory of neutron matter: a) the fusing of QMC with chiral effective field theory interactions, focusing on local chiral 3N forces, and b) the first attempt to find an ab initio solution to the problem of static response.

  4. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo

    SciTech Connect

    Zen, Andrea; Luo, Ye Mazzola, Guglielmo Sorella, Sandro; Guidoni, Leonardo

    2015-04-14

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems.

  5. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo.

    PubMed

    Zen, Andrea; Luo, Ye; Mazzola, Guglielmo; Guidoni, Leonardo; Sorella, Sandro

    2015-04-14

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems. PMID:25877566

  6. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Zen, Andrea; Luo, Ye; Mazzola, Guglielmo; Guidoni, Leonardo; Sorella, Sandro

    2015-04-01

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems.

  7. Torsional path integral Monte Carlo method for the quantum simulation of large molecules

    NASA Astrophysics Data System (ADS)

    Miller, Thomas F.; Clary, David C.

    2002-05-01

    A molecular application is introduced for calculating quantum statistical mechanical expectation values of large molecules at nonzero temperatures. The Torsional Path Integral Monte Carlo (TPIMC) technique applies an uncoupled winding number formalism to the torsional degrees of freedom in molecular systems. The internal energy of the molecules ethane, n-butane, n-octane, and enkephalin are calculated at standard temperature using the TPIMC technique and compared to the expectation values obtained using the harmonic oscillator approximation and a variational technique. All studied molecules exhibited significant quantum mechanical contributions to their internal energy expectation values according to the TPIMC technique. The harmonic oscillator approximation approach to calculating the internal energy performs well for the molecules presented in this study but is limited by its neglect of both anharmonicity effects and the potential coupling of intramolecular torsions.

  8. Ab initio molecular dynamics simulation of liquid water by quantum Monte Carlo.

    PubMed

    Zen, Andrea; Luo, Ye; Mazzola, Guglielmo; Guidoni, Leonardo; Sorella, Sandro

    2015-04-14

    Although liquid water is ubiquitous in chemical reactions at roots of life and climate on the earth, the prediction of its properties by high-level ab initio molecular dynamics simulations still represents a formidable task for quantum chemistry. In this article, we present a room temperature simulation of liquid water based on the potential energy surface obtained by a many-body wave function through quantum Monte Carlo (QMC) methods. The simulated properties are in good agreement with recent neutron scattering and X-ray experiments, particularly concerning the position of the oxygen-oxygen peak in the radial distribution function, at variance of previous density functional theory attempts. Given the excellent performances of QMC on large scale supercomputers, this work opens new perspectives for predictive and reliable ab initio simulations of complex chemical systems.

  9. Excited states from quantum Monte Carlo in the basis of Slater determinants

    SciTech Connect

    Humeniuk, Alexander; Mitrić, Roland

    2014-11-21

    Building on the full configuration interaction quantum Monte Carlo (FCIQMC) algorithm introduced recently by Booth et al. [J. Chem. Phys. 131, 054106 (2009)] to compute the ground state of correlated many-electron systems, an extension to the computation of excited states (exFCIQMC) is presented. The Hilbert space is divided into a large part consisting of pure Slater determinants and a much smaller orthogonal part (the size of which is controlled by a cut-off threshold), from which the lowest eigenstates can be removed efficiently. In this way, the quantum Monte Carlo algorithm is restricted to the orthogonal complement of the lower excited states and projects out the next highest excited state. Starting from the ground state, higher excited states can be found one after the other. The Schrödinger equation in imaginary time is solved by the same population dynamics as in the ground state algorithm with modified probabilities and matrix elements, for which working formulae are provided. As a proof of principle, the method is applied to lithium hydride in the 3-21G basis set and to the helium dimer in the aug-cc-pVDZ basis set. It is shown to give the correct electronic structure for all bond lengths. Much more testing will be required before the applicability of this method to electron correlation problems of interesting size can be assessed.

  10. Quantum Monte Carlo Assessment of the Relevance of Electronic Correlations in Defects and EOS in Metals

    SciTech Connect

    Hood, R Q; Williamson, A J; Dubois, J L; Reboredo, F A

    2008-02-07

    We have developed a highly accurate computational capability to calculate the equation of state (EOS) and defect formation energies of metallic systems. We are using a newly developed algorithm that enables the study of metallic systems with quantum Monte Carlo (QMC) methods. To date, technical limitations have restricted the application of QMC methods to semiconductors, insulators and the homogeneous electron gas. Using this new 'QMC for metals' we can determine, for the first time, the significance of correlation effects in the EOS and in the formation energies of point defects, impurities, surfaces and interfaces in metallic systems. These calculations go beyond the state-of-the-art accuracy which is currently obtained with Density Functional Theory approaches. Such benchmark calculations can provide more accurate predictions for the EOS and the formation energies of vacancies and interstitials in simple metals. These are important parameters in determining the mechanical properties as well as the micro-structural evolution of metals in irradiated materials or under extreme conditions. We describe the development of our 'QMC for metals' code, which has been adapted to run efficiently on a variety of computer architectures including BG/L. We present results of the first accurate quantum Monte Carlo calculation of an EOS of a realistic metallic system that goes beyond the homogeneous electron gas.

  11. Quantum critical point of Dirac fermions studied using efficient continuous-time projector quantum Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Wang, Lei; Iazzi, Mauro; Corboz, Philippe; Troyer, Matthias

    2015-03-01

    Quantum phase transition (QPT) of Dirac fermions is a fascinating topic both in condensed matter and in high energy physics. Besides its immediate connection to fundamental problems like mass generation and exotic phases of matter, it provides a common playground where state of the art numerical simulations can be crosschecked with various effective field theory predictions, thus deepen our understanding of both fields. The universality class of the QPT is fundamentally different from the usual bosonic field theory because of the coupling to the gapless fermionic mode at the critical point. We study lattice models with spinless and multi-flavor Dirac fermions using the newly developed efficient continuous-time projector quantum Monte Carlo method. Besides eliminating the Trotter error, the method also enables us to directly calculate derivative observables in a continuous range of interaction strengths, thus greatly enhancing the resolution of the quantum critical region. Compatible results are also obtained from infinite projected entangled-pair states calculations. We compare these numerical results with predictions of the Gross-Neveu theory and discuss their physical implications.

  12. Aneesu-Rahman Prize Lecture: The ``sign problem'' in Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Ceperley, D. M.

    1998-03-01

    Quantum simulation methods have been quite successful in giving exact results for certain systems, primarily bosons(Ceperley, D.M. , Rev. Mod. Phys. 67), 279 (1995).. Use of the same techniques in general quantum systems leads to the so-called ``sign problem''; the results are correct but the methods are very inefficient. There are two important questions to ask of a proposed method. Given enough computer time can arbitrarily accurate results be obtained? If so, how long does it take to achieve a given error? There are several methods (released-node or transient estimate) that are exact; the difficulty is in finding a method which also scales well with the number of quantum degrees of freedom. Exact methods, in general, scale exponentially with the number of fermions and in the inverse temperature (or accuracy). At root, the fact that wavefunction is complex or changes sign, gives rise to the poor scaling and the ``sign problem.'' It is not the fermion nature of the system, per se, that causes the difficulty. The desired state is not the absolute ground state. Methods which cancel random walks from positive and negative regions have also been limited to quite small systems because they scale poorly. There are a variety of approximate simulation methods which do scale well, such as variational Monte Carlo, and a variety of fixed-node methods (restricted Path Integral Monte Carlo at non-zero temperature and constrained path methods for lattice models) which fix only boundary conditions not the sampling function. For many systems, the variational and fixed-node methods can be very accurate. The lecture notes and references are on my group's homepage.

  13. Influence of single particle orbital sets and configuration selection on multideterminant wavefunctions in quantum Monte Carlo.

    PubMed

    Clay, Raymond C; Morales, Miguel A

    2015-06-21

    Multideterminant wavefunctions, while having a long history in quantum chemistry, are increasingly being used in highly accurate quantum Monte Carlo calculations. Since the accuracy of QMC is ultimately limited by the quality of the trial wavefunction, multi-Slater determinants wavefunctions offer an attractive alternative to Slater-Jastrow and more sophisticated wavefunction ansatz for several reasons. They can be efficiently calculated, straightforwardly optimized, and systematically improved by increasing the number of included determinants. In spite of their potential, however, the convergence properties of multi-Slater determinant wavefunctions with respect to orbital set choice and excited determinant selection are poorly understood, which hinders the application of these wavefunctions to large systems and solids. In this paper, by performing QMC calculations on the equilibrium and stretched carbon dimer, we find that convergence of the recovered correlation energy with respect to number of determinants can depend quite strongly on basis set and determinant selection methods, especially where there is strong correlation. We demonstrate that properly chosen orbital sets and determinant selection techniques from quantum chemistry methods can dramatically reduce the required number of determinants (and thus the computational cost) to reach a given accuracy, which we argue shows clear need for an automatic QMC-only method for selecting determinants and generating optimal orbital sets. PMID:26093546

  14. Influence of single particle orbital sets and configuration selection on multideterminant wavefunctions in quantum Monte Carlo

    SciTech Connect

    Clay, Raymond C.; Morales, Miguel A.

    2015-06-21

    Multideterminant wavefunctions, while having a long history in quantum chemistry, are increasingly being used in highly accurate quantum Monte Carlo calculations. Since the accuracy of QMC is ultimately limited by the quality of the trial wavefunction, multi-Slater determinants wavefunctions offer an attractive alternative to Slater-Jastrow and more sophisticated wavefunction ansatz for several reasons. They can be efficiently calculated, straightforwardly optimized, and systematically improved by increasing the number of included determinants. In spite of their potential, however, the convergence properties of multi-Slater determinant wavefunctions with respect to orbital set choice and excited determinant selection are poorly understood, which hinders the application of these wavefunctions to large systems and solids. In this paper, by performing QMC calculations on the equilibrium and stretched carbon dimer, we find that convergence of the recovered correlation energy with respect to number of determinants can depend quite strongly on basis set and determinant selection methods, especially where there is strong correlation. We demonstrate that properly chosen orbital sets and determinant selection techniques from quantum chemistry methods can dramatically reduce the required number of determinants (and thus the computational cost) to reach a given accuracy, which we argue shows clear need for an automatic QMC-only method for selecting determinants and generating optimal orbital sets.

  15. Influence of single particle orbital sets and configuration selection on multideterminant wavefunctions in quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Clay, Raymond C.; Morales, Miguel A.

    2015-06-01

    Multideterminant wavefunctions, while having a long history in quantum chemistry, are increasingly being used in highly accurate quantum Monte Carlo calculations. Since the accuracy of QMC is ultimately limited by the quality of the trial wavefunction, multi-Slater determinants wavefunctions offer an attractive alternative to Slater-Jastrow and more sophisticated wavefunction ansatz for several reasons. They can be efficiently calculated, straightforwardly optimized, and systematically improved by increasing the number of included determinants. In spite of their potential, however, the convergence properties of multi-Slater determinant wavefunctions with respect to orbital set choice and excited determinant selection are poorly understood, which hinders the application of these wavefunctions to large systems and solids. In this paper, by performing QMC calculations on the equilibrium and stretched carbon dimer, we find that convergence of the recovered correlation energy with respect to number of determinants can depend quite strongly on basis set and determinant selection methods, especially where there is strong correlation. We demonstrate that properly chosen orbital sets and determinant selection techniques from quantum chemistry methods can dramatically reduce the required number of determinants (and thus the computational cost) to reach a given accuracy, which we argue shows clear need for an automatic QMC-only method for selecting determinants and generating optimal orbital sets.

  16. Quantum Monte Carlo study of strange correlator in interacting topological insulators

    NASA Astrophysics Data System (ADS)

    Wu, Han-Qing; He, Yuan-Yao; You, Yi-Zhuang; Xu, Cenke; Meng, Zi Yang; Lu, Zhong-Yi

    2015-10-01

    Distinguishing the nontrivial symmetry-protected topological (SPT) phase from the trivial insulator phase in the presence of electron-electron interaction is an urgent question to the study of topological insulators, due to the fact that most of the topological indices defined for free electron systems are very likely unsuitable for interacting cases. In this work, we demonstrate that the strange correlator is a sensitive diagnosis to detect SPT states in interacting systems. Employing large-scale quantum Monte Carlo (QMC) simulations, we investigate the interaction-driven quantum phase transition in the Kane-Mele-Hubbard model. The transition from the quantum spin Hall insulator at weak interaction to an antiferromagnetic Mott insulator at strong interaction can be readily detected by the momentum space behavior of the strange correlator in single-particle, spin, and pairing sectors. The interaction effects on the symmetry-protected edge states in various sectors, i.e., the helical Luttinger liquid behavior, are well captured in the QMC measurements of strange correlators. Moreover, we demonstrate that the strange correlator is technically easier to implement in QMC and more robust in performance than other proposed numerical diagnoses for interacting topological states, as only static correlations are needed. The attempt in this work paves the way for using the strange correlator to study interaction-driven topological phase transitions in fermionic as well as bosonic systems.

  17. Quantum Monte Carlo study of strange correlator in interacting topological insulators

    NASA Astrophysics Data System (ADS)

    Wu, Han-Qing; He, Yuan-Yao; You, Yi-Zhuang; Xu, Cenke; Meng, Zi Yang; Lu, Zhong-Yi

    Distinguishing the nontrivial symmetry-protected topological (SPT) phase from the trivial insulator phase in the presence of electron-electron interaction is an urgent question to the study of topological insulators. In this work, we demonstrate that the strange correlator is a sensitive diagnosis to detect SPT states in interacting systems. Employing large-scale quantum Monte Carlo (QMC) simulations, we investigate the interaction-driven quantum phase transition in the Kane-Mele-Hubbard model. The transition from the quantum spin Hall insulator at weak interaction to an antiferromagnetic Mott insulator at strong interaction can be readily detected by the momentum space behavior of the strange correlator in single-particle, spin, and pairing sectors. The interaction e?ects on the symmetry-protected edge states in various sectors are well captured in the QMC measurements of strange correlators. Moreover, we demonstrate that the strange correlator is technically easier to implement in QMC and more robust in performance than other proposed numerical diagnoses for interacting topological states, as only static correlations are needed. The attempt in this work paves the way for using the strange correlator to study interaction-driven topological phase transitions.

  18. The many-body Wigner Monte Carlo method for time-dependent ab-initio quantum simulations

    SciTech Connect

    Sellier, J.M. Dimov, I.

    2014-09-15

    The aim of ab-initio approaches is the simulation of many-body quantum systems from the first principles of quantum mechanics. These methods are traditionally based on the many-body Schrödinger equation which represents an incredible mathematical challenge. In this paper, we introduce the many-body Wigner Monte Carlo method in the context of distinguishable particles and in the absence of spin-dependent effects. Despite these restrictions, the method has several advantages. First of all, the Wigner formalism is intuitive, as it is based on the concept of a quasi-distribution function. Secondly, the Monte Carlo numerical approach allows scalability on parallel machines that is practically unachievable by means of other techniques based on finite difference or finite element methods. Finally, this method allows time-dependent ab-initio simulations of strongly correlated quantum systems. In order to validate our many-body Wigner Monte Carlo method, as a case study we simulate a relatively simple system consisting of two particles in several different situations. We first start from two non-interacting free Gaussian wave packets. We, then, proceed with the inclusion of an external potential barrier, and we conclude by simulating two entangled (i.e. correlated) particles. The results show how, in the case of negligible spin-dependent effects, the many-body Wigner Monte Carlo method provides an efficient and reliable tool to study the time-dependent evolution of quantum systems composed of distinguishable particles.

  19. Itinerant Ferromagnetism of a Repulsive Atomic Fermi Gas: A Quantum Monte Carlo Study

    SciTech Connect

    Pilati, S.; Troyer, M.; Bertaina, G.; Giorgini, S.

    2010-07-16

    We investigate the phase diagram of a two-component repulsive Fermi gas at T=0 by means of quantum Monte Carlo simulations. Both purely repulsive and resonant attractive model potentials are considered in order to analyze the limits of the universal regime where the details of interatomic forces can be neglected. The equation of state of both balanced and unbalanced systems is calculated as a function of the interaction strength and the critical density for the onset of ferromagnetism is determined. The energy of the strongly polarized gas is calculated and parametrized in terms of the physical properties of repulsive polarons, which are relevant for the stability of the fully ferromagnetic state. Finally, we analyze the phase diagram in the interaction-polarization plane under the assumption that only phases with homogeneous magnetization can be produced.

  20. An excited-state approach within full configuration interaction quantum Monte Carlo

    SciTech Connect

    Blunt, N. S.; Smart, Simon D.; Booth, George H.; Alavi, Ali

    2015-10-07

    We present a new approach to calculate excited states with the full configuration interaction quantum Monte Carlo (FCIQMC) method. The approach uses a Gram-Schmidt procedure, instantaneously applied to the stochastically evolving distributions of walkers, to orthogonalize higher energy states against lower energy ones. It can thus be used to study several of the lowest-energy states of a system within the same symmetry. This additional step is particularly simple and computationally inexpensive, requiring only a small change to the underlying FCIQMC algorithm. No trial wave functions or partitioning of the space is needed. The approach should allow excited states to be studied for systems similar to those accessible to the ground-state method due to a comparable computational cost. As a first application, we consider the carbon dimer in basis sets up to quadruple-zeta quality and compare to existing results where available.

  1. Many-body effects on graphene conductivity: Quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Boyda, D. L.; Braguta, V. V.; Katsnelson, M. I.; Ulybyshev, M. V.

    2016-08-01

    Optical conductivity of graphene is studied using quantum Monte Carlo calculations. We start from a Euclidean current-current correlator and extract σ (ω ) from Green-Kubo relations using the Backus-Gilbert method. Calculations were performed both for long-range interactions and taking into account only the contact term. In both cases we vary interaction strength and study its influence on optical conductivity. We compare our results with previous theoretical calculations choosing ω ≈κ , thus working in the region of the plateau in σ (ω ) which corresponds to optical conductivity of Dirac quasiparticles. No dependence of optical conductivity on interaction strength is observed unless we approach the antiferromagnetic phase transition in the case of an artificially enhanced contact term. Our results strongly support previous theoretical studies that claimed very weak regularization of graphene conductivity.

  2. Semi-stochastic full configuration interaction quantum Monte Carlo: Developments and application.

    PubMed

    Blunt, N S; Smart, Simon D; Kersten, J A F; Spencer, J S; Booth, George H; Alavi, Ali

    2015-05-14

    We expand upon the recent semi-stochastic adaptation to full configuration interaction quantum Monte Carlo (FCIQMC). We present an alternate method for generating the deterministic space without a priori knowledge of the wave function and present stochastic efficiencies for a variety of both molecular and lattice systems. The algorithmic details of an efficient semi-stochastic implementation are presented, with particular consideration given to the effect that the adaptation has on parallel performance in FCIQMC. We further demonstrate the benefit for calculation of reduced density matrices in FCIQMC through replica sampling, where the semi-stochastic adaptation seems to have even larger efficiency gains. We then combine these ideas to produce explicitly correlated corrected FCIQMC energies for the beryllium dimer, for which stochastic errors on the order of wavenumber accuracy are achievable. PMID:25978883

  3. Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer.

    PubMed

    Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2016-06-28

    Chemical accuracy is difficult to achieve for systems with transition metal atoms. Third row transition metal atoms are particularly challenging due to strong electron-electron correlation in localized d-orbitals. The Cr2 molecule is an outstanding example, which we previously treated with highly accurate auxiliary-field quantum Monte Carlo (AFQMC) calculations [W. Purwanto et al., J. Chem. Phys. 142, 064302 (2015)]. Somewhat surprisingly, computational description of the isoelectronic Mo2 dimer has also, to date, been scattered and less than satisfactory. We present high-level theoretical benchmarks of the Mo2 singlet ground state (X(1)Σg (+)) and first triplet excited state (a(3)Σu (+)), using the phaseless AFQMC calculations. Extrapolation to the complete basis set limit is performed. Excellent agreement with experimental spectroscopic constants is obtained. We also present a comparison of the correlation effects in Cr2 and Mo2. PMID:27369514

  4. Quantum Monte Carlo simulation of the ferroelectric or ferrielectric nanowire with core shell morphology

    NASA Astrophysics Data System (ADS)

    Feraoun, A.; Zaim, A.; Kerouad, M.

    2016-09-01

    By using the Quantum Monte Carlo simulation; the electric properties of a nanowire, consisting of a ferroelectric core of spin-1/2 surrounded by a ferroelectric shell of spin-1/2 with ferro- or anti-ferroelectric interfacial coupling have been studied within the framework of the Transverse Ising Model (TIM). We have examined the effects of the shell coupling Js, the interfacial coupling JInt, the transverse field Ω, and the temperature T on the hysteresis behavior and on the electric properties of the system. The remanent polarization and the coercive field as a function of the transverse field and the temperature are examined. A number of characteristic behavior have been found such as the appearance of triple hysteresis loops for appropriate values of the system parameters.

  5. Auxiliary-field based trial wave functions in quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Chang, Chia-Chen; Rubenstein, Brenda; Morales, Miguel

    We propose a simple scheme for generating correlated multi-determinant trial wave functions for quantum Monte Carlo algorithms. The method is based on the Hubbard-Stratonovich transformation which decouples a two-body Jastrow-type correlator into one-body projectors coupled to auxiliary fields. We apply the technique to generate stochastic representations of the Gutzwiller wave function, and present benchmark resuts for the ground state energy of the Hubbard model in one dimension. Extensions of the proposed scheme to chemical systems will also be discussed. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344, 15-ERD-013.

  6. Semi-stochastic full configuration interaction quantum Monte Carlo: Developments and application

    SciTech Connect

    Blunt, N. S. Kersten, J. A. F.; Smart, Simon D.; Spencer, J. S.; Booth, George H.; Alavi, Ali

    2015-05-14

    We expand upon the recent semi-stochastic adaptation to full configuration interaction quantum Monte Carlo (FCIQMC). We present an alternate method for generating the deterministic space without a priori knowledge of the wave function and present stochastic efficiencies for a variety of both molecular and lattice systems. The algorithmic details of an efficient semi-stochastic implementation are presented, with particular consideration given to the effect that the adaptation has on parallel performance in FCIQMC. We further demonstrate the benefit for calculation of reduced density matrices in FCIQMC through replica sampling, where the semi-stochastic adaptation seems to have even larger efficiency gains. We then combine these ideas to produce explicitly correlated corrected FCIQMC energies for the beryllium dimer, for which stochastic errors on the order of wavenumber accuracy are achievable.

  7. An auxiliary-field quantum Monte Carlo study of the chromium dimer

    SciTech Connect

    Purwanto, Wirawan Zhang, Shiwei; Krakauer, Henry

    2015-02-14

    The chromium dimer (Cr{sub 2}) presents an outstanding challenge for many-body electronic structure methods. Its complicated nature of binding, with a formal sextuple bond and an unusual potential energy curve (PEC), is emblematic of the competing tendencies and delicate balance found in many strongly correlated materials. We present an accurate calculation of the PEC and ground state properties of Cr{sub 2}, using the auxiliary-field quantum Monte Carlo (AFQMC) method. Unconstrained, exact AFQMC calculations are first carried out for a medium-sized but realistic basis set. Elimination of the remaining finite-basis errors and extrapolation to the complete basis set limit are then achieved with a combination of phaseless and exact AFQMC calculations. Final results for the PEC and spectroscopic constants are in excellent agreement with experiment.

  8. Constrained-path quantum Monte Carlo approach for non-yrast states within the shell model

    NASA Astrophysics Data System (ADS)

    Bonnard, J.; Juillet, O.

    2016-04-01

    The present paper intends to present an extension of the constrained-path quantum Monte Carlo approach allowing to reconstruct non-yrast states in order to reach the complete spectroscopy of nuclei within the interacting shell model. As in the yrast case studied in a previous work, the formalism involves a variational symmetry-restored wave function assuming two central roles. First, it guides the underlying Brownian motion to improve the efficiency of the sampling. Second, it constrains the stochastic paths according to the phaseless approximation to control sign or phase problems that usually plague fermionic QMC simulations. Proof-of-principle results in the sd valence space are reported. They prove the ability of the scheme to offer remarkably accurate binding energies for both even- and odd-mass nuclei irrespective of the considered interaction.

  9. Ab Initio Quantum Monte Carlo Simulation of the Warm Dense Electron Gas in the Thermodynamic Limit

    NASA Astrophysics Data System (ADS)

    Dornheim, Tobias; Groth, Simon; Sjostrom, Travis; Malone, Fionn D.; Foulkes, W. M. C.; Bonitz, Michael

    2016-10-01

    We perform ab initio quantum Monte Carlo (QMC) simulations of the warm dense uniform electron gas in the thermodynamic limit. By combining QMC data with the linear response theory, we are able to remove finite-size errors from the potential energy over the substantial parts of the warm dense regime, overcoming the deficiencies of the existing finite-size corrections by Brown et al. [Phys. Rev. Lett. 110, 146405 (2013)]. Extensive new QMC results for up to N =1000 electrons enable us to compute the potential energy V and the exchange-correlation free energy Fxc of the macroscopic electron gas with an unprecedented accuracy of |Δ V |/|V |,|Δ Fxc|/|F |xc˜10-3 . A comparison of our new data to the recent parametrization of Fxc by Karasiev et al. [Phys. Rev. Lett. 112, 076403 (2014)] reveals significant deviations to the latter.

  10. Lazy skip-lists: An algorithm for fast hybridization-expansion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Sémon, P.; Yee, Chuck-Hou; Haule, Kristjan; Tremblay, A.-M. S.

    2014-08-01

    The solution of a generalized impurity model lies at the heart of electronic structure calculations with dynamical mean field theory. In the strongly correlated regime, the method of choice for solving the impurity model is the hybridization-expansion continuous-time quantum Monte Carlo (CT-HYB). Enhancements to the CT-HYB algorithm are critical for bringing new physical regimes within reach of current computational power. Taking advantage of the fact that the bottleneck in the algorithm is a product of hundreds of matrices, we present optimizations based on the introduction and combination of two concepts of more general applicability: (a) skip lists and (b) fast rejection of proposed configurations based on matrix bounds. Considering two very different test cases with d electrons, we find speedups of ˜25 up to ˜500 compared to the direct evaluation of the matrix product. Even larger speedups are likely with f electron systems and with clusters of correlated atoms.

  11. Quantum Monte Carlo Studies of Bulk and Few- or Single-Layer Black Phosphorus

    NASA Astrophysics Data System (ADS)

    Shulenburger, Luke; Baczewski, Andrew; Zhu, Zhen; Guan, Jie; Tomanek, David

    2015-03-01

    The electronic and optical properties of phosphorus depend strongly on the structural properties of the material. Given the limited experimental information on the structure of phosphorene, it is natural to turn to electronic structure calculations to provide this information. Unfortunately, given phosphorus' propensity to form layered structures bound by van der Waals interactions, standard density functional theory methods provide results of uncertain accuracy. Recently, it has been demonstrated that Quantum Monte Carlo (QMC) methods achieve high accuracy when applied to solids in which van der Waals forces play a significant role. In this talk, we will present QMC results from our recent calculations on black phosphorus, focusing on the structural and energetic properties of monolayers, bilayers and bulk structures. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  12. Theory of melting at high pressures: Amending density functional theory with quantum Monte Carlo

    DOE PAGES

    Shulenburger, L.; Desjarlais, M. P.; Mattsson, T. R.

    2014-10-01

    We present an improved first-principles description of melting under pressure based on thermodynamic integration comparing Density Functional Theory (DFT) and quantum Monte Carlo (QMC) treatments of the system. The method is applied to address the longstanding discrepancy between density functional theory (DFT) calculations and diamond anvil cell (DAC) experiments on the melting curve of xenon, a noble gas solid where van der Waals binding is challenging for traditional DFT methods. The calculations show excellent agreement with data below 20 GPa and that the high-pressure melt curve is well described by a Lindemann behavior up to at least 80 GPa, amore » finding in stark contrast to DAC data.« less

  13. Benchmarking exchange-correlation functionals for hydrogen at high pressures using quantum Monte Carlo

    SciTech Connect

    Clay, Raymond C.; Mcminis, Jeremy; McMahon, Jeffrey M.; Pierleoni, Carlo; Ceperley, David M.; Morales, Miguel A.

    2014-05-01

    The ab initio phase diagram of dense hydrogen is very sensitive to errors in the treatment of electronic correlation. Recently, it has been shown that the choice of the density functional has a large effect on the predicted location of both the liquid-liquid phase transition and the solid insulator-to-metal transition in dense hydrogen. To identify the most accurate functional for dense hydrogen applications, we systematically benchmark some of the most commonly used functionals using quantum Monte Carlo. By considering several measures of functional accuracy, we conclude that the van der Waals and hybrid functionals significantly outperform local density approximation and Perdew-Burke-Ernzerhof. We support these conclusions by analyzing the impact of functional choice on structural optimization in the molecular solid, and on the location of the liquid-liquid phase transition.

  14. Ground-state properties of LiH by reptation quantum Monte Carlo methods.

    PubMed

    Ospadov, Egor; Oblinsky, Daniel G; Rothstein, Stuart M

    2011-05-01

    We apply reptation quantum Monte Carlo to calculate one- and two-electron properties for ground-state LiH, including all tensor components for static polarizabilities and hyperpolarizabilities to fourth-order in the field. The importance sampling is performed with a large (QZ4P) STO basis set single determinant, directly obtained from commercial software, without incurring the overhead of optimizing many-parameter Jastrow-type functions of the inter-electronic and internuclear distances. We present formulas for the electrical response properties free from the finite-field approximation, which can be problematic for the purposes of stochastic estimation. The α, γ, A and C polarizability values are reasonably consistent with recent determinations reported in the literature, where they exist. A sum rule is obeyed for components of the B tensor, but B(zz,zz) as well as β(zzz) differ from what was reported in the literature. PMID:21445452

  15. Linear-scaling evaluation of the local energy in quantum MonteCarlo

    SciTech Connect

    Austin, Brian; Aspuru-Guzik, Alan; Salomon-Ferrer, Romelia; Lester Jr., William A.

    2006-02-11

    For atomic and molecular quantum Monte Carlo calculations, most of the computational effort is spent in the evaluation of the local energy. We describe a scheme for reducing the computational cost of the evaluation of the Slater determinants and correlation function for the correlated molecular orbital (CMO) ansatz. A sparse representation of the Slater determinants makes possible efficient evaluation of molecular orbitals. A modification to the scaled distance function facilitates a linear scaling implementation of the Schmidt-Moskowitz-Boys-Handy (SMBH) correlation function that preserves the efficient matrix multiplication structure of the SMBH function. For the evaluation of the local energy, these two methods lead to asymptotic linear scaling with respect to the molecule size.

  16. Boosting the accuracy and speed of quantum Monte Carlo: Size consistency and time step

    NASA Astrophysics Data System (ADS)

    Zen, Andrea; Sorella, Sandro; Gillan, Michael J.; Michaelides, Angelos; Alfè, Dario

    2016-06-01

    Diffusion Monte Carlo (DMC) simulations for fermions are becoming the standard for providing high-quality reference data in systems that are too large to be investigated via quantum chemical approaches. DMC with the fixed-node approximation relies on modifications of the Green's function to avoid singularities near the nodal surface of the trial wave function. Here we show that these modifications affect the DMC energies in a way that is not size consistent, resulting in large time-step errors. Building on the modifications of Umrigar et al. and DePasquale et al. we propose a simple Green's function modification that restores size consistency to large values of the time step, which substantially reduces time-step errors. This algorithm also yields remarkable speedups of up to two orders of magnitude in the calculation of molecule-molecule binding energies and crystal cohesive energies, thus extending the horizons of what is possible with DMC.

  17. Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures

    PubMed Central

    Drummond, N. D.; Monserrat, Bartomeu; Lloyd-Williams, Jonathan H.; Ríos, P. López; Pickard, Chris J.; Needs, R. J.

    2015-01-01

    Establishing the phase diagram of hydrogen is a major challenge for experimental and theoretical physics. Experiment alone cannot establish the atomic structure of solid hydrogen at high pressure, because hydrogen scatters X-rays only weakly. Instead, our understanding of the atomic structure is largely based on density functional theory (DFT). By comparing Raman spectra for low-energy structures found in DFT searches with experimental spectra, candidate atomic structures have been identified for each experimentally observed phase. Unfortunately, DFT predicts a metallic structure to be energetically favoured at a broad range of pressures up to 400 GPa, where it is known experimentally that hydrogen is non-metallic. Here we show that more advanced theoretical methods (diffusion quantum Monte Carlo calculations) find the metallic structure to be uncompetitive, and predict a phase diagram in reasonable agreement with experiment. This greatly strengthens the claim that the candidate atomic structures accurately model the experimentally observed phases. PMID:26215251

  18. Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer

    NASA Astrophysics Data System (ADS)

    Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2016-06-01

    Chemical accuracy is difficult to achieve for systems with transition metal atoms. Third row transition metal atoms are particularly challenging due to strong electron-electron correlation in localized d-orbitals. The Cr2 molecule is an outstanding example, which we previously treated with highly accurate auxiliary-field quantum Monte Carlo (AFQMC) calculations [W. Purwanto et al., J. Chem. Phys. 142, 064302 (2015)]. Somewhat surprisingly, computational description of the isoelectronic Mo2 dimer has also, to date, been scattered and less than satisfactory. We present high-level theoretical benchmarks of the Mo2 singlet ground state (X1Σg+) and first triplet excited state (a3Σu+), using the phaseless AFQMC calculations. Extrapolation to the complete basis set limit is performed. Excellent agreement with experimental spectroscopic constants is obtained. We also present a comparison of the correlation effects in Cr2 and Mo2.

  19. Note: A pure-sampling quantum Monte Carlo algorithm with independent Metropolis

    NASA Astrophysics Data System (ADS)

    Vrbik, Jan; Ospadov, Egor; Rothstein, Stuart M.

    2016-07-01

    Recently, Ospadov and Rothstein published a pure-sampling quantum Monte Carlo algorithm (PSQMC) that features an auxiliary Path Z that connects the midpoints of the current and proposed Paths X and Y, respectively. When sufficiently long, Path Z provides statistical independence of Paths X and Y. Under those conditions, the Metropolis decision used in PSQMC is done without any approximation, i.e., not requiring microscopic reversibility and without having to introduce any G(x → x'; τ) factors into its decision function. This is a unique feature that contrasts with all competing reptation algorithms in the literature. An example illustrates that dependence of Paths X and Y has adverse consequences for pure sampling.

  20. One-dimensional multicomponent Fermi gas in a trap: quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Matveeva, N.; Astrakharchik, G. E.

    2016-06-01

    A one-dimensional world is very unusual as there is an interplay between quantum statistics and geometry, and a strong short-range repulsion between atoms mimics Fermi exclusion principle, fermionizing the system. Instead, a system with a large number of components with a single atom in each, on the opposite acquires many bosonic properties. We study the ground-state properties of a multicomponent repulsive Fermi gas trapped in a harmonic trap by a fixed-node diffusion Monte Carlo method. The interaction between all components is considered to be the same. We investigate how the energetic properties (energy, contact) and correlation functions (density profile and momentum distribution) evolve as the number of components is changed. It is shown that the system fermionizes in the limit of strong interactions. Analytical expressions are derived in the limit of weak interactions within the local density approximation for an arbitrary number of components and for one plus one particle using an exact solution.

  1. Quantum Monte Carlo study of the reaction: C1 + CH3OH -->CH2OH+ HCl

    SciTech Connect

    Kollias, A.C.; Couronne, O.; Lester Jr., W.A.

    2003-12-01

    A theoretical study is reported of the Cl + CH{sub 3}OH {yields} CH{sub 2}OH + HCl reaction based on the diffusion Monte Carlo (DMC) variant of the quantum Monte Carlo method. Using a DMC trial function constructed as a product of Hartree-Fock and correlation functions, we have computed the barrier height, heat of reaction, atomization energies and heats of formation of reagents and products. The DMC heat of reaction, atomization energies, and heats of formation are found to agree with experiment to within the error bounds of computation and experiment. Moller-Plesset second order perturbation theory (MP2) and density functional theory, the latter in the B3LYP generalized gradient approximation, are found to overestimate the experimental heat of reaction. Intrinsic reaction coordinate calculations at the MP2 level of theory demonstrate that the reaction is predominantly direct, i.e., proceeds without formation of intermediates, which is consistent with a recent molecular beam experiment. The reaction barrier as determined from MP2 calculations is found to be 2.24 kcal/mol and by DMC it is computed to be 2.39(49) kcal/mol.

  2. Dynamic load balancing for petascale quantum Monte Carlo applications: The Alias method

    NASA Astrophysics Data System (ADS)

    Sudheer, C. D.; Krishnan, S.; Srinivasan, A.; Kent, P. R. C.

    2013-02-01

    Diffusion Monte Carlo is a highly accurate Quantum Monte Carlo method for electronic structure calculations of materials, but it requires frequent load balancing or population redistribution steps to maintain efficiency on parallel machines. This step can be a significant factor affecting performance, and will become more important as the number of processing elements increases. We propose a new dynamic load balancing algorithm, the Alias Method, and evaluate it theoretically and empirically. An important feature of the new algorithm is that the load can be perfectly balanced with each process receiving at most one message. It is also optimal in the maximum size of messages received by any process. We also optimize its implementation to reduce network contention, a process facilitated by the low messaging requirement of the algorithm: a simple renumbering of the MPI ranks based on proximity and a space filling curve significantly improves the MPI Allgather performance. Empirical results on the petaflop Cray XT Jaguar supercomputer at ORNL show up to 30% improvement in performance on 120,000 cores. The load balancing algorithm may be straightforwardly implemented in existing codes. The algorithm may also be employed by any method with many near identical computational tasks that require load balancing.

  3. Accurate band gaps of semiconductors and insulators from Quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Nazarov, Roman; Hood, Randolph; Morales, Miguel

    2015-03-01

    Ab initio calculations are useful tools in developing materials with targeted band gaps for semiconductor industry. Unfortunately, the main workhorse of ab initio calculations - density functional theory (DFT) in local density approximation (LDA) or generalized gradient approximation (GGA) underestimates band gaps. Several approaches have been proposed starting from empirical corrections to more elaborate exchange-correlation functionals to deal with this problem. But none of these work well for the entire range of semiconductors and insulators. Deficiencies of DFT as a mean field method can be overcome using many-body techniques. Quantum Monte Carlo (QMC) methods can obtain a nearly exact numerical solutions of both total energies and spectral properties. Diffusion Monte Carlo (DMC), the most widely used QMC method, has been shown to provide gold standard results for different material properties, including spectroscopic constants of dimers and clusters, equation of state for solids, accurate descriptions of defects in metals and insulators. To test DMC's accuracy in a wider range of semiconductors and insulators we have computed band gaps of several semiconductors and insulators. We show that DMC can provide superior agreement with experiment compared with more traditional DFT approaches including high level exchange-correlation functionals (e.g. HSE).

  4. Auxiliary-field quantum Monte Carlo simulations of neutron matter in chiral effective field theory.

    PubMed

    Wlazłowski, G; Holt, J W; Moroz, S; Bulgac, A; Roche, K J

    2014-10-31

    We present variational Monte Carlo calculations of the neutron matter equation of state using chiral nuclear forces. The ground-state wave function of neutron matter, containing nonperturbative many-body correlations, is obtained from auxiliary-field quantum Monte Carlo simulations of up to about 340 neutrons interacting on a 10(3) discretized lattice. The evolution Hamiltonian is chosen to be attractive and spin independent in order to avoid the fermion sign problem and is constructed to best reproduce broad features of the chiral nuclear force. This is facilitated by choosing a lattice spacing of 1.5 fm, corresponding to a momentum-space cutoff of Λ=414  MeV/c, a resolution scale at which strongly repulsive features of nuclear two-body forces are suppressed. Differences between the evolution potential and the full chiral nuclear interaction (Entem and Machleidt Λ=414  MeV [L. Coraggio et al., Phys. Rev. C 87, 014322 (2013).

  5. Quantum Monte Carlo calculations of neutron matter with chiral three-body forces

    DOE PAGES

    Tews, I.; Gandolfi, Stefano; Gezerlis, A.; Schwenk, A.

    2016-02-02

    Chiral effective field theory (EFT) enables a systematic description of low-energy hadronic interactions with controlled theoretical uncertainties. For strongly interacting systems, quantum Monte Carlo (QMC) methods provide some of the most accurate solutions, but they require as input local potentials. We have recently constructed local chiral nucleon-nucleon (NN) interactions up to next-to-next-to-leading order (N2LO). Chiral EFT naturally predicts consistent many-body forces. In this paper, we consider the leading chiral three-nucleon (3N) interactions in local form. These are included in auxiliary field diffusion Monte Carlo (AFDMC) simulations. We present results for the equation of state of neutron matter and for themore » energies and radii of neutron drops. Specifically, we study the regulator dependence at the Hartree-Fock level and in AFDMC and find that present local regulators lead to less repulsion from 3N forces compared to the usual nonlocal regulators.« less

  6. Dynamic load balancing for petascale quantum Monte Carlo applications: The Alias method

    SciTech Connect

    Sudheer, C. D.; Krishnan, S.; Srinivasan, A.; Kent, P. R. C.

    2013-02-01

    Diffusion Monte Carlo is the most accurate widely used Quantum Monte Carlo method for the electronic structure of materials, but it requires frequent load balancing or population redistribution steps to maintain efficiency and avoid accumulation of systematic errors on parallel machines. The load balancing step can be a significant factor affecting performance, and will become more important as the number of processing elements increases. We propose a new dynamic load balancing algorithm, the Alias Method, and evaluate it theoretically and empirically. An important feature of the new algorithm is that the load can be perfectly balanced with each process receiving at most one message. It is also optimal in the maximum size of messages received by any process. We also optimize its implementation to reduce network contention, a process facilitated by the low messaging requirement of the algorithm. Empirical results on the petaflop Cray XT Jaguar supercomputer at ORNL showing up to 30% improvement in performance on 120,000 cores. The load balancing algorithm may be straightforwardly implemented in existing codes. The algorithm may also be employed by any method with many near identical computational tasks that requires load balancing.

  7. State-of-the-art molecular applications of full configuration interaction quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Thomas, Robert; Overy, Catherine; Shepherd, James; Booth, George; Alavi, Ali

    2013-03-01

    Full configuration interaction quantum Monte Carlo (FCIQMC)1 and its initiator adaptation (i-FCIQMC)2 provide, in principle, exact (FCI) energies via a population dynamics algorithm of an ensemble of discrete, signed walkers in Slater-determinant space. We demonstrate that a novel choice of reference state has the potential to widen the scope of this already versatile method, and corroborate the finding that an extension of the algorithm to allow non-integer walkers can yield significantly reduced stochastic error without a commensurate increase in computational cost3. New applications of FCIQMC to transition-metal systems of general and biological interest are presented, many of which have, to date, posed serious challenges for traditional quantum chemical methods 45. 1 G. H. Booth, A. J. W. Thom, and A. Alavi, J. Chem. Phys., 131, 054106 (2009) 2 D. M. Cleland, G. H. Booth, and A. Alavi, J. Chem. Phys., 132, 041103 (2010) 3 F. R. Petruzielo, A. A. Holmes, H. J. Changlani, M. P. Nightingale and C. J. Umrigar, arXiv:1207.6138 4 N. B. Balabanov and K. A. Peterson, J. Chem. Phys., 125, 074110 (2006) 5 C. J. Cramer, M. Wloch, P. Piecuch, C. Puzzarini and L. Gagliardi, J. Phys. Chem. A, 110, 1991 (2006)

  8. Thermochemistry and Charge Delocalization in Cyclization Reactions Using Accurate Quantum Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    Saritas, Kayahan; Grossman, Jeffrey C.

    2015-03-01

    Molecules that undergo pericyclic isomerization reactions find interesting optical and energy storage applications, because of their usually high quantum yields, large spectral shifts and small structural changes upon light absorption. These reactions induce a drastic change in the conjugated structure such that substituents that become a part of the conjugated system upon isomerization can play an important role in determining properties such as enthalpy of isomerization and HOMO-LUMO gap. Therefore, theoretical investigations dealing with such systems should be capable of accurately capturing the interplay between electron correlation and exchange effects. In this work, we examine the dihydroazulene isomerization as an example conjugated system. We employ the highly accurate quantum Monte Carlo (QMC) method to predict thermochemical properties and to benchmark results from density functional theory (DFT) methods. Although DFT provides sufficient accuracy for similar systems, in this particular system, DFT predictions of ground state and reaction paths are inconsistent and non-systematic errors arise. We present a comparison between QMC and DFT results for enthalpy of isomerization, HOMO-LUMO gap and charge densities with a range of DFT functionals.

  9. Bayesian inference and the analytic continuation of imaginary-time quantum Monte Carlo data

    NASA Astrophysics Data System (ADS)

    Jarrell, Mark; Gubernatis, J. E.

    1996-05-01

    We present a way to use Bayesian statistical inference and the principle of maximum entropy to analytically continue imaginary-time quantum Monte Carlo data. We supply the details that are lacking in the seminal literature but are important for the motivated reader to understand the assumptions and approximations embodied in these methods. First, we summarize the general relations between quantum correlation functions and spectral densities. We then review the basic principles, formalism, and philosophy of Bayesian inference and discuss the application of this approach in the context of the analytic continuation problem. Next, we present a detailed case study for the symmetric, infinite-dimension Anderson Hamiltonian. We chose this Hamiltonian because the qualitative features of its spectral density are well established and because a particularly convenient algorithm exists to produce the imaginary-time Green's function data. Shown are all the intermediate steps of data and solution qualification. The importance of careful data preparation and error propagation in the analytic continuation is discussed in the context of this example. Then, we review the different physical systems and physical quantities to which these, or related, procedures have been applied. Finally, we describe other features concerning the application of our methods, their possible improvement, and areas for additional study.

  10. Use of the Sumudu transform to extract response functions from Quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Pederiva, Francesco; Roggero, Alessandro; Orlandini, Giuseppina

    2014-07-01

    We review an ab-initio method for calculating the dynamical structure function of an interacting many-body quantum system. The method consists in coupling a generalized integral transform approach with imaginary time Quantum Monte Carlo calculations. The strength of the method has been tested on the excitation spectrum of bulk atomic 4He. The peculiar form of the kernel as a representation of the delta-function has allowed to minimize the ill-posedness of the integral transform inversion. In fact it has been possible to obtain, at a considerable degree of reliability, both position and width of the collective excitations in the maxon-roton region, as well as the second collective peak. What we stress here is the ability of such a 4-function-like kernel, for which one can control position and width, to maintain in the transformed space the characteristics of the collective structures. The application to the coherent and incoherent density excitation spectrum of liquid 4He is discussed.

  11. A Hardware-Accelerated Quantum Monte Carlo framework (HAQMC) for N-body systems

    NASA Astrophysics Data System (ADS)

    Gothandaraman, Akila; Peterson, Gregory D.; Warren, G. Lee; Hinde, Robert J.; Harrison, Robert J.

    2009-12-01

    Interest in the study of structural and energetic properties of highly quantum clusters, such as inert gas clusters has motivated the development of a hardware-accelerated framework for Quantum Monte Carlo simulations. In the Quantum Monte Carlo method, the properties of a system of atoms, such as the ground-state energies, are averaged over a number of iterations. Our framework is aimed at accelerating the computations in each iteration of the QMC application by offloading the calculation of properties, namely energy and trial wave function, onto reconfigurable hardware. This gives a user the capability to run simulations for a large number of iterations, thereby reducing the statistical uncertainty in the properties, and for larger clusters. This framework is designed to run on the Cray XD1 high performance reconfigurable computing platform, which exploits the coarse-grained parallelism of the processor along with the fine-grained parallelism of the reconfigurable computing devices available in the form of field-programmable gate arrays. In this paper, we illustrate the functioning of the framework, which can be used to calculate the energies for a model cluster of helium atoms. In addition, we present the capabilities of the framework that allow the user to vary the chemical identities of the simulated atoms. Program summaryProgram title: Hardware Accelerated Quantum Monte Carlo (HAQMC) Catalogue identifier: AEEP_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEEP_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 691 537 No. of bytes in distributed program, including test data, etc.: 5 031 226 Distribution format: tar.gz Programming language: C/C++ for the QMC application, VHDL and Xilinx 8.1 ISE/EDK tools for FPGA design and development Computer: Cray XD

  12. Speeding Up and Quantifying Approximation Error in Continuum Quantum Monte Carlo Solid-State Calculations

    NASA Astrophysics Data System (ADS)

    Parker, William David

    Quantum theory has successfully explained the mechanics of much of the microscopic world. However, Schrodinger's equations are difficult to solve for many-particle systems. Mean-field theories such as Hartree-Fock and density functional theory account for much of the total energy of electronic systems but fail on the crucial correlation energy that predicts solid cohesion and material properties. Monte Carlo methods solve differential and integral equations with error independent of the number of dimensions in the problem. Variational Monte Carlo (VMC) applies the variational principle to optimize the wave function used in the Monte Carlo integration of Schrodinger's time-independent equation. Diffusion Monte Carlo (DMC) represents the wave function by electron configurations diffusing stochastically in imaginary time to the ground state. Approximations in VMC and DMC make the problem tractable but introduce error in parameter-controlled and uncontrolled ways. The many-electron wave function consists of single-particle orbitals. The orbitals are combined in a functional form to account for electron exchange and correlation. Plane waves are a convenient basis for the orbitals. However, plane-wave orbitals grow in evaluation cost with basis-set completeness and system size. To speed up the calculation, polynomials approximate the plane-wave sum. Four polynomial methods tested are: Lagrange interpolation, pp-spline interpolation, B-spline interpolation and B-spline approximation. The polynomials all increase speed by an order of the number of particles. B-spline approximation most consistently maintains accuracy in the seven systems tested. However, polynomials increase the memory needed by a factor of two to eight. B-spline approximation with a separate approximation for the Laplacian of the orbitals increases the memory by a factor of four over plane waves. Polynomial-based orbitals enable larger calculations and careful examination of error introduced by

  13. Retrodictive derivation of the radical-ion-pair master equation and Monte Carlo simulation with single-molecule quantum trajectories.

    PubMed

    Kritsotakis, M; Kominis, I K

    2014-10-01

    Radical-ion-pair reactions, central in photosynthesis and the avian magnetic compass mechanism, have been recently shown to be a paradigm system for applying quantum information science in a biochemical setting. The fundamental quantum master equation describing radical-ion-pair reactions is still under debate. Here we use quantum retrodiction to formally refine the theory put forward in the paper by Kominis [I. K. Kominis, Phys. Rev. E 83, 056118 (2011)]. We also provide a rigorous analysis of the measure of singlet-triplet coherence required for deriving the radical-pair master equation. A Monte Carlo simulation with single-molecule quantum trajectories supports the self-consistency of our approach. PMID:25375535

  14. Retrodictive derivation of the radical-ion-pair master equation and Monte Carlo simulation with single-molecule quantum trajectories

    NASA Astrophysics Data System (ADS)

    Kritsotakis, M.; Kominis, I. K.

    2014-10-01

    Radical-ion-pair reactions, central in photosynthesis and the avian magnetic compass mechanism, have been recently shown to be a paradigm system for applying quantum information science in a biochemical setting. The fundamental quantum master equation describing radical-ion-pair reactions is still under debate. Here we use quantum retrodiction to formally refine the theory put forward in the paper by Kominis [I. K. Kominis, Phys. Rev. E 83, 056118 (2011), 10.1103/PhysRevE.83.056118]. We also provide a rigorous analysis of the measure of singlet-triplet coherence required for deriving the radical-pair master equation. A Monte Carlo simulation with single-molecule quantum trajectories supports the self-consistency of our approach.

  15. Quantum Monte Carlo Treatment of the Charge Transfer and Diradical Electronic Character in a Retinal Chromophore Minimal Model

    PubMed Central

    2015-01-01

    The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis–trans isomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron–electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and

  16. Quantum Monte Carlo Treatment of the Charge Transfer and Diradical Electronic Character in a Retinal Chromophore Minimal Model.

    PubMed

    Zen, Andrea; Coccia, Emanuele; Gozem, Samer; Olivucci, Massimo; Guidoni, Leonardo

    2015-03-10

    The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis–trans isomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron–electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and

  17. Quantum Monte Carlo Treatment of the Charge Transfer and Diradical Electronic Character in a Retinal Chromophore Minimal Model.

    PubMed

    Zen, Andrea; Coccia, Emanuele; Gozem, Samer; Olivucci, Massimo; Guidoni, Leonardo

    2015-03-10

    The penta-2,4-dieniminium cation (PSB3) displays similar ground state and first excited state potential energy features as those of the retinal protonated Schiff base (RPSB) chromophore in rhodopsin. Recently, PSB3 has been used to benchmark several electronic structure methods, including highly correlated multireference wave function approaches, highlighting the necessity to accurately describe the electronic correlation in order to obtain reliable properties even along the ground state (thermal) isomerization paths. In this work, we apply two quantum Monte Carlo approaches, the variational Monte Carlo and the lattice regularized diffusion Monte Carlo, to study the energetics and electronic properties of PSB3 along representative minimum energy paths and scans related to its thermal cis–trans isomerization. Quantum Monte Carlo is used in combination with the Jastrow antisymmetrized geminal power ansatz, which guarantees an accurate and balanced description of the static electronic correlation thanks to the multiconfigurational nature of the antisymmetrized geminal power term, and of the dynamical correlation, due to the presence of the Jastrow factor explicitly depending on electron–electron distances. Along the two ground state isomerization minimum energy paths of PSB3, CASSCF calculations yield wave functions having either charge transfer or diradical character in proximity of the two transition state configurations. Here, we observe that at the quantum Monte Carlo level of theory, only the transition state with charge transfer character can be located. The conical intersection, which becomes highly sloped, is observed only if the path connecting the two original CASSCF transition states is extended beyond the diradical one, namely by increasing the bond-length-alternation (BLA). These findings are in good agreement with the results obtained by MRCISD+Q calculations, and they demonstrate the importance of having an accurate description of the static and

  18. Study of Atoms and Molecules with Auxiliary-Field Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Purwanto, Wirawan; Suewattana, Malliga; Krakauer, Henry; Zhang, Shiwei; Walter, Eric J.

    2006-03-01

    We study the ground-state properties of second-row atoms and molecules using the phaseless auxiliary-field quantum Monte Carlo (AF QMC) method. This method projects the many-body ground state from a trial wave function by means of random walks in the Slater-determinant space. We use a single Slater-determinant trial wave function obtained from density-functional theory (DFT) or Hartree-Fock (HF) calculations. The calculations were done with a plane-wave basis and supercells with periodic boundary condition. We investigate the finite-size effects and the accuracy of pseudopotentials within DFT, HF, and AF QMC frameworks. Pseudopotentials generated from both LDA (OPIUM) and HF are employed. We find that the many-body QMC calculations show a greater sensitivity to the accuracy of the pseudopotentials. With reliable pseudopotentials, the ionization potentials and dissociation energies obtained using AF QMC are in excellent agreement with the experimental results. S. Zhang and H. Krakauer, Phys. Rev. Lett. 90, 136401 (2003) http://opium.sourceforge.net I. Ovcharenko, A. Aspuru-Guzik, and W. A. Lester, J. Chem. Phys. 114, 7790 (2001)

  19. Quantum Monte Carlo calculation of the singlet--triplet splitting in methylene

    SciTech Connect

    Reynolds, P.J.; Dupuis, M.; Lester W.A. Jr.

    1985-02-15

    The fixed-node quantum Monte Carlo (QMC) method is used to calculate the total energy of CH/sub 2/ in the /sup 3/B/sub 1/ and /sup 1/A/sub 1/ states. For both states, the best QMC variationally bounded energies lie more than 15 kcal/mol (0.024 h) below the best previous variational calculations. Subtracting these energies to obtain the singlet--triplet splitting yields T/sub e/ = 9.4 +- 2.2 kcal/mol. Adjusting for zero-point energies and relativistic effects, we obtain T/sub 0/ = 8.9 +- 2.2 kcal/mol. This result is in excellent agreement with the recent direct measurements of McKellar et al. of T/sub 0/ = 9.05 +- 0.06 kcal/mol, and of Leopold et al. of approx.9 kcal/mol, as well as with recent threoretical investigations which indicate an energy gap of 9--11 kcal/mol. We summarize the QMC method, discuss a possible scheme for iteratively correcting the procedure, and note that the present results were obtained using only single determinant functions for both states, in contrast to conventional ab initio approaches which must use at least two configurations to properly describe the singlet state.

  20. Quantum and Molecular Mechanical (QM/MM) Monte Carlo Techniques for Modeling Condensed-Phase Reactions

    PubMed Central

    Jorgensen, Wiliiam L.

    2014-01-01

    A recent review (Acc. Chem. Res. 2010, 43:142–151) examined our use and development of a combined quantum and molecular mechanical (QM/MM) technique for modelling organic and enzymatic reactions. Advances included the PDDG/PM3 semiempirical QM (SQM) method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo simulations, and a polynomial quadrature method for rapidly treating proton-transfer reactions. The current article serves as a follow up on our progress. Highlights include new reactions, alternative SQM methods, a polarizable OPLS force field, and novel solvent environments, e.g., “on water” and room temperature ionic liquids. The methodology is strikingly accurate across a wide range of condensed-phase and antibody-catalyzed reactions including substitution, decarboxylation, elimination, isomerization, and pericyclic classes. Comparisons are made to systems treated with continuum-based solvents and ab initio or density functional theory (DFT) methods. Overall, the QM/MM methodology provides detailed characterization of reaction paths, proper configurational sampling, several advantages over implicit solvent models, and a reasonable computational cost. PMID:25431625

  1. Quantum Monte Carlo for large chemical systems: implementing efficient strategies for petascale platforms and beyond.

    PubMed

    Scemama, Anthony; Caffarel, Michel; Oseret, Emmanuel; Jalby, William

    2013-04-30

    Various strategies to implement efficiently quantum Monte Carlo (QMC) simulations for large chemical systems are presented. These include: (i) the introduction of an efficient algorithm to calculate the computationally expensive Slater matrices. This novel scheme is based on the use of the highly localized character of atomic Gaussian basis functions (not the molecular orbitals as usually done), (ii) the possibility of keeping the memory footprint minimal, (iii) the important enhancement of single-core performance when efficient optimization tools are used, and (iv) the definition of a universal, dynamic, fault-tolerant, and load-balanced framework adapted to all kinds of computational platforms (massively parallel machines, clusters, or distributed grids). These strategies have been implemented in the QMC=Chem code developed at Toulouse and illustrated with numerical applications on small peptides of increasing sizes (158, 434, 1056, and 1731 electrons). Using 10-80 k computing cores of the Curie machine (GENCI-TGCC-CEA, France), QMC=Chem has been shown to be capable of running at the petascale level, thus demonstrating that for this machine a large part of the peak performance can be achieved. Implementation of large-scale QMC simulations for future exascale platforms with a comparable level of efficiency is expected to be feasible.

  2. Schwarzschild radius from Monte Carlo calculation of the Wilson loop in supersymmetric matrix quantum mechanics.

    PubMed

    Hanada, Masanori; Miwa, Akitsugu; Nishimura, Jun; Takeuchi, Shingo

    2009-05-01

    In the string-gauge duality it is important to understand how the space-time geometry is encoded in gauge theory observables. We address this issue in the case of the D0-brane system at finite temperature T. Based on the duality, the temporal Wilson loop W in gauge theory is expected to contain the information of the Schwarzschild radius RSch of the dual black hole geometry as log(W)=RSch/(2pialpha'T). This translates to the power-law behavior log(W)=1.89(T/lambda 1/3)-3/5, where lambda is the 't Hooft coupling constant. We calculate the Wilson loop on the gauge theory side in the strongly coupled regime by performing Monte Carlo simulations of supersymmetric matrix quantum mechanics with 16 supercharges. The results reproduce the expected power-law behavior up to a constant shift, which is explainable as alpha' corrections on the gravity side. Our conclusion also demonstrates manifestly the fuzzball picture of black holes. PMID:19518857

  3. Quantum Monte Carlo models of substitutional point defects in zinc oxide and zinc selenide

    NASA Astrophysics Data System (ADS)

    Yu, Jaehyung; Ertekin, Elif

    2015-03-01

    Introducing dopants into semiconductors allows manipulation of electrical and optical properties, useful for applications such as optoelectronics and photovoltaics. While first principles quantitative descriptions of the defects properties in semiconductors are critical to understanding and engineering dopants in semiconductors, obtaining accurate descriptions has proven challenging in the past. Here we demonstrate the use of quantum Monte Carlo (QMC) methods to describing the properties of point defects in zinc oxide and zinc selenide. Due to its direct treatment of electron correlation, the QMC method is capable of accurate calculation of band gaps and defect behaviors. We describe the energetics and potential barrier to forming gallium DX-center defects according to QMC in zinc selenide, and compare the description to those of conventional and hybrid DFT. We also use QMC to determine the defect transition levels for nitrogen defects in zinc oxide, and show that QMC obtains descriptions that are in good agreement with GW and beyond-DFT approaches. Our results demonstrate the importance of accurate descriptions of electron correlation in the calculation of defect properties of semiconductors.

  4. A deterministic alternative to the full configuration interaction quantum Monte Carlo method.

    PubMed

    Tubman, Norm M; Lee, Joonho; Takeshita, Tyler Y; Head-Gordon, Martin; Whaley, K Birgitta

    2016-07-28

    Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. However, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr2 molecule. We demonstrate for systems like Cr2 that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. In addition our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C2. PMID:27475353

  5. A deterministic alternative to the full configuration interaction quantum Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Tubman, Norm M.; Lee, Joonho; Takeshita, Tyler Y.; Head-Gordon, Martin; Whaley, K. Birgitta

    2016-07-01

    Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. However, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr2 molecule. We demonstrate for systems like Cr2 that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. In addition our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C2.

  6. Assessment of multireference approaches to explicitly correlated full configuration interaction quantum Monte Carlo.

    PubMed

    Kersten, J A F; Booth, George H; Alavi, Ali

    2016-08-01

    The Full Configuration Interaction Quantum Monte Carlo (FCIQMC) method has proved able to provide near-exact solutions to the electronic Schrödinger equation within a finite orbital basis set, without relying on an expansion about a reference state. However, a drawback to the approach is that being based on an expansion of Slater determinants, the FCIQMC method suffers from a basis set incompleteness error that decays very slowly with the size of the employed single particle basis. The FCIQMC results obtained in a small basis set can be improved significantly with explicitly correlated techniques. Here, we present a study that assesses and compares two contrasting "universal" explicitly correlated approaches that fit into the FCIQMC framework: the [2]R12 method of Kong and Valeev [J. Chem. Phys. 135, 214105 (2011)] and the explicitly correlated canonical transcorrelation approach of Yanai and Shiozaki [J. Chem. Phys. 136, 084107 (2012)]. The former is an a posteriori internally contracted perturbative approach, while the latter transforms the Hamiltonian prior to the FCIQMC simulation. These comparisons are made across the 55 molecules of the G1 standard set. We found that both methods consistently reduce the basis set incompleteness, for accurate atomization energies in small basis sets, reducing the error from 28 mEh to 3-4 mEh. While many of the conclusions hold in general for any combination of multireference approaches with these methodologies, we also consider FCIQMC-specific advantages of each approach. PMID:27497549

  7. Diffusion Quantum Monte Carlo predictions for bulk MnNiO3

    NASA Astrophysics Data System (ADS)

    Mitra, Chandrima; Krogel, Jaron; Reboredo, Fernando A.

    MnNiO3 is a strongly correlated transition metal oxide that has recently been investigated theoretically for its potential application as an oxygen-evolution photo-catalyst. However, there is no experimental report on critical quantities like its band gap or its bulk modulus. Recent theoretical predictions with standard functionals, such as PBE +U and HSE show large discrepancies in the band-gaps (about 1.23 eV), depending on the nature of the functional used. Hence, there is clearly a need for an accurate quantitative prediction of the band-gap in order to decide its usefulness as a photo-catalyst. In this work, we present Diffusion Quantum Monte Carlo (DMC) study of the bulk properties of MnNiO3. This includes the quasiparticle band gap for the two spin channels, the equilibrium lattice parameter and the bulk modulus. The DMC approach has already been shown to achieve excellent agreement with experimental results for other oxides such as ZnO NiO and Fe2O3. To our knowledge, MnNiO3 is the first case where this theory is applied before experiments are done. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  8. Quantum monte carlo study of the energetics of small hydrogenated and fluoride lithium clusters.

    PubMed

    Moreira, N L; Brito, B G A; Rabelo, J N Teixeira; Cândido, Ladir

    2016-06-30

    An investigation of the energetics of small lithium clusters doped either with a hydrogen or with a fluorine atom as a function of the number of lithium atoms using fixed-node diffusion quantum Monte Carlo (DMC) simulation is reported. It is found that the binding energy (BE) for the doped clusters increases in absolute values leading to a more stable system than for the pure ones in excellent agreement with available experimental measurements. The BE increases for pure, remains almost constant for hydrogenated, and decreases rapidly toward the bulk lithium for the fluoride as a function of the number of lithium atoms in the clusters. The BE, dissociation energy as well as the second difference in energy display a pronounced odd-even oscillation with the number of lithium atoms. The electron correlation inverts the odd-even oscillation pattern for the doped in comparison with the pure clusters and has an impact of 29%-83% to the BE being higher in the pure cluster followed by the hydrogenated and then by the fluoride. The dissociation energy and the second difference in energy indicate that the doped cluster Li3 H is the most stable whereas among the pure ones the more stable are Li2 , Li4 , and Li6 . The electron correlation energy is crucial for the stabilization of Li3 H. © 2016 Wiley Periodicals, Inc. PMID:26992447

  9. Quantum Monte Carlo simulations of Ti4 O7 Magnéli phase

    NASA Astrophysics Data System (ADS)

    Benali, Anouar; Shulenburger, Luke; Krogel, Jaron; Zhong, Xiaoliang; Kent, Paul; Heinonen, Olle

    2015-03-01

    Ti4O7 is ubiquitous in Ti-oxides. It has been extensively studied, both experimentally and theoretically in the past decades using multiple levels of theories, resulting in multiple diverse results. The latest DFT +SIC methods and state of the art HSE06 hybrid functionals even propose a new anti-ferromagnetic state at low temperature. Using Quantum Monte Carlo (QMC), as implemented in the QMCPACK simulation package, we investigated the electronic and magnetic properties of Ti4O7 at low (120K) and high (298K) temperatures and at different magnetic states. This research used resources of the Argonne Leadership Computing Facility at Argonne National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under contract DE-AC02-06CH11357. L.S, J.K and P.K were supported through Predictive Theory and Modeling for Materials and Chemical Science program by the Office of Basic Energy Sciences (BES), Department of Energy (DOE) Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.

  10. Frozen-Orbital and Downfolding Calculations with Auxiliary-Field Quantum Monte Carlo.

    PubMed

    Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2013-11-12

    We describe the implementation of the frozen-orbital and downfolding approximations in the auxiliary-field quantum Monte Carlo (AFQMC) method. These approaches can provide significant computational savings, compared to fully correlating all of the electrons. While the many-body wave function is never explicit in AFQMC, its random walkers are Slater determinants, whose orbitals may be expressed in terms of any one-particle orbital basis. It is therefore straightforward to partition the full N-particle Hilbert space into active and inactive parts to implement the frozen-orbital method. In the frozen-core approximation, for example, the core electrons can be eliminated in the correlated part of the calculations, greatly increasing the computational efficiency, especially for heavy atoms. Scalar relativistic effects are easily included using the Douglas-Kroll-Hess theory. Using this method, we obtain a way to effectively eliminate the error due to single-projector, norm-conserving pseudopotentials in AFQMC. We also illustrate a generalization of the frozen-orbital approach that downfolds high-energy basis states to a physically relevant low-energy sector, which allows a systematic approach to produce realistic model Hamiltonians to further increase efficiency for extended systems.

  11. Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces

    NASA Astrophysics Data System (ADS)

    Clay, Raymond C.; Holzmann, Markus; Ceperley, David M.; Morales, Miguel A.

    2016-01-01

    An accurate understanding of the phase diagram of dense hydrogen and helium mixtures is a crucial component in the construction of accurate models of Jupiter, Saturn, and Jovian extrasolar planets. Though density-functional-theory-based first-principles methods have the potential to provide the accuracy and computational efficiency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quantification of the errors introduced. In this work, we present a quantum Monte Carlo (QMC) -based benchmarking study of a wide range of density functionals for use in hydrogen-helium mixtures at thermodynamic conditions relevant for Jovian planets. Not only do we continue our program of benchmarking energetics and pressures, but we deploy QMC-based force estimators and use them to gain insight into how well the local liquid structure is captured by different density functionals. We find that TPSS, BLYP, and vdW-DF are the most accurate functionals by most metrics, and that the enthalpy, energy, and pressure errors are very well behaved as a function of helium concentration. Beyond this, we highlight and analyze the major error trends and relative differences exhibited by the major classes of functionals, and we estimate the magnitudes of these effects when possible.

  12. Properties of Solar Thermal Fuels by Accurate Quantum Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    Saritas, Kayahan; Ataca, Can; Grossman, Jeffrey C.

    2014-03-01

    Efficient utilization of the sun as a renewable and clean energy source is one of the major goals of this century due to increasing energy demand and environmental impact. Solar thermal fuels are materials that capture and store the sun's energy in the form of chemical bonds, which can then be released as heat on demand and charged again. Previous work on solar thermal fuels faced challenges related to the cyclability of the fuel over time, as well as the need for higher energy densities. Recently, it was shown that by templating photoswitches onto carbon nanostructures, both high energy density as well as high stability can be achieved. In this work, we explore alternative molecules to azobenzene in such a nano-templated system. We employ the highly accurate quantum Monte Carlo (QMC) method to predict the energy storage potential for each molecule. Our calculations show that in many cases the level of accuracy provided by density functional theory (DFT) is sufficient. However, in some cases, such as dihydroazulene, the drastic change in conjugation upon light absorption causes the DFT predictions to be inconsistent and incorrect. For this case, we compare our QMC results for the geometric structure, band gap and reaction enthalpy with different DFT functionals.

  13. Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo

    SciTech Connect

    Thomas, Robert E.; Overy, Catherine; Opalka, Daniel; Alavi, Ali; Knowles, Peter J.; Booth, George H.

    2015-08-07

    Unbiased stochastic sampling of the one- and two-body reduced density matrices is achieved in full configuration interaction quantum Monte Carlo with the introduction of a second, “replica” ensemble of walkers, whose population evolves in imaginary time independently from the first and which entails only modest additional computational overheads. The matrices obtained from this approach are shown to be representative of full configuration-interaction quality and hence provide a realistic opportunity to achieve high-quality results for a range of properties whose operators do not necessarily commute with the Hamiltonian. A density-matrix formulated quasi-variational energy estimator having been already proposed and investigated, the present work extends the scope of the theory to take in studies of analytic nuclear forces, molecular dipole moments, and polarisabilities, with extensive comparison to exact results where possible. These new results confirm the suitability of the sampling technique and, where sufficiently large basis sets are available, achieve close agreement with experimental values, expanding the scope of the method to new areas of investigation.

  14. Quantum Monte Carlo Method for Heavy Atomic and Molecular Systems with Spin-Orbit Interactions

    NASA Astrophysics Data System (ADS)

    Melton, Cody; Mitas, Lubos

    We present a new quantum Monte Carlo (QMC) method that can treat spin-orbit and other types of spin-depentent interactions explicitly. It is based on generalization of the fixed-phase and projection of the nonlocal operators with spinor trial wave functions. For testing the method we calculate several atomic and molecular systems such as Bi, W, Pb, PbH and PbO, some of them with both large- and small-core pseudopotentials. We validate the quality of the results against other correlated methods such as configuration interaction in two-component formalism. We find excellent agreement with extrapolated values for the total energies and we are able to reliably reproduce experimental values of excitation energies, electron affinity and molecular binding. We show that in order to obtain the agreement with experimental values the explicit inclusion of the spin-orbit interactions is crucial. U.S. D.O.E. grant de-sc0012314 and NERSC Contract No. DE-AC02-05CH11231.

  15. Assessment of multireference approaches to explicitly correlated full configuration interaction quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Kersten, J. A. F.; Booth, George H.; Alavi, Ali

    2016-08-01

    The Full Configuration Interaction Quantum Monte Carlo (FCIQMC) method has proved able to provide near-exact solutions to the electronic Schrödinger equation within a finite orbital basis set, without relying on an expansion about a reference state. However, a drawback to the approach is that being based on an expansion of Slater determinants, the FCIQMC method suffers from a basis set incompleteness error that decays very slowly with the size of the employed single particle basis. The FCIQMC results obtained in a small basis set can be improved significantly with explicitly correlated techniques. Here, we present a study that assesses and compares two contrasting "universal" explicitly correlated approaches that fit into the FCIQMC framework: the [2]R12 method of Kong and Valeev [J. Chem. Phys. 135, 214105 (2011)] and the explicitly correlated canonical transcorrelation approach of Yanai and Shiozaki [J. Chem. Phys. 136, 084107 (2012)]. The former is an a posteriori internally contracted perturbative approach, while the latter transforms the Hamiltonian prior to the FCIQMC simulation. These comparisons are made across the 55 molecules of the G1 standard set. We found that both methods consistently reduce the basis set incompleteness, for accurate atomization energies in small basis sets, reducing the error from 28 mEh to 3-4 mEh. While many of the conclusions hold in general for any combination of multireference approaches with these methodologies, we also consider FCIQMC-specific advantages of each approach.

  16. Characterizing the three-orbital Hubbard model with determinant quantum Monte Carlo

    DOE PAGES

    Kung, Y. F.; Chen, C. -C.; Wang, Yao; Huang, E. W.; Nowadnick, E. A.; Moritz, B.; Scalettar, R. T.; Johnston, S.; Devereaux, T. P.

    2016-04-29

    Here, we characterize the three-orbital Hubbard model using state-of-the-art determinant quantum Monte Carlo (DQMC) simulations with parameters relevant to the cuprate high-temperature superconductors. The simulations find that doped holes preferentially reside on oxygen orbitals and that the (π,π) antiferromagnetic ordering vector dominates in the vicinity of the undoped system, as known from experiments. The orbitally-resolved spectral functions agree well with photoemission spectroscopy studies and enable identification of orbital content in the bands. A comparison of DQMC results with exact diagonalization and cluster perturbation theory studies elucidates how these different numerical techniques complement one another to produce a more complete understandingmore » of the model and the cuprates. Interestingly, our DQMC simulations predict a charge-transfer gap that is significantly smaller than the direct (optical) gap measured in experiment. Most likely, it corresponds to the indirect gap that has recently been suggested to be on the order of 0.8 eV, and demonstrates the subtlety in identifying charge gaps.« less

  17. Quantum and Molecular Mechanical (QM/MM) Monte Carlo Techniques for Modeling Condensed-Phase Reactions.

    PubMed

    Acevedo, Orlando; Jorgensen, Wiliiam L

    2014-09-01

    A recent review (Acc. Chem. Res. 2010, 43:142-151) examined our use and development of a combined quantum and molecular mechanical (QM/MM) technique for modelling organic and enzymatic reactions. Advances included the PDDG/PM3 semiempirical QM (SQM) method, computation of multi-dimensional potentials of mean force (PMF), incorporation of on-the-fly QM in Monte Carlo simulations, and a polynomial quadrature method for rapidly treating proton-transfer reactions. The current article serves as a follow up on our progress. Highlights include new reactions, alternative SQM methods, a polarizable OPLS force field, and novel solvent environments, e.g., "on water" and room temperature ionic liquids. The methodology is strikingly accurate across a wide range of condensed-phase and antibody-catalyzed reactions including substitution, decarboxylation, elimination, isomerization, and pericyclic classes. Comparisons are made to systems treated with continuum-based solvents and ab initio or density functional theory (DFT) methods. Overall, the QM/MM methodology provides detailed characterization of reaction paths, proper configurational sampling, several advantages over implicit solvent models, and a reasonable computational cost. PMID:25431625

  18. Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces

    DOE PAGES

    Clay, Raymond C.; Holzmann, Markus; Ceperley, David M.; Morales, Maguel A.

    2016-01-19

    An accurate understanding of the phase diagram of dense hydrogen and helium mixtures is a crucial component in the construction of accurate models of Jupiter, Saturn, and Jovian extrasolar planets. Though DFT based rst principles methods have the potential to provide the accuracy and computational e ciency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quanti cation of the errors introduced. In this work, we present a quantum Monte Carlo based benchmarking study of a wide range of density functionals for use in hydrogen-helium mixtures atmore » thermodynamic conditions relevant for Jovian planets. Not only do we continue our program of benchmarking energetics and pressures, but we deploy QMC based force estimators and use them to gain insights into how well the local liquid structure is captured by di erent density functionals. We nd that TPSS, BLYP and vdW-DF are the most accurate functionals by most metrics, and that the enthalpy, energy, and pressure errors are very well behaved as a function of helium concentration. Beyond this, we highlight and analyze the major error trends and relative di erences exhibited by the major classes of functionals, and estimate the magnitudes of these e ects when possible.« less

  19. Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo

    SciTech Connect

    Santana, Juan A.; Krogel, Jaron T.; Kim, Jeongnim; Reboredo, Fernando A.; Kent, Paul R. C.

    2015-04-28

    We have applied the many-body ab initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure and the energetics of the oxygen vacancy, zinc interstitial, and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory (DFT) approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O{sub 2}, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.

  20. Towards prediction of correlated material properties using quantum Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas

    Correlated electron systems offer a richness of physics far beyond noninteracting systems. If we would like to pursue the dream of designer correlated materials, or, even to set a more modest goal, to explain in detail the properties and effective physics of known materials, then accurate simulation methods are required. Using modern computational resources, quantum Monte Carlo (QMC) techniques offer a way to directly simulate electron correlations. I will show some recent results on a few extremely challenging materials including the metal-insulator transition of VO2, the ground state of the doped cuprates, and the pressure dependence of magnetic properties in FeSe. By using a relatively simple implementation of QMC, at least some properties of these materials can be described truly from first principles, without any adjustable parameters. Using the QMC platform, we have developed a way of systematically deriving effective lattice models from the simulation. This procedure is particularly attractive for correlated electron systems because the QMC methods treat the one-body and many-body components of the wave function and Hamiltonian on completely equal footing. I will show some examples of using this downfolding technique and the high accuracy of QMC to connect our intuitive ideas about interacting electron systems with high fidelity simulations. The work in this presentation was supported in part by NSF DMR 1206242, the U.S. Department of Energy, Office of Science, Office of Advanced Scientific Computing Research, Scientific Discovery through Advanced Computing (SciDAC) program under Award Number FG02-12ER46875, and the Center for Emergent Superconductivity, Department of Energy Frontier Research Center under Grant No. DEAC0298CH1088. Computing resources were provided by a Blue Waters Illinois grant and INCITE PhotSuper and SuperMatSim allocations.

  1. Structural Stability and Defect Energetics of ZnO from Diffusion Quantum Monte Carlo

    DOE PAGES

    Santana Palacio, Juan A.; Krogel, Jaron T.; Kim, Jeongnim; Kent, Paul R.; Reboredo, Fernando A.

    2015-04-28

    We have applied the many-body ab-initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure, and the energetics of the oxygen vacancy, zinc interstitial and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy asmore » a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type, and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.« less

  2. Structural Stability and Defect Energetics of ZnO from Diffusion Quantum Monte Carlo

    SciTech Connect

    Santana Palacio, Juan A.; Krogel, Jaron T.; Kim, Jeongnim; Kent, Paul R.; Reboredo, Fernando A.

    2015-04-28

    We have applied the many-body ab-initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure, and the energetics of the oxygen vacancy, zinc interstitial and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type, and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.

  3. Quantum Monte Carlo benchmark of exchange-correlation functionals for bulk water

    SciTech Connect

    Morales, Miguel A; Gergely, John; McMinis, Jeremy; McMahon, Jeffrey; Kim, Jeongnim; Ceperley, David M.

    2014-01-01

    The accurate description of the thermodynamic and dynamical properties of liquid water from first-principles is a very important challenge to the theoretical community. This represents not only a critical test of the predictive capabilities of first-principles methods, but it will also shed light into the microscopic properties of such an important substance. Density Functional Theory, the main workhorse in the field of first-principles methods, has been so far unable to properly describe water and its unusual properties in the liquid state. With the recent introduction of exact exchange and an improved description of dispersion interaction, the possibility of an accurate description of the liquid is finally within reach. Unfortunately, there is still no way to systematically improve exchange-correlation functionals and the number of available functionals is very large. In this article we use highly accurate quantum Monte Carlo calculations to benchmark a selection of exchange-correlation functionals typically used in Density Functional Theory simulations of bulk water. This allows us to test the predictive capabilities of these functionals in water, giving us a way not only to choose optimal functionals for first-principles simulations, but also giving us a route for the optimization of the functionals for the system at hand. We compare and contrast the importance of different features of functionals, including the hybrid component, the vdW component, and their importance within different aspects of the PES. In addition, we test a recently introduce scheme that combines Density Functional Theory with Coupled Cluster Calculations through a Many-Body expansion of the energy, in order to correct the inaccuracies in the description of short range interactions in the liquid.

  4. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

    NASA Astrophysics Data System (ADS)

    Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio

    2014-01-01

    We investigate here the vertical n → π* and π → π* transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π* case and also improve considerably the shift for the π → π* transition.

  5. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

    SciTech Connect

    Floris, Franca Maria Amovilli, Claudio; Filippi, Claudia

    2014-01-21

    We investigate here the vertical n → π{sup *} and π → π{sup *} transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π{sup *} case and also improve considerably the shift for the π → π{sup *} transition.

  6. Monte Carlo-quantum mechanics study of magnetic properties of hydrogen peroxide in liquid water.

    PubMed

    Caputo, María Cristina; Provasi, Patricio F; Benitez, Lucía; Georg, Herbert C; Canuto, Sylvio; Coutinho, Kaline

    2014-08-14

    A theoretical study of magnetic properties of hydrogen peroxide in water has been carried out by means of Monte Carlo simulation and quantum mechanics calculations. The solvent effects were evaluated in supermolecular structures generated by simulations in the NPT ensemble. The solute-solvent structure was analyzed in terms of radial distribution functions, and the solute-solvent hydrogen bonds were identified with geometric and energetic criteria. Approximately three water molecules are hydrogen bonded to H2O2 (0.6 and 0.8 in each hydrogen and oxygen atom, respectively, of the H2O2). Although, on average, both hydroxyls of the peroxide are equivalent, the distribution of hydrogen-bonded water molecules is highly asymmetric. Analyzing the statistics of the hydrogen bonds, we identify that only 34% of the configurations give symmetric distributions around the two hydroxyls of the H2O2 simultaneously. The magnetic shieldings and the indirect spin-spin coupling constants were calculated at the B3LYP/aug-cc-pVTZ and aug-cc-pVTZ-J computational level. We find that the solvent shields the oxygen and unshields the hydrogen atoms of the peroxide (+5.5 and -2.9 ppm, respectively), with large fluctuation from configuration to configuration in the oxygen case, an effect largely accounted for in terms of a single hydrogen bond with H2O2 as the proton donor. The most sensitive coupling in the presence of the solvent is observed to be the one-bond J(O,H).

  7. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: acrolein in water.

    PubMed

    Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio

    2014-01-21

    We investigate here the vertical n → π(*) and π → π(*) transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π(*) case and also improve considerably the shift for the π → π(*) transition.

  8. Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Santana, Juan A.; Krogel, Jaron T.; Kim, Jeongnim; Kent, Paul R. C.; Reboredo, Fernando A.

    2015-04-01

    We have applied the many-body ab initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure and the energetics of the oxygen vacancy, zinc interstitial, and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory (DFT) approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.

  9. Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo.

    PubMed

    Santana, Juan A; Krogel, Jaron T; Kim, Jeongnim; Kent, Paul R C; Reboredo, Fernando A

    2015-04-28

    We have applied the many-body ab initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure and the energetics of the oxygen vacancy, zinc interstitial, and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory (DFT) approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O2, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV. PMID:25933782

  10. Multiple-Resonance Local Wave Functions for Accurate Excited States in Quantum Monte Carlo.

    PubMed

    Zulfikri, Habiburrahman; Amovilli, Claudio; Filippi, Claudia

    2016-03-01

    We introduce a novel class of local multideterminant Jastrow-Slater wave functions for the efficient and accurate treatment of excited states in quantum Monte Carlo. The wave function is expanded as a linear combination of excitations built from multiple sets of localized orbitals that correspond to the bonding patterns of the different Lewis resonance structures of the molecule. We capitalize on the concept of orbital domains of local coupled-cluster methods, which is here applied to the active space to select the orbitals to correlate and construct the important transitions. The excitations are further grouped into classes, which are ordered in importance and can be systematically included in the Jastrow-Slater wave function to ensure a balanced description of all states of interest. We assess the performance of the proposed wave function in the calculation of vertical excitation energies and excited-state geometry optimization of retinal models whose π → π* state has a strong intramolecular charge-transfer character. We find that our multiresonance wave functions recover the reference values of the total energies of the ground and excited states with only a small number of excitations and that the same expansion can be flexibly used at very different geometries. Furthermore, significant computational saving can also be gained in the orbital optimization step by selectively mixing occupied and virtual orbitals based on spatial considerations without loss of accuracy on the excitation energy. Our multiresonance wave functions are therefore compact, accurate, and very promising for the calculation of multiple excited states of different character in large molecules.

  11. Ab initio quantum Monte Carlo simulations of the uniform electron gas without fixed nodes: The unpolarized case

    NASA Astrophysics Data System (ADS)

    Dornheim, T.; Groth, S.; Schoof, T.; Hann, C.; Bonitz, M.

    2016-05-01

    In a recent publication [S. Groth et al., Phys. Rev. B 93, 085102 (2016), 10.1103/PhysRevB.93.085102], we have shown that the combination of two complementary quantum Monte Carlo approaches, namely configuration path integral Monte Carlo [T. Schoof et al., Phys. Rev. Lett. 115, 130402 (2015), 10.1103/PhysRevLett.115.130402] and permutation blocking path integral Monte Carlo [T. Dornheim et al., New J. Phys. 17, 073017 (2015), 10.1088/1367-2630/17/7/073017], allows for the accurate computation of thermodynamic properties of the spin-polarized uniform electron gas over a wide range of temperatures and densities without the fixed-node approximation. In the present work, we extend this concept to the unpolarized case, which requires nontrivial enhancements that we describe in detail. We compare our simulation results with recent restricted path integral Monte Carlo data [E. W. Brown et al., Phys. Rev. Lett. 110, 146405 (2013), 10.1103/PhysRevLett.110.146405] for different energy contributions and pair distribution functions and find, for the exchange correlation energy, overall better agreement than for the spin-polarized case, while the separate kinetic and potential contributions substantially deviate.

  12. Creation of a GUI for Zori, a Quantum Monte Carlo program, usingRappture

    SciTech Connect

    Olivares-Amaya, R.; Salomon Ferrer, R.; Lester Jr., W.A.; Amador-Bedolla, C.

    2007-12-01

    In their research laboratories, academic institutions produce some of the most advanced software for scientific applications. However, this software is usually developed only for local application in the research laboratory or for method development. In spite of having the latest advances in the particular field of science, such software often lacks adequate documentation and therefore is difficult to use by anyone other than the code developers. As such codes become more complex, so typically do the input files and command statements necessary to operate them. Many programs offer the flexibility of performing calculations based on different methods that have their own set of variables and options to be specified. Moreover, situations can arise in which certain options are incompatible with each other. For this reason, users outside the development group can be unaware of how the program runs in detail. The opportunity can be lost to make the software readily available outside of the laboratory of origin. This is a long-standing problem in scientific programming. Rappture, Rapid Application Infrastructure [1], is a new GUI development kit that enables a developer to build an I/O interface for a specific application. This capability enables users to work only with the generated GUI and avoids the problem of the user needing to learn details of the code. Further, it reduces input errors by explicitly specifying the variables required. Zori, a quantum Monte Carlo (QMC) program, developed by the Lester group at the University of California, Berkeley [2], is one of the few free tools available for this field. Like many scientific computer packages, Zori suffers from the problems described above. Potential users outside the research group have acquired it, but some have found the code difficult to use. Furthermore, new members of the Lester group usually have to take considerable time learning all the options the code has to offer before they can use it successfully. In

  13. Quantum Monte Carlo Simulation of Vibrational Frequency Shifts of CO in Solid para-HYDROGEN

    NASA Astrophysics Data System (ADS)

    Wang, Lecheng; Le Roy, Robert; Roy, Pierre-Nicholas

    2014-06-01

    Stimulated by Fajardo's remarkable study of the rovibrational spectra of CO isotopologues trapped in solid para-hydrogen, we have performed quantum Monte Carlo simulations to predict his observed vibrational frequency shifts and inertial rotational constants using 2-body potentials based on the best available models for the pH_2-pH_2 and CO-pH_2, potential energy functions. We started by fitting an analytic `Morse/Long-Range' (MLR) function to the 1D ``adiabaic hindered rotor" version of Hinde's 5D pH_2-pH_2 potential developed by Faruk et al. We then modified it to take account of many-body effects by scaling it until it yielded the correct equilibrium lattice parameters for the fcc and hcp structures of pure solid para-hydrogen. A CO molecule was then placed at different interstitial or substitution sites in large equilibrated fcc or hcp para-hydrogen lattices, and the structural and dynamical behaviors of the micro-solvation environment around CO were simulated with a PIMC algorithm using a 2D effective pH_2-CO potential based on the 5D H_2--CO potential energy surface recently reported by Li et al., with a lattice sum of values of the 2D CO vibrational difference potential being use to predict the vibrational frequency shift. The effective rotational constants Beff for CO in different solid para-hydrogen structures were also calculated and compared with the experimental observations and with predicted Beff values for CO in large-sized para-hydrogen--CO clusters. M. E. Fajardo, J. Phys. Chem. A 117, 13504 (2013). R. Hinde, J. Chem. Phys., 128, 154308 (2008). H. Li, X-L. Zhang, R.J. Le Roy, and P.-N. Roy, J. Chem. Phys. 139, 164315 (2013). R.J. Le Roy, C.C. Haugen, J. Tao and Hui Li, Mol. Phys., 109, 435 (2011) N. Faruk, R.J. Le Roy, and P.-N. Roy, J. Chem. Phys. (submitted December 2013). Y. Mizumoto and Y. Ohtsuki, Chem. Phys. Lett. 501, 304 (2011).

  14. Quantum Monte Carlo study of long-range transverse-field Ising models on the triangular lattice

    NASA Astrophysics Data System (ADS)

    Humeniuk, Stephan

    2016-03-01

    Motivated by recent experiments with a Penning ion trap quantum simulator, we perform numerically exact Stochastic Series Expansion quantum Monte Carlo simulations of long-range transverse-field Ising models on a triangular lattice for different decay powers α of the interactions. The phase boundary for the ferromagnet is obtained as a function of α . For antiferromagnetic interactions, there is strong indication that the transverse field stabilizes a clock ordered phase with sublattice magnetization (M ,-M/2 ,-M/2 ) with unsaturated M <1 in a process known as "order by disorder" similar to the nearest-neighbor antiferromagnet on the triangular lattice. Connecting the known limiting cases of nearest-neighbor and infinite-range interactions, a semiquantitative phase diagram is obtained. Magnetization curves for the ferromagnet for experimentally relevant system sizes and with open boundary conditions are presented.

  15. Recent developments in quantum Monte Carlo simulations with applications for cold gases.

    PubMed

    Pollet, Lode

    2012-09-01

    This is a review of recent developments in Monte Carlo methods in the field of ultracold gases. For bosonic atoms in an optical lattice we discuss path-integral Monte Carlo simulations with worm updates and show the excellent agreement with cold atom experiments. We also review recent progress in simulating bosonic systems with long-range interactions, disordered bosons, mixtures of bosons and spinful bosonic systems. For repulsive fermionic systems, determinantal methods at half filling are sign free, but in general no sign-free method exists. We review the developments in diagrammatic Monte Carlo for the Fermi polaron problem and the Hubbard model, and show the connection with dynamical mean-field theory. We end the review with diffusion Monte Carlo for the Stoner problem in cold gases.

  16. Magnetic ``three states of matter'' in two and three dimensions: a quantum Monte Carlo study of the extended toric codes

    NASA Astrophysics Data System (ADS)

    Kamiya, Yoshitomo

    The possibility of quantum spin liquids, characterized by nontrivial entanglement properties or a topological nonlocal order parameter, has long been debated both theoretically and experimentally. Since candidate systems (e.g., frustrated quantum magnets or 5 d transition metal oxides) may host other competing phases including conventional magnetic ordered phases, it is natural to ask what types of global phase diagrams can be anticipated depending on coupling constants, temperature, dimensionality, etc. In this talk, by considering an extension of the Kitaev toric code Hamiltonians by Ising interactions on 2D (square) and 3D (cubic) lattices, I will present thermodynamic phase diagrams featuring magnetic ``three states of matter,'' namely, quantum spin liquid, paramagnetic, and magnetically ordered phases (analogous to liquid, gas, and solid, respectively, in conventional matter) obtained by unbiased quantum Monte Carlo simulations [YK, Y. Kato, J. Nasu, and Y. Motome, PRB 92, 100403(R) (2015)]. We find that the ordered phase borders on the spin liquid around the exactly solvable point by a discontinuous transition line in 3D, while it grows continuously from the quantum critical point in 2D. In both cases, peculiar proximity effects to the nearby spin liquid phases are observed at high temperature even when the ground state is magnetically ordered. Such proximity effects include flux-shrinking and a tricritical behavior in 3D and a ``fractionalization'' of the order parameter field at the quantum critical point in 2D, both of which can be detected by measuring critical exponents. Work done in collaboration with Yasuyuki Kato, Joji Nasu, and Yukitoshi Motome.

  17. Quantum Monte Carlo estimation of complex-time correlations for the study of the ground-state dynamic structure function

    SciTech Connect

    Rota, R.; Casulleras, J.; Mazzanti, F.; Boronat, J.

    2015-03-21

    We present a method based on the path integral Monte Carlo formalism for the calculation of ground-state time correlation functions in quantum systems. The key point of the method is the consideration of time as a complex variable whose phase δ acts as an adjustable parameter. By using high-order approximations for the quantum propagator, it is possible to obtain Monte Carlo data all the way from purely imaginary time to δ values near the limit of real time. As a consequence, it is possible to infer accurately the spectral functions using simple inversion algorithms. We test this approach in the calculation of the dynamic structure function S(q, ω) of two one-dimensional model systems, harmonic and quartic oscillators, for which S(q, ω) can be exactly calculated. We notice a clear improvement in the calculation of the dynamic response with respect to the common approach based on the inverse Laplace transform of the imaginary-time correlation function.

  18. Comparing Vibrationally Averaged Nuclear Shielding Constants by Quantum Diffusion Monte Carlo and Second-Order Perturbation Theory.

    PubMed

    Ng, Yee-Hong; Bettens, Ryan P A

    2016-03-01

    Using the method of modified Shepard's interpolation to construct potential energy surfaces of the H2O, O3, and HCOOH molecules, we compute vibrationally averaged isotropic nuclear shielding constants ⟨σ⟩ of the three molecules via quantum diffusion Monte Carlo (QDMC). The QDMC results are compared to that of second-order perturbation theory (PT), to see if second-order PT is adequate for obtaining accurate values of nuclear shielding constants of molecules with large amplitude motions. ⟨σ⟩ computed by the two approaches differ for the hydrogens and carbonyl oxygen of HCOOH, suggesting that for certain molecules such as HCOOH where big displacements away from equilibrium happen (internal OH rotation), ⟨σ⟩ of experimental quality may only be obtainable with the use of more sophisticated and accurate methods, such as quantum diffusion Monte Carlo. The approach of modified Shepard's interpolation is also extended to construct shielding constants σ surfaces of the three molecules. By using a σ surface with the equilibrium geometry as a single data point to compute isotropic nuclear shielding constants for each descendant in the QDMC ensemble representing the ground state wave function, we reproduce the results obtained through ab initio computed σ to within statistical noise. Development of such an approach could thereby alleviate the need for any future costly ab initio σ calculations.

  19. Ab initio molecular dynamics with noisy forces: Validating the quantum Monte Carlo approach with benchmark calculations of molecular vibrational properties

    SciTech Connect

    Luo, Ye Sorella, Sandro; Zen, Andrea

    2014-11-21

    We present a systematic study of a recently developed ab initio simulation scheme based on molecular dynamics and quantum Monte Carlo. In this approach, a damped Langevin molecular dynamics is employed by using a statistical evaluation of the forces acting on each atom by means of quantum Monte Carlo. This allows the use of an highly correlated wave function parametrized by several variational parameters and describing quite accurately the Born-Oppenheimer energy surface, as long as these parameters are determined at the minimum energy condition. However, in a statistical method both the minimization method and the evaluation of the atomic forces are affected by the statistical noise. In this work, we study systematically the accuracy and reliability of this scheme by targeting the vibrational frequencies of simple molecules such as the water monomer, hydrogen sulfide, sulfur dioxide, ammonia, and phosphine. We show that all sources of systematic errors can be controlled and reliable frequencies can be obtained with a reasonable computational effort. This work provides convincing evidence that this molecular dynamics scheme can be safely applied also to realistic systems containing several atoms.

  20. Quantum Monte Carlo estimation of complex-time correlations for the study of the ground-state dynamic structure function.

    PubMed

    Rota, R; Casulleras, J; Mazzanti, F; Boronat, J

    2015-03-21

    We present a method based on the path integral Monte Carlo formalism for the calculation of ground-state time correlation functions in quantum systems. The key point of the method is the consideration of time as a complex variable whose phase δ acts as an adjustable parameter. By using high-order approximations for the quantum propagator, it is possible to obtain Monte Carlo data all the way from purely imaginary time to δ values near the limit of real time. As a consequence, it is possible to infer accurately the spectral functions using simple inversion algorithms. We test this approach in the calculation of the dynamic structure function S(q, ω) of two one-dimensional model systems, harmonic and quartic oscillators, for which S(q, ω) can be exactly calculated. We notice a clear improvement in the calculation of the dynamic response with respect to the common approach based on the inverse Laplace transform of the imaginary-time correlation function. PMID:25796238

  1. Statistical Exploration of Electronic Structure of Molecules from Quantum Monte-Carlo Simulations

    SciTech Connect

    Prabhat, Mr; Zubarev, Dmitry; Lester, Jr., William A.

    2010-12-22

    In this report, we present results from analysis of Quantum Monte Carlo (QMC) simulation data with the goal of determining internal structure of a 3N-dimensional phase space of an N-electron molecule. We are interested in mining the simulation data for patterns that might be indicative of the bond rearrangement as molecules change electronic states. We examined simulation output that tracks the positions of two coupled electrons in the singlet and triplet states of an H2 molecule. The electrons trace out a trajectory, which was analyzed with a number of statistical techniques. This project was intended to address the following scientific questions: (1) Do high-dimensional phase spaces characterizing electronic structure of molecules tend to cluster in any natural way? Do we see a change in clustering patterns as we explore different electronic states of the same molecule? (2) Since it is hard to understand the high-dimensional space of trajectories, can we project these trajectories to a lower dimensional subspace to gain a better understanding of patterns? (3) Do trajectories inherently lie in a lower-dimensional manifold? Can we recover that manifold? After extensive statistical analysis, we are now in a better position to respond to these questions. (1) We definitely see clustering patterns, and differences between the H2 and H2tri datasets. These are revealed by the pamk method in a fairly reliable manner and can potentially be used to distinguish bonded and non-bonded systems and get insight into the nature of bonding. (2) Projecting to a lower dimensional subspace ({approx}4-5) using PCA or Kernel PCA reveals interesting patterns in the distribution of scalar values, which can be related to the existing descriptors of electronic structure of molecules. Also, these results can be immediately used to develop robust tools for analysis of noisy data obtained during QMC simulations (3) All dimensionality reduction and estimation techniques that we tried seem to

  2. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods.

    PubMed

    Ganesh, P; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A; Kent, Paul R C

    2014-12-01

    Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium-carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches. PMID:26583215

  3. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

    SciTech Connect

    Ganesh, P.; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A.; Kent, Paul R. C.

    2014-11-03

    In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.

  4. Path-Integral Monte Carlo Study on a Droplet of a Dipolar Bose–Einstein Condensate Stabilized by Quantum Fluctuation

    NASA Astrophysics Data System (ADS)

    Saito, Hiroki

    2016-05-01

    Motivated by recent experiments [H. Kadau et al., Nature (London) 530, 194 (2016); I. Ferrier-Barbut et al., arXiv:1601.03318] and theoretical prediction (F. Wächtler and L. Santos, arXiv:1601.04501), the ground state of a dysprosium Bose-Einstein condensate with strong dipole-dipole interaction is studied by the path-integral Monte Carlo method. It is shown that quantum fluctuation can stabilize the condensate against dipolar collapse.

  5. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods.

    PubMed

    Ganesh, P; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A; Kent, Paul R C

    2014-12-01

    Highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based on point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. The results demonstrate that the lithium-carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.

  6. Triplet p + ip pairing correlations in the doped Kane-Mele-Hubbard model: A quantum Monte Carlo study

    DOE PAGES

    Ma, Tianxing; Lin, Hai-Qing; Gubernatis, James E.

    2015-09-01

    By using the constrained-phase quantum Monte Carlo method, we performed a systematic study of the pairing correlations in the ground state of the doped Kane-Mele-Hubbard model on a honeycomb lattice. We find that pairing correlations with d + id symmetry dominate close to half filling, but pairing correlations with p+ip symmetry dominate as hole doping moves the system below three-quarters filling. We correlate these behaviors of the pairing correlations with the topology of the Fermi surfaces of the non-interacting problem. We also find that the effective pairing correlation is enhanced greatly as the interaction increases, and these superconducting correlations aremore » robust against varying the spin-orbit coupling strength. Finally, our numerical results suggest a possible way to realize spin triplet superconductivity in doped honeycomb-like materials or ultracold atoms in optical traps.« less

  7. Wang-Landau method for calculating Rényi entropies in finite-temperature quantum Monte Carlo simulations.

    PubMed

    Inglis, Stephen; Melko, Roger G

    2013-01-01

    We implement a Wang-Landau sampling technique in quantum Monte Carlo (QMC) simulations for the purpose of calculating the Rényi entanglement entropies and associated mutual information. The algorithm converges an estimate for an analog to the density of states for stochastic series expansion QMC, allowing a direct calculation of Rényi entropies without explicit thermodynamic integration. We benchmark results for the mutual information on two-dimensional (2D) isotropic and anisotropic Heisenberg models, a 2D transverse field Ising model, and a three-dimensional Heisenberg model, confirming a critical scaling of the mutual information in cases with a finite-temperature transition. We discuss the benefits and limitations of broad sampling techniques compared to standard importance sampling methods.

  8. Toward Accurate Reaction Energetics for Molecular Line Growth at Surface: Quantum Monte Carlo and Density Functional Theory Calculations

    SciTech Connect

    Kanai, Y; Takeuchi, N

    2009-10-14

    We revisit the molecular line growth mechanism of styrene on the hydrogenated Si(001) 2x1 surface. In particular, we investigate the energetics of the radical chain reaction mechanism by means of diffusion quantum Monte Carlo (QMC) and density functional theory (DFT) calculations. For the exchange correlation (XC) functional we use the non-empirical generalized-gradient approximation (GGA) and meta-GGA. We find that the QMC result also predicts the intra dimer-row growth of the molecular line over the inter dimer-row growth, supporting the conclusion based on DFT results. However, the absolute magnitudes of the adsorption and reaction energies, and the heights of the energy barriers differ considerably between the QMC and DFT with the GGA/meta-GGA XC functionals.

  9. Triplet p + ip pairing correlations in the doped Kane-Mele-Hubbard model: A quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Ma, Tianxing; Lin, Hai-Qing; Gubernatis, J. E.

    2015-08-01

    By using the constrained-phase quantum Monte Carlo method, we performed a systematic study of the pairing correlations in the ground state of the doped Kane-Mele-Hubbard model on a honeycomb lattice. We find that pairing correlations with d + id symmetry dominate close to half-filling, but pairing correlations with p + ip symmetry dominate as hole doping moves the system below three-quarters filling. We correlate these behaviors of the pairing correlations with the topology of the Fermi surfaces of the non-interacting problem. We also find that the effective pairing correlation is enhanced greatly as the interaction increases, and these superconducting correlations are robust against varying the spin-orbit coupling strength. Our numerical results suggest a possible way to realize spin triplet superconductivity in doped honeycomb-like materials or ultracold atoms in optical traps.

  10. Quantum Monte Carlo Calculation for the Equation of State of MgSiO3 perovskite at high pressures

    NASA Astrophysics Data System (ADS)

    Lin, Yangzheng; Cohen, R. E.; Driver, Kevin P.; Militzer, Burkhard; Shulenburger, Luke; Kim, Jeongnim

    2014-03-01

    Magnesium silicate (MgSiO3) is among the most abundant minerals in the Earth's mantle. Its phase behavior under high pressure has important implications for the physical properties of deep Earth and the core-mantle boundary. A number of experiments and density functional theory calculations have studied perovskite and its transition to the post-perovskite phase. Here, we present our initial work on the equation of state of perovskite at pressures up to 200 GPa using quantum Monte Carlo (QMC), a benchmark ab initio method. Our QMC calculations optimize electron correlation by using a Slater-Jastrow type wave function with a single determinant comprised of single-particle orbitals extracted from fully converged DFT calculations. The equation of state obtained from QMC calculations agrees with experimental data. E-mail: rcohen@carnegiescience.edu; This work is supported by NSF.

  11. N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

    NASA Astrophysics Data System (ADS)

    Zhuang, Gui-lin; Chen, Wu-lin; Zheng, Jun; Yu, Hui-you; Wang, Jian-guo

    2012-08-01

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H3SIDA) and Ln(NO3)3 (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd3+ ions for anti-anti and syn-anti carboxylate bridges are -1.0×10-3 and -5.0×10-3 cm-1, respectively, which reveals weak antiferromagnetic interaction in 4.

  12. Quantum Mechanical Single Molecule Partition Function from PathIntegral Monte Carlo Simulations

    SciTech Connect

    Chempath, Shaji; Bell, Alexis T.; Predescu, Cristian

    2006-10-01

    An algorithm for calculating the partition function of a molecule with the path integral Monte Carlo method is presented. Staged thermodynamic perturbation with respect to a reference harmonic potential is utilized to evaluate the ratio of partition functions. Parallel tempering and a new Monte Carlo estimator for the ratio of partition functions are implemented here to achieve well converged simulations that give an accuracy of 0.04 kcal/mol in the reported free energies. The method is applied to various test systems, including a catalytic system composed of 18 atoms. Absolute free energies calculated by this method lead to corrections as large as 2.6 kcal/mol at 300 K for some of the examples presented.

  13. Benchmark study of the two-dimensional Hubbard model with auxiliary-field quantum Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Qin, Mingpu; Shi, Hao; Zhang, Shiwei

    2016-08-01

    Ground-state properties of the Hubbard model on a two-dimensional square lattice are studied by the auxiliary-field quantum Monte Carlo method. Accurate results for energy, double occupancy, effective hopping, magnetization, and momentum distribution are calculated for interaction strengths of U /t from 2 to 8, for a range of densities including half-filling and n =0.3 ,0.5 ,0.6 ,0.75 , and 0.875 . At half-filling, the results are numerically exact. Away from half-filling, the constrained path Monte Carlo method is employed to control the sign problem. Our results are obtained with several advances in the computational algorithm, which are described in detail. We discuss the advantages of generalized Hartree-Fock trial wave functions and its connection to pairing wave functions, as well as the interplay with different forms of Hubbard-Stratonovich decompositions. We study the use of different twist angle sets when applying the twist averaged boundary conditions. We propose the use of quasirandom sequences, which improves the convergence to the thermodynamic limit over pseudorandom and other sequences. With it and a careful finite size scaling analysis, we are able to obtain accurate values of ground-state properties in the thermodynamic limit. Detailed results for finite-sized systems up to 16 ×16 are also provided for benchmark purposes.

  14. A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

    SciTech Connect

    Bauer, Thilo; Jäger, Christof M.; Jordan, Meredith J. T.; Clark, Timothy

    2015-07-28

    We have developed a multi-agent quantum Monte Carlo model to describe the spatial dynamics of multiple majority charge carriers during conduction of electric current in the channel of organic field-effect transistors. The charge carriers are treated by a neglect of diatomic differential overlap Hamiltonian using a lattice of hydrogen-like basis functions. The local ionization energy and local electron affinity defined previously map the bulk structure of the transistor channel to external potentials for the simulations of electron- and hole-conduction, respectively. The model is designed without a specific charge-transport mechanism like hopping- or band-transport in mind and does not arbitrarily localize charge. An electrode model allows dynamic injection and depletion of charge carriers according to source-drain voltage. The field-effect is modeled by using the source-gate voltage in a Metropolis-like acceptance criterion. Although the current cannot be calculated because the simulations have no time axis, using the number of Monte Carlo moves as pseudo-time gives results that resemble experimental I/V curves.

  15. Fermionic quantum criticality in honeycomb and π -flux Hubbard models: Finite-size scaling of renormalization-group-invariant observables from quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Parisen Toldin, Francesco; Hohenadler, Martin; Assaad, Fakher F.; Herbut, Igor F.

    2015-04-01

    We numerically investigate the critical behavior of the Hubbard model on the honeycomb and the π -flux lattice, which exhibits a direct transition from a Dirac semimetal to an antiferromagnetically ordered Mott insulator. We use projective auxiliary-field quantum Monte Carlo simulations and a careful finite-size scaling analysis that exploits approximately improved renormalization-group-invariant observables. This approach, which is successfully verified for the three-dimensional XY transition of the Kane-Mele-Hubbard model, allows us to extract estimates for the critical couplings and the critical exponents. The results confirm that the critical behavior for the semimetal to Mott insulator transition in the Hubbard model belongs to the Gross-Neveu-Heisenberg universality class on both lattices.

  16. Characterization and Monte Carlo simulation of single ion Geiger mode avalanche diodes integrated with a quantum dot nanostructure

    NASA Astrophysics Data System (ADS)

    Sharma, Peter; Abraham, J. B. S.; Ten Eyck, G.; Childs, K. D.; Bielejec, E.; Carroll, M. S.

    Detection of single ion implantation within a nanostructure is necessary for the high yield fabrication of implanted donor-based quantum computing architectures. Single ion Geiger mode avalanche (SIGMA) diodes with a laterally integrated nanostructure capable of forming a quantum dot were fabricated and characterized using photon pulses. The detection efficiency of this design was measured as a function of wavelength, lateral position, and for varying delay times between the photon pulse and the overbias detection window. Monte Carlo simulations based only on the random diffusion of photo-generated carriers and the geometrical placement of the avalanche region agrees qualitatively with device characterization. Based on these results, SIGMA detection efficiency appears to be determined solely by the diffusion of photo-generated electron-hole pairs into a buried avalanche region. Device performance is then highly dependent on the uniformity of the underlying silicon substrate and the proximity of photo-generated carriers to the silicon-silicon dioxide interface, which are the most important limiting factors for reaching the single ion detection limit with SIGMA detectors. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  17. Variational Monte Carlo study of chiral spin liquid in quantum antiferromagnet on the triangular lattice

    NASA Astrophysics Data System (ADS)

    Hu, Wenjun; Gong, Shoushu; Sheng, Donna; Donna Sheng Team

    We investigate the Heisenberg model with chiral coupling on the triangular lattice by using Gutzwiller projected fermionic states and the variational Monte Carlo technique. As the chiral coupling grows, a gapped spin liquid with non-trivial magnetic fluxes and nonzero chiral order is stabilized. Furthermore, we calculate the topological Chern number and the degeneracy of the ground state, both of which lead us to identify this flux state as the chiral spin liquid with C = 1 / 2 fractionalized Chern number. Finally, we add spatial anisotropy in the model to study the effects for the chiral order.

  18. Electronic structure of solid FeO at high pressures by quantum Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Kolorenč, Jindřich; Mitas, Lubos

    2010-02-01

    We determine equation of state of stoichiometric FeO by employing the diffusion Monte Carlo method. The fermionic nodes of the many-body wave function are fixed by a single Slater determinant of one-particle orbitals extracted from spin-unrestricted Kohn-Sham equations utilizing a hybrid exchange-correlation functional. The calculated ambient pressure properties agree very well with available experimental data. At approximately 65 GPa, the atomic lattice is found to change from the rocksalt B1 to the NiAs-type inverse B8 structure.

  19. BCS-BEC crossover in two dimensions: A quantum Monte Carlo study

    SciTech Connect

    Bertaina, G.

    2012-09-26

    We investigate the crossover from Bardeen-Cooper-Schrieffer (BCS) superfluidity to Bose-Einstein condensation (BEC) in a two-dimensional Fermi gas at T= 0 using the fixed-node diffusion Monte Carlo method. We calculate the equation of state and the gap parameter as a function of the interaction strength, observing large deviations compared to mean-field predictions. In the BEC regime our results show the important role of dimer-dimer and atom-dimer interaction effects that are completely neglected in the mean-field picture. We also consider the highly polarized gas and the competition between a polaronic and a molecular picture.

  20. Quantum Monte Carlo calculation of the equation of state of neutron matter

    SciTech Connect

    Gandolfi, S.; Illarionov, A. Yu.; Schmidt, K. E.; Pederiva, F.; Fantoni, S.

    2009-05-15

    We calculated the equation of state of neutron matter at zero temperature by means of the auxiliary field diffusion Monte Carlo (AFDMC) method combined with a fixed-phase approximation. The calculation of the energy was carried out by simulating up to 114 neutrons in a periodic box. Special attention was given to reducing finite-size effects at the energy evaluation by adding to the interaction the effect due to the truncation of the simulation box, and by performing several simulations using different numbers of neutrons. The finite-size effects due to kinetic energy were also checked by employing the twist-averaged boundary conditions. We considered a realistic nuclear Hamiltonian containing modern two- and three-body interactions of the Argonne and Urbana family. The equation of state can be used to compare and calibrate other many-body calculations and to predict properties of neutron stars.

  1. Quantum Monte Carlo calculation of the binding energy of the beryllium dimer

    SciTech Connect

    Deible, Michael J.; Kessler, Melody; Gasperich, Kevin E.; Jordan, Kenneth D.

    2015-08-28

    The accurate calculation of the binding energy of the beryllium dimer is a challenging theoretical problem. In this study, the binding energy of Be{sub 2} is calculated using the diffusion Monte Carlo (DMC) method, using single Slater determinant and multiconfigurational trial functions. DMC calculations using single-determinant trial wave functions of orbitals obtained from density functional theory calculations overestimate the binding energy, while DMC calculations using Hartree-Fock or CAS(4,8), complete active space trial functions significantly underestimate the binding energy. In order to obtain an accurate value of the binding energy of Be{sub 2} from DMC calculations, it is necessary to employ trial functions that include excitations outside the valence space. Our best estimate DMC result for the binding energy of Be{sub 2}, obtained by using configuration interaction trial functions and extrapolating in the threshold for the configurations retained in the trial function, is 908 cm{sup −1}, only slightly below the 935 cm{sup −1} value derived from experiment.

  2. Microscopic distribution functions, structure, and kinetic energy of liquid and solid neon: quantum Monte Carlo simulations.

    PubMed

    Neumann, Martin; Zoppi, Marco

    2002-03-01

    We have performed extensive path integral Monte Carlo simulations of liquid and solid neon, in order to derive the kinetic energy as well as the single-particle and pair distribution functions of neon atoms in the condensed phases. From the single-particle distribution function n(r) one can derive the momentum distribution and thus obtain an independent estimate of the kinetic energy. The simulations have been carried out using mostly the semiempirical HFD-C2 pair potential by Aziz et al. [R. A. Aziz, W. J. Meath, and A. R. Allnatt, Chem. Phys. 79, 295 (1983)], but, in a few cases, we have also used the Lennard-Jones potential. The differences between the potentials, as measured by the properties investigated, are not very large, especially when compared with the actual precision of the experimental data. The simulation results have been compared with all the experimental information that is available from neutron scattering. The overall agreement with the experiments is very good.

  3. Self-healing diffusion quantum Monte Carlo algorithms: Theory and Applications

    NASA Astrophysics Data System (ADS)

    Reboredo, F. A.; Kent, P. R. C.; Tiago, M. L.; Hood, R. Q.

    2009-03-01

    We present a method to obtain the fixed node ground state wave function from an importance sampling Diffusion Monte Carlo (DMC) run. The fixed node ground state wave-function is altered to obtain an improved trial wave-function for the next DMC run. The theory behind this approach will be discussed. Two iterative algorithms are presented and validated in a model system by direct comparison with full configuration interaction (CI) wave functions and energies. We find that the trial wave-function is systematically improved. The scalar product of the trial wave-function with the CI result converges to 1 even starting from wave-functions orthogonal to the CI ground state. Similarly, the DMC total energy and density converges to the CI result. In the optimization process we find an optimal non-interacting nodal potential of density-functional-like form. An extension to a model system with full Coulomb interactions demonstrates that we can obtain the exact Kohn-Sham effective potential from the DMC data. Subsequently we apply our method to real molecules such as benzene and find that we can improve the ground state energy as compared with the single determinant result even starting from random wave-functions. Results for other molecular systems and comparison with alternative methods will be presented.

  4. Reaction pathways by quantum Monte Carlo: Insight on the torsion barrier of 1,3-butadiene, and the conrotatory ring opening of cyclobutene

    PubMed Central

    Barborini, Matteo; Guidoni, Leonardo

    2014-01-01

    Quantum Monte Carlo (QMC) methods are used to investigate the intramolecular reaction pathways of 1,3-butadiene. The ground state geometries of the three conformers s-trans, s-cis, and gauche, as well as the cyclobutene structure are fully optimised at the variational Monte Carlo (VMC) level, obtaining an excellent agreement with the experimental results and other quantum chemistry high level calculations. Transition state geometries are also estimated at the VMC level for the s-trans to gauche torsion barrier of 1,3-butadiene and for the conrotatory ring opening of cyclobutene to the gauche-1,3-butadiene conformer. The energies of the conformers and the reaction barriers are calculated at both variational and diffusional Monte Carlo levels providing a precise picture of the potential energy surface of 1,3-butadiene and supporting one of the two model profiles recently obtained by Raman spectroscopy [Boopalachandran et al., J. Phys. Chem. A 115, 8920 (2011)]. Considering the good scaling of QMC techniques with the system’s size, our results also demonstrate how variational Monte Carlo calculations can be applied in the future to properly investigate the reaction pathways of large and correlated molecular systems. PMID:23249005

  5. Quantum partition functions of composite particles in a hydrogen-helium plasma via path integral Monte Carlo

    SciTech Connect

    Wendland, D.; Ballenegger, V.; Alastuey, A.

    2014-11-14

    We compute two- and three-body cluster functions that describe contributions of composite entities, like hydrogen atoms, ions H{sup −}, H{sub 2}{sup +}, and helium atoms, and also charge-charge and atom-charge interactions, to the equation of state of a hydrogen-helium mixture at low density. A cluster function has the structure of a truncated virial coefficient and behaves, at low temperatures, like a usual partition function for the composite entity. Our path integral Monte Carlo calculations use importance sampling to sample efficiently the cluster partition functions even at low temperatures where bound state contributions dominate. We also employ a new and efficient adaptive discretization scheme that allows one not only to eliminate Coulomb divergencies in discretized path integrals, but also to direct the computational effort where particles are close and thus strongly interacting. The numerical results for the two-body function agree with the analytically known quantum second virial coefficient. The three-body cluster functions are compared at low temperatures with familiar partition functions for composite entities.

  6. Auxiliary-field quantum Monte Carlo study of first- and second-row post-d elements

    NASA Astrophysics Data System (ADS)

    Al-Saidi, W. A.; Krakauer, Henry; Zhang, Shiwei

    2006-10-01

    A series of calculations for the first- and second-row post-d elements (Ga-Br and In-I) are presented using the phaseless auxiliary-field quantum Monte Carlo (AF QMC) method. This method is formulated in a Hilbert space defined by any chosen one-particle basis and maps the many-body problem into a linear combination of independent-particle solutions with external auxiliary fields. The phase/sign problem is handled approximately by the phaseless formalism using a trial wave function, which in our calculations was chosen to be the Hartree-Fock solution. We used the consistent correlated basis sets of Peterson et al. [J. Chem. Phys. 119, 11099 (2003); 119, 11113 (2003)], which employ a small-core relativistic pseudopotential. The AF QMC results are compared with experiment and with those from density functional (generalized gradient approximation and B3LYP) and CCSD(T) calculations. The AF QMC total energies agree with CCSD(T) to within a few millihartrees across the systems and over several basis sets. The calculated atomic electron affinities, ionization energies, and spectroscopic properties of dimers are, at large basis sets, in excellent agreement with experiment.

  7. Quantum Monte Carlo simulation of antiferromagnetic spin ladder (C5H12N)2CuBr4

    NASA Astrophysics Data System (ADS)

    Freitas, Augusto S.

    2016-07-01

    In this paper I present a Quantum Monte Carlo (QMC) study of the magnetic properties of an antiferromagnetic spin ladder (C5H12N)2CuBr4. This compound is the prototype of the Heisenberg model for a two leg spin ladder in the presence of an external magnetic field. The susceptibility phase diagram has a rounded peak in the vicinity of T=7.4 K, obeys Troyer's law for low temperatures, and Curie's law for high temperatures. I also study the susceptibility diagram in low temperatures and I found the spin gap Δ=9.26 K, in good concordance with the experimental value, 9.5 K. In high field, I present a diagram of magnetization as a function of temperature. In the vicinity of a critical field, Hci, the magnetization scales with T1/2 and this result was found also in the QMC simulation. In all the results, there is a very good concordance with the experimental data. I also show in this paper that the spin gap is null and the susceptibility is proportional to T for low temperatures when relatively high values of the ladders' coupling is taken in account.

  8. Many-body ab initio diffusion quantum Monte Carlo applied to the strongly correlated oxide NiO

    DOE PAGES

    Mitra, Chandrima; Krogel, Jaron T.; Santana, Juan A.; Reboredo, Fernando A.

    2015-10-28

    We present a many-body diffusion quantum Monte Carlo (DMC) study of the bulk and defect properties of NiO. We find excellent agreement with experimental values, within 0.3%, 0.6%, and 3.5% for the lattice constant, cohesive energy, and bulk modulus, respectively. The quasiparticle bandgap was also computed, and the DMC result of 4.72 (0.17) eV compares well with the experimental value of 4.3 eV. Furthermore, DMC calculations of excited states at the L, Z, and the gamma point of the Brillouin zone reveal a flat upper valence band for NiO, in good agreement with Angle Resolved Photoemission Spectroscopy results. To studymore » defect properties, we evaluated the formation energies of the neutral and charged vacancies of oxygen and nickel in NiO. A formation energy of 7.2 (0.15) eV was found for the oxygen vacancy under oxygen rich conditions. For the Ni vacancy, we obtained a formation energy of 3.2 (0.15) eV under Ni rich conditions. Lastly, these results confirm that NiO occurs as a p-type material with the dominant intrinsic vacancy defect being Ni vacancy. (C) 2015 AIP Publishing LLC.« less

  9. Many-body ab initio diffusion quantum Monte Carlo applied to the strongly correlated oxide NiO

    SciTech Connect

    Mitra, Chandrima; Krogel, Jaron T.; Santana, Juan A.; Reboredo, Fernando A.

    2015-10-28

    We present a many-body diffusion quantum Monte Carlo (DMC) study of the bulk and defect properties of NiO. We find excellent agreement with experimental values, within 0.3%, 0.6%, and 3.5% for the lattice constant, cohesive energy, and bulk modulus, respectively. The quasiparticle bandgap was also computed, and the DMC result of 4.72 (0.17) eV compares well with the experimental value of 4.3 eV. Furthermore, DMC calculations of excited states at the L, Z, and the gamma point of the Brillouin zone reveal a flat upper valence band for NiO, in good agreement with Angle Resolved Photoemission Spectroscopy results. To study defect properties, we evaluated the formation energies of the neutral and charged vacancies of oxygen and nickel in NiO. A formation energy of 7.2 (0.15) eV was found for the oxygen vacancy under oxygen rich conditions. For the Ni vacancy, we obtained a formation energy of 3.2 (0.15) eV under Ni rich conditions. These results confirm that NiO occurs as a p-type material with the dominant intrinsic vacancy defect being Ni vacancy.

  10. Competing collinear magnetic structures in superconducting FeSe by first-principles quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Busemeyer, Brian; Dagrada, Mario; Sorella, Sandro; Casula, Michele; Wagner, Lucas K.

    2016-07-01

    Resolving the interplay between magnetic interactions and structural properties in strongly correlated materials through a quantitatively accurate approach has been a major challenge in condensed-matter physics. Here we apply highly accurate first-principles quantum Monte Carlo (QMC) techniques to obtain structural and magnetic properties of the iron selenide (FeSe) superconductor under pressure. Where comparable, the computed properties are very close to the experimental values. Of potential ordered magnetic configurations, collinear spin configurations are the most energetically favorable over the explored pressure range. They become nearly degenerate in energy with bicollinear spin orderings at around 7 GPa, when the experimental critical temperature Tc is the highest. On the other hand, ferromagnetic, checkerboard, and staggered dimer configurations become relatively higher in energy as the pressure increases. The behavior under pressure is explained by an analysis of the local charge compressibility and the orbital occupation as described by the QMC many-body wave function, which reveals how spin, charge, and orbital degrees of freedom are strongly coupled in this compound. This remarkable pressure evolution suggests that stripelike magnetic fluctuations may be responsible for the enhanced Tc in FeSe and that higher Tc is associated with nearness to a crossover between collinear and bicollinear ordering.

  11. Post-DFT methods for Earth materials: Quantum Monte Carlo simulations of (Mg,Fe)O (Invited)

    NASA Astrophysics Data System (ADS)

    Driver, K. P.; Militzer, B.; Cohen, R. E.

    2013-12-01

    (Mg,Fe)O is a major mineral phase in Earth's lower mantle that plays a key role in determining the structural and dynamical properties of deep Earth. A pressure-induced spin-pairing transition of Fe has been the subject of numerous theoretical and experimental studies due to the consequential effects on lower mantle physics. The standard density functional theory (DFT) method does not treat strongly correlated electrons properly and results can have dependence on the choice of exchange-correlation functional. DFT+U, offers significant improvement over standard DFT for treating strongly correlated electrons. Indeed, DFT+U calculations and experiments have narrowed the ambient spin-transition between 40-60 GPa in (Mg,Fe)O. However, DFT+U, is not an ideal method due to dependence on Hubbard U parameter among other approximations. In order to further clarify details of the spin transition, it is necessary to use methods that explicitly treat effects of electron exchange and correlation, such as quantum Monte Carlo (QMC). Here, we will discuss methods of going beyond standard DFT and present QMC results on the (Mg,Fe)O elastic properties and spin-transition pressure in order to benchmark DFT+U results.

  12. Energy benchmarks for methane-water systems from quantum Monte Carlo and second-order Møller-Plesset calculations.

    PubMed

    Gillan, M J; Alfè, D; Manby, F R

    2015-09-14

    The quantum Monte Carlo (QMC) technique is used to generate accurate energy benchmarks for methane-water clusters containing a single methane monomer and up to 20 water monomers. The benchmarks for each type of cluster are computed for a set of geometries drawn from molecular dynamics simulations. The accuracy of QMC is expected to be comparable with that of coupled-cluster calculations, and this is confirmed by comparisons for the CH4-H2O dimer. The benchmarks are used to assess the accuracy of the second-order Møller-Plesset (MP2) approximation close to the complete basis-set limit. A recently developed embedded many-body technique is shown to give an efficient procedure for computing basis-set converged MP2 energies for the large clusters. It is found that MP2 values for the methane binding energies and the cohesive energies of the water clusters without methane are in close agreement with the QMC benchmarks, but the agreement is aided by partial cancelation between 2-body and beyond-2-body errors of MP2. The embedding approach allows MP2 to be applied without loss of accuracy to the methane hydrate crystal, and it is shown that the resulting methane binding energy and the cohesive energy of the water lattice agree almost exactly with recently reported QMC values. PMID:26374005

  13. Multi-level quantum Monte Carlo wave functions for complex reactions: the decomposition of α-hydroxy-dimethylnitrosamine.

    PubMed

    Fracchia, Francesco; Filippi, Claudia; Amovilli, Claudio

    2014-01-01

    We present here several novel features of our recently proposed Jastrow linear generalized valence bond (J-LGVB) wave functions, which allow a consistently accurate description of complex potential energy surfaces (PES) of medium-large systems within quantum Monte Carlo (QMC). In particular, we develop a multilevel scheme to treat different regions of the molecule at different levels of the theory. As prototypical study case, we investigate the decomposition of α-hydroxy-dimethylnitrosamine, a carcinogenic metabolite of dimethylnitrosamine (NDMA), through a two-step mechanism of isomerization followed by a retro-ene reaction. We compute a reliable reaction path with the quadratic configuration interaction method and employ QMC for the calculation of the electronic energies. We show that the use of multideterminantal wave functions is very important to correctly describe the critical points of this PES within QMC, and that our multilevel J-LGVB approach is an effective tool to significantly reduce the cost of QMC calculations without loss of accuracy. As regards the complex PES of α-hydroxy-dimethylnitrosamine, the accurate energies computed with our approach allows us to confirm the validity of the two-step reaction mechanism of decomposition originally proposed within density functional theory, but with some important differences in the barrier heights of the individual steps.

  14. Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods

    DOE PAGES

    Ganesh, P.; Kim, Jeongnim; Park, Changwon; Yoon, Mina; Reboredo, Fernando A.; Kent, Paul R. C.

    2014-11-03

    In highly accurate diffusion quantum Monte Carlo (QMC) studies of the adsorption and diffusion of atomic lithium in AA-stacked graphite are compared with van der Waals-including density functional theory (DFT) calculations. Predicted QMC lattice constants for pure AA graphite agree with experiment. Pure AA-stacked graphite is shown to challenge many van der Waals methods even when they are accurate for conventional AB graphite. Moreover, the highest overall DFT accuracy, considering pure AA-stacked graphite as well as lithium binding and diffusion, is obtained by the self-consistent van der Waals functional vdW-DF2, although errors in binding energies remain. Empirical approaches based onmore » point charges such as DFT-D are inaccurate unless the local charge transfer is assessed. Our results demonstrate that the lithium carbon system requires a simultaneous highly accurate description of both charge transfer and van der Waals interactions, favoring self-consistent approaches.« less

  15. Using Monte Carlo ray tracing simulations to model the quantum harmonic oscillator modes observed in uranium nitride

    SciTech Connect

    Lin, J. Y. Y.; Aczel, Adam A; Abernathy, Douglas L; Nagler, Stephen E; Buyers, W. J. L.; Granroth, Garrett E

    2014-01-01

    Recently an extended series of equally spaced vibrational modes was observed in uranium nitride (UN) by performing neutron spectroscopy measurements using the ARCS and SEQUOIA time-of- flight chopper spectrometers [A.A. Aczel et al, Nature Communications 3, 1124 (2012)]. These modes are well described by 3D isotropic quantum harmonic oscillator (QHO) behavior of the nitrogen atoms, but there are additional contributions to the scattering that complicate the measured response. In an effort to better characterize the observed neutron scattering spectrum of UN, we have performed Monte Carlo ray tracing simulations of the ARCS and SEQUOIA experiments with various sample kernels, accounting for the nitrogen QHO scattering, contributions that arise from the acoustic portion of the partial phonon density of states (PDOS), and multiple scattering. These simulations demonstrate that the U and N motions can be treated independently, and show that multiple scattering contributes an approximate Q-independent background to the spectrum at the oscillator mode positions. Temperature dependent studies of the lowest few oscillator modes have also been made with SEQUOIA, and our simulations indicate that the T-dependence of the scattering from these modes is strongly influenced by the uranium lattice.

  16. Improved measurement scheme of the self energy in the worm-sampled hybridization-expansion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Han, Mancheon; Lee, Choong-Ki; Choi, Hyoung Joon

    Hybridization-expansion continuous-time quantum Monte Carlo (CT-HYB) is a popular approach in real material researches because it allows to deal with non-density-density-type interaction. In the conventional CT-HYB, we measure Green's function and find the self energy from the Dyson equation. Because one needs to compute the inverse of the statistical data in this approach, obtained self energy is very sensitive to statistical noise. For that reason, the measurement is not reliable except for low frequencies. Such an error can be suppressed by measuring a special type of higher-order correlation function and is implemented for density-density-type interaction. With the help of the recently reported worm-sampling measurement, we developed an improved self energy measurement scheme which can be applied to any type of interactions. As an illustration, we calculated the self energy for the 3-orbital Hubbard-Kanamori-type Hamiltonian with our newly developed method. This work was supported by NRF of Korea (Grant No. 2011-0018306) and KISTI supercomputing center (Project No. KSC-2015-C3-039)

  17. Simple Impurity Embedded in a Spherical Jellium: Approximations of Density Functional Theory compared to Quantum Monte Carlo Benchmarks

    SciTech Connect

    Bajdich, Michal; Kent, Paul R; Kim, Jeongnim; Reboredo, Fernando A

    2011-01-01

    We study the electronic structure of a spherical jellium in the presence of a central Gaussian impurity. We test how well the resulting inhomogeneity effects beyond spherical jellium are reproduced by several approximations of density functional theory (DFT). Four rungs of Perdew's ladder of DFT functionals, namely, local density approximation, generalized gradient approximation (GGA), meta-GGA, and orbital-dependent hybrid functionals are compared against our quantum Monte Carlo (QMC) benchmarks. We identify several distinct transitions in the ground state of the system as the electronic occupation changes between delocalized and localized states. We examine the parameter space of realistic densities (1{open_square}r{sub s}{open_square}5) and moderate depths of the Gaussian impurity (Z<7). The selected 18-electron system (with closed-shell ground state) presents 1d{yields}2s transitions, while the 30-electron system (with open-shell ground state) exhibits 1f{yields}2p transitions. For the former system, the accuracy for the transitions is clearly improving with increasing sophistication of functionals with meta-GGA and hybrid functionals having only small deviations from QMC. However, for the latter system, we find much larger differences for the underlying transitions between our pool of DFT functionals and QMC. We attribute these failures to an insufficiently accurate treatment of exchange by these functionals. Additionally, we amplify the inhomogeneity effects by creating the system with spherical shell, which leads to even larger errors in DFT approximations.

  18. Energy benchmarks for methane-water systems from quantum Monte Carlo and second-order Møller-Plesset calculations

    SciTech Connect

    Gillan, M. J.; Alfè, D.; Manby, F. R.

    2015-09-14

    The quantum Monte Carlo (QMC) technique is used to generate accurate energy benchmarks for methane-water clusters containing a single methane monomer and up to 20 water monomers. The benchmarks for each type of cluster are computed for a set of geometries drawn from molecular dynamics simulations. The accuracy of QMC is expected to be comparable with that of coupled-cluster calculations, and this is confirmed by comparisons for the CH{sub 4}-H{sub 2}O dimer. The benchmarks are used to assess the accuracy of the second-order Møller-Plesset (MP2) approximation close to the complete basis-set limit. A recently developed embedded many-body technique is shown to give an efficient procedure for computing basis-set converged MP2 energies for the large clusters. It is found that MP2 values for the methane binding energies and the cohesive energies of the water clusters without methane are in close agreement with the QMC benchmarks, but the agreement is aided by partial cancelation between 2-body and beyond-2-body errors of MP2. The embedding approach allows MP2 to be applied without loss of accuracy to the methane hydrate crystal, and it is shown that the resulting methane binding energy and the cohesive energy of the water lattice agree almost exactly with recently reported QMC values.

  19. Computation of dynamical correlation functions for many-fermion systems with auxiliary-field quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Vitali, Ettore; Shi, Hao; Qin, Mingpu; Zhang, Shiwei

    2016-08-01

    We address the calculation of dynamical correlation functions for many fermion systems at zero temperature, using the auxiliary-field quantum Monte Carlo method. The two-dimensional Hubbard hamiltonian is used as a model system. Although most of the calculations performed here are for cases where the sign problem is absent, the discussions are kept general for applications to physical problems when the sign problem does arise. We study the use of twisted boundary conditions to improve the extrapolation of the results to the thermodynamic limit. A strategy is proposed to drastically reduce finite size effects relying on a minimization among the twist angles. This approach is demonstrated by computing the charge gap at half filling. We obtain accurate results showing the scaling of the gap with the interaction strength U in two dimensions, connecting to the scaling of the unrestricted Hartree-Fock method at small U and Bethe ansatz exact result in one dimension at large U . An alternative algorithm is then proposed to compute dynamical Green functions and correlation functions which explicitly varies the number of particles during the random walks in the manifold of Slater determinants. In dilute systems, such as ultracold Fermi gases, this algorithm enables calculations with much more favorable complexity, with computational cost proportional to basis size or the number of lattice sites.

  20. Quantum Monte Carlo analysis of a charge ordered insulating antiferromagnet: The Ti4O7 Magneli phase

    DOE PAGES

    Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T.; Zhong, Xiaoling; Kent, Paul R. C.; Heinonen, Olle

    2016-06-07

    The Magneli phase Ti4O7 is an important transition metal oxide with a wide range of applications because of its interplay between charge, spin, and lattice degrees of freedom. At low temperatures, it has non-trivial magnetic states very close in energy, driven by electronic exchange and correlation interactions. We have examined three low- lying states, one ferromagnetic and two antiferromagnetic, and calculated their energies as well as Ti spin moment distributions using highly accurate Quantum Monte Carlo methods. We compare our results to those obtained from density functional theory- based methods that include approximate corrections for exchange and correlation. Our resultsmore » confirm the nature of the states and their ordering in energy, as compared with density-functional theory methods. However, the energy differences and spin distributions differ. Here, a detailed analysis suggests that non-local exchange-correlation functionals, in addition to other approximations such as LDA+U to account for correlations, are needed to simultaneously obtain better estimates for spin moments, distributions, energy differences and energy gaps.« less

  1. Cohesive energy and structural parameters of binary oxides of groups IIA and IIIB from diffusion quantum Monte Carlo

    DOE PAGES

    Santana, Juan A.; Krogel, Jaron T.; Kent, Paul R. C.; Reboredo, Fernando A.

    2016-05-03

    We have applied the diffusion quantum Monte Carlo (DMC) method to calculate the cohesive energy and the structural parameters of the binary oxides CaO, SrO, BaO, Sc2O3, Y2O3 and La2O3. The aim of our calculations is to systematically quantify the accuracy of the DMC method to study this type of metal oxides. The DMC results were compared with local and semi-local Density Functional Theory (DFT) approximations as well as with experimental measurements. The DMC method yields cohesive energies for these oxides with a mean absolute deviation from experimental measurements of 0.18(2) eV, while with local and semi-local DFT approximations themore » deviation is 3.06 and 0.94 eV, respectively. For lattice constants, the mean absolute deviation in DMC, local and semi-local DFT approximations, are 0.017(1), 0.07 and 0.05 , respectively. In conclusion, DMC is highly accurate method, outperforming the local and semi-local DFT approximations in describing the cohesive energies and structural parameters of these binary oxides.« less

  2. Quantum Monte Carlo analysis of a charge ordered insulating antiferromagnet: the Ti4O7 Magnéli phase.

    PubMed

    Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T; Zhong, Xiaoliang; Kent, Paul R C; Heinonen, Olle

    2016-07-21

    The Magnéli phase Ti4O7 is an important transition metal oxide with a wide range of applications because of its interplay between charge, spin, and lattice degrees of freedom. At low temperatures, it has non-trivial magnetic states very close in energy, driven by electronic exchange and correlation interactions. We have examined three low-lying states, one ferromagnetic and two antiferromagnetic, and calculated their energies as well as Ti spin moment distributions using highly accurate quantum Monte Carlo methods. We compare our results to those obtained from density functional theory-based methods that include approximate corrections for exchange and correlation. Our results confirm the nature of the states and their ordering in energy, as compared with density-functional theory methods. However, the energy differences and spin distributions differ. A detailed analysis suggests that non-local exchange-correlation functionals, in addition to other approximations such as LDA+U to account for correlations, are needed to simultaneously obtain better estimates for spin moments, distributions, energy differences and energy gaps. PMID:27334262

  3. Variational Monte Carlo study of chiral spin liquid in quantum antiferromagnet on the triangular lattice

    NASA Astrophysics Data System (ADS)

    Hu, Wen-Jun; Gong, Shou-Shu; Sheng, D. N.

    2016-08-01

    By using Gutzwiller projected fermionic wave functions and variational Monte Carlo technique, we study the spin-1 /2 Heisenberg model with the first-neighbor (J1), second-neighbor (J2), and additional scalar chiral interaction JχSi.(Sj×Sk) on the triangular lattice. In the nonmagnetic phase of the J1-J2 triangular model with 0.08 ≲J2/J1≲0.16 , recent density-matrix renormalization group (DMRG) studies [Zhu and White, Phys. Rev. B 92, 041105(R) (2015), 10.1103/PhysRevB.92.041105 and Hu, Gong, Zhu, and Sheng, Phys. Rev. B 92, 140403(R) (2015), 10.1103/PhysRevB.92.140403] find a possible gapped spin liquid with the signal of a competition between a chiral and a Z2 spin liquid. Motivated by the DMRG results, we consider the chiral interaction JχSi.(Sj×Sk) as a perturbation for this nonmagnetic phase. We find that with growing Jχ, the gapless U(1) Dirac spin liquid, which has the best variational energy for Jχ=0 , exhibits the energy instability towards a gapped spin liquid with nontrivial magnetic fluxes and nonzero chiral order. We calculate topological Chern number and ground-state degeneracy, both of which identify this flux state as the chiral spin liquid with fractionalized Chern number C =1 /2 and twofold topological degeneracy. Our results indicate a positive direction to stabilize a chiral spin liquid near the nonmagnetic phase of the J1-J2 triangular model.

  4. Instantons and scaling of the transitions rates in Quantum Monte Carlo simulations of thermally-assisted quantum tunneling in spin systems

    NASA Astrophysics Data System (ADS)

    Smelyanskiy, Vadim; Jiang, Zhang; Boixo, Sergio; Issakov, Sergei; Mazzola, Guglielmo; Troyer, Matthias; Neven, Hartmut

    We study analytically and numerically the dynamics of the quantum Monte Carlo (QMC) algorithm to simulate thermally-assisted tunneling in mean-field spin models without conservation of total spin. We use Kramers escape rate theory to calculate the scaling of the QMC time with the problem size to simulate the tunneling transitions. We develop path-integral instanton approach in coherent state and Suzuki-Trotter representations to calculate the escape rate and most probable escape path in QMC dynamics. Analtytical results are in a good agreement with numerical studies. We identify the class of models where the exponent in the scaling of the QMC time is the same as that in physical tunneling but the pre-factor depends very significantly on the QMC path representation. We propose the classes of problems where QMC can fail to simulate tunneling efficiently. The work of GM and MT has been supported by the Swiss National Science Foundation through the National Competence Center in Research QSIT and by ODNI, IARPA via MIT Lincoln Laboratory Air Force Contract No. FA8721-05-C-0002.

  5. Rapid Bacterial Detection via an All-Electronic CMOS Biosensor

    PubMed Central

    Nikkhoo, Nasim; Cumby, Nichole; Gulak, P. Glenn; Maxwell, Karen L.

    2016-01-01

    The timely and accurate diagnosis of infectious diseases is one of the greatest challenges currently facing modern medicine. The development of innovative techniques for the rapid and accurate identification of bacterial pathogens in point-of-care facilities using low-cost, portable instruments is essential. We have developed a novel all-electronic biosensor that is able to identify bacteria in less than ten minutes. This technology exploits bacteriocins, protein toxins naturally produced by bacteria, as the selective biological detection element. The bacteriocins are integrated with an array of potassium-selective sensors in Complementary Metal Oxide Semiconductor technology to provide an inexpensive bacterial biosensor. An electronic platform connects the CMOS sensor to a computer for processing and real-time visualization. We have used this technology to successfully identify both Gram-positive and Gram-negative bacteria commonly found in human infections. PMID:27618185

  6. Rapid Bacterial Detection via an All-Electronic CMOS Biosensor.

    PubMed

    Nikkhoo, Nasim; Cumby, Nichole; Gulak, P Glenn; Maxwell, Karen L

    2016-01-01

    The timely and accurate diagnosis of infectious diseases is one of the greatest challenges currently facing modern medicine. The development of innovative techniques for the rapid and accurate identification of bacterial pathogens in point-of-care facilities using low-cost, portable instruments is essential. We have developed a novel all-electronic biosensor that is able to identify bacteria in less than ten minutes. This technology exploits bacteriocins, protein toxins naturally produced by bacteria, as the selective biological detection element. The bacteriocins are integrated with an array of potassium-selective sensors in Complementary Metal Oxide Semiconductor technology to provide an inexpensive bacterial biosensor. An electronic platform connects the CMOS sensor to a computer for processing and real-time visualization. We have used this technology to successfully identify both Gram-positive and Gram-negative bacteria commonly found in human infections. PMID:27618185

  7. Combined rate equation and Monte Carlo studies of electron transport in a GaAs/Al0.45Ga0.55As quantum-cascade laser

    NASA Astrophysics Data System (ADS)

    Borowik, Piotr; Thobel, Jean-Luc; Adamowicz, Leszek

    2012-11-01

    Comparison of the Monte Carlo and rate equation methods as applied to the study of electron transport in a mid-infrared quantum cascade laser structure initially proposed by Page et al (2001 Appl. Phys. Lett. 78 3529) is presented for a range of realistic injector doping levels. An analysis of the difference between these two methods is given. It is suggested that justified approximations of the rate equation method, originated by imposing Fermi-Dirac statistics and the same electron effective temperature for each of the energy sub-bands, can be interpreted as partial inclusion of electron-electron interactions. Results of the rate equation method may be used as good initial conditions for a more precise Monte Carlo simulation. An algorithm combining rate equation and Monte Carlo simulations is examined. A reasonable agreement between the introduced method and a fully self-consistent resolution of Monte Carlo and Schrödinger coupled with Poisson equations is demonstrated. The computation time may be reduced when the combined algorithm is used.

  8. Dynamic Cluster Quantum Monte Carlo Simulations of a Two-Dimensional Hubbard Model with Stripelike Charge-Density-Wave Modulations: Interplay between Inhomogeneities and the Superconducting State

    SciTech Connect

    Maier, Thomas A; Alvarez, Gonzalo; Summers, Michael Stuart; Schulthess, Thomas C

    2010-01-01

    Using dynamic cluster quantum Monte Carlo simulations, we study the superconducting behavior of a 1=8 doped two-dimensional Hubbard model with imposed unidirectional stripelike charge-density-wave modulation. We find a significant increase of the pairing correlations and critical temperature relative to the homogeneous system when the modulation length scale is sufficiently large. With a separable form of the irreducible particle-particle vertex, we show that optimized superconductivity is obtained for a moderate modulation strength due to a delicate balance between the modulation enhanced pairing interaction, and a concomitant suppression of the bare particle-particle excitations by a modulation reduction of the quasiparticle weight.

  9. Label-free all-electronic biosensing in microfluidic systems

    NASA Astrophysics Data System (ADS)

    Stanton, Michael A.

    Label-free, all-electronic detection techniques offer great promise for advancements in medical and biological analysis. Electrical sensing can be used to measure both interfacial and bulk impedance changes in conducting solutions. Electronic sensors produced using standard microfabrication processes are easily integrated into microfluidic systems. Combined with the sensitivity of radiofrequency electrical measurements, this approach offers significant advantages over competing biological sensing methods. Scalable fabrication methods also provide a means of bypassing the prohibitive costs and infrastructure associated with current technologies. We describe the design, development and use of a radiofrequency reflectometer integrated into a microfluidic system towards the specific detection of biologically relevant materials. We developed a detection protocol based on impedimetric changes caused by the binding of antibody/antigen pairs to the sensing region. Here we report the surface chemistry that forms the necessary capture mechanism. Gold-thiol binding was utilized to create an ordered alkane monolayer on the sensor surface. Exposed functional groups target the N-terminus, affixing a protein to the monolayer. The general applicability of this method lends itself to a wide variety of proteins. To demonstrate specificity, commercially available mouse anti- Streptococcus Pneumoniae monoclonal antibody was used to target the full-length recombinant pneumococcal surface protein A, type 2 strain D39 expressed by Streptococcus Pneumoniae. We demonstrate the RF response of the sensor to both the presence of the surface decoration and bound SPn cells in a 1x phosphate buffered saline solution. The combined microfluidic sensor represents a powerful platform for the analysis and detection of cells and biomolecules.

  10. Molecular Properties by Quantum Monte Carlo: An Investigation on the Role of the Wave Function Ansatz and the Basis Set in the Water Molecule

    PubMed Central

    Zen, Andrea; Luo, Ye; Sorella, Sandro; Guidoni, Leonardo

    2014-01-01

    Quantum Monte Carlo methods are accurate and promising many body techniques for electronic structure calculations which, in the last years, are encountering a growing interest thanks to their favorable scaling with the system size and their efficient parallelization, particularly suited for the modern high performance computing facilities. The ansatz of the wave function and its variational flexibility are crucial points for both the accurate description of molecular properties and the capabilities of the method to tackle large systems. In this paper, we extensively analyze, using different variational ansatzes, several properties of the water molecule, namely, the total energy, the dipole and quadrupole momenta, the ionization and atomization energies, the equilibrium configuration, and the harmonic and fundamental frequencies of vibration. The investigation mainly focuses on variational Monte Carlo calculations, although several lattice regularized diffusion Monte Carlo calculations are also reported. Through a systematic study, we provide a useful guide to the choice of the wave function, the pseudopotential, and the basis set for QMC calculations. We also introduce a new method for the computation of forces with finite variance on open systems and a new strategy for the definition of the atomic orbitals involved in the Jastrow-Antisymmetrised Geminal power wave function, in order to drastically reduce the number of variational parameters. This scheme significantly improves the efficiency of QMC energy minimization in case of large basis sets. PMID:24526929

  11. Molecular Properties by Quantum Monte Carlo: An Investigation on the Role of the Wave Function Ansatz and the Basis Set in the Water Molecule.

    PubMed

    Zen, Andrea; Luo, Ye; Sorella, Sandro; Guidoni, Leonardo

    2013-10-01

    Quantum Monte Carlo methods are accurate and promising many body techniques for electronic structure calculations which, in the last years, are encountering a growing interest thanks to their favorable scaling with the system size and their efficient parallelization, particularly suited for the modern high performance computing facilities. The ansatz of the wave function and its variational flexibility are crucial points for both the accurate description of molecular properties and the capabilities of the method to tackle large systems. In this paper, we extensively analyze, using different variational ansatzes, several properties of the water molecule, namely, the total energy, the dipole and quadrupole momenta, the ionization and atomization energies, the equilibrium configuration, and the harmonic and fundamental frequencies of vibration. The investigation mainly focuses on variational Monte Carlo calculations, although several lattice regularized diffusion Monte Carlo calculations are also reported. Through a systematic study, we provide a useful guide to the choice of the wave function, the pseudopotential, and the basis set for QMC calculations. We also introduce a new method for the computation of forces with finite variance on open systems and a new strategy for the definition of the atomic orbitals involved in the Jastrow-Antisymmetrised Geminal power wave function, in order to drastically reduce the number of variational parameters. This scheme significantly improves the efficiency of QMC energy minimization in case of large basis sets. PMID:24526929

  12. Synergies from using higher order symplectic decompositions both for ordinary differential equations and quantum Monte Carlo methods

    SciTech Connect

    Matuttis, Hans-Georg; Wang, Xiaoxing

    2015-03-10

    Decomposition methods of the Suzuki-Trotter type of various orders have been derived in different fields. Applying them both to classical ordinary differential equations (ODEs) and quantum systems allows to judge their effectiveness and gives new insights for many body quantum mechanics where reference data are scarce. Further, based on data for 6 × 6 system we conclude that sampling with sign (minus-sign problem) is probably detrimental to the accuracy of fermionic simulations with determinant algorithms.

  13. Equations of state and stability of MgSiO3 perovskite and post-perovskite phases from quantum Monte Carlo simulations

    SciTech Connect

    Lin, Yangzheng; Cohen, Ronald E.; Stackhouse, Stephen; Driver, Kevin P.; Militzer, Burkhard; Shulenburger, Luke; Kim, Jeongnim

    2014-11-10

    In this study, we have performed quantum Monte Carlo (QMC) simulations and density functional theory calculations to study the equations of state of MgSiO3 perovskite (Pv, bridgmanite) and post-perovskite (PPv) up to the pressure and temperature conditions of the base of Earth's lower mantle. The ground-state energies were derived using QMC simulations and the temperature-dependent Helmholtz free energies were calculated within the quasiharmonic approximation and density functional perturbation theory. The equations of state for both phases of MgSiO3 agree well with experiments, and better than those from generalized gradient approximation calculations. The Pv-PPv phase boundary calculated from our QMC equations of state is also consistent with experiments, and better than previous local density approximation calculations. Lastly, we discuss the implications for double crossing of the Pv-PPv boundary in the Earth.

  14. Equations of state and stability of MgSiO3 perovskite and post-perovskite phases from quantum Monte Carlo simulations

    DOE PAGES

    Lin, Yangzheng; Cohen, Ronald E.; Stackhouse, Stephen; Driver, Kevin P.; Militzer, Burkhard; Shulenburger, Luke; Kim, Jeongnim

    2014-11-10

    In this study, we have performed quantum Monte Carlo (QMC) simulations and density functional theory calculations to study the equations of state of MgSiO3 perovskite (Pv, bridgmanite) and post-perovskite (PPv) up to the pressure and temperature conditions of the base of Earth's lower mantle. The ground-state energies were derived using QMC simulations and the temperature-dependent Helmholtz free energies were calculated within the quasiharmonic approximation and density functional perturbation theory. The equations of state for both phases of MgSiO3 agree well with experiments, and better than those from generalized gradient approximation calculations. The Pv-PPv phase boundary calculated from our QMC equationsmore » of state is also consistent with experiments, and better than previous local density approximation calculations. Lastly, we discuss the implications for double crossing of the Pv-PPv boundary in the Earth.« less

  15. Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction

    NASA Astrophysics Data System (ADS)

    Shepherd, James J.; Henderson, Thomas M.; Scuseria, Gustavo E.

    2016-03-01

    Over the past few years, pair coupled cluster doubles (pCCD) has shown promise for the description of strong correlation. This promise is related to its apparent ability to match results from doubly occupied configuration interaction (DOCI), even though the latter method has exponential computational cost. Here, by modifying the full configuration interaction quantum Monte Carlo algorithm to sample only the seniority zero sector of Hilbert space, we show that the DOCI and pCCD energies are in agreement for a variety of 2D Hubbard models, including for systems well out of reach for conventional configuration interaction algorithms. Our calculations are aided by the sign problem being much reduced in the seniority zero space compared with the full space. We present evidence for this and then discuss the sign problem in terms of the wave function of the system which appears to have a simplified sign structure.

  16. Investigating Disjoint Non-Kekulé Diradicals with Quantum Monte Carlo: The Tetramethyleneethane Molecule through the Jastrow Antisymmetrized Geminal Power Wave Function.

    PubMed

    Barborini, Matteo; Coccia, Emanuele

    2015-12-01

    Disjoint non-Kekulé molecules are diradicals that present two independent radical centers and can violate Hund's rule, according to which the ground state should have triplet spin symmetry. The prototype of this class of systems is the tetramethyleneethane (TME) molecule for which indeed ion photoelectron spectroscopy (IPS) experiments revealed the singlet (1)A state to be more stable than the triplet (3)Bu. In this work we investigate the potential energy curves of the two spin states of TME and of the two anionic states of TME(-) ((2)A and (2)B1) as a function of the torsion of the central dihedral angle, with quantum Monte Carlo methods and a Jastrow Antisymmetrized Geminal Power wave function. Through ab initio geometrical optimizations we study the possible structural interconversions between the states, finding results which are in full agreement with the IPS experimental data.

  17. Convergence of the variational parameter without convergence of the energy in Quantum Monte Carlo (QMC) calculations using the Stochastic Gradient Approximation

    NASA Astrophysics Data System (ADS)

    Nissenbaum, Daniel; Lin, Hsin; Barbiellini, Bernardo; Bansil, Arun

    2009-03-01

    To study the performance of the Stochastic Gradient Approximation (SGA) for variational Quantum Monte Carlo methods, we have considered lithium nano-clusters [1] described by Hartree-Fock wavefunctions multiplied by two-body Jastrow factors with a single variational parameter b. Even when the system size increases, we have shown the feasibility of obtaining an accurate value of b that minimizes the energy without an explicit calculation of the energy itself. The present SGA algorithm is so efficient because an analytic gradient formula is used and because the statistical noise in the gradient is smaller than in the energy [2]. Interestingly, in this scheme the absolute value of the gradient is less important than the sign of the gradient. Work supported in part by U.S. DOE. [1] D. Nissenbaum et al., Phys. Rev. B 76, 033412 (2007). [2] A. Harju, J. Low. Temp. Phys. 140, 181 (2005).

  18. Triplet p + ip pairing correlations in the doped Kane-Mele-Hubbard model: A quantum Monte Carlo study

    SciTech Connect

    Ma, Tianxing; Lin, Hai-Qing; Gubernatis, James E.

    2015-09-01

    By using the constrained-phase quantum Monte Carlo method, we performed a systematic study of the pairing correlations in the ground state of the doped Kane-Mele-Hubbard model on a honeycomb lattice. We find that pairing correlations with d + id symmetry dominate close to half filling, but pairing correlations with p+ip symmetry dominate as hole doping moves the system below three-quarters filling. We correlate these behaviors of the pairing correlations with the topology of the Fermi surfaces of the non-interacting problem. We also find that the effective pairing correlation is enhanced greatly as the interaction increases, and these superconducting correlations are robust against varying the spin-orbit coupling strength. Finally, our numerical results suggest a possible way to realize spin triplet superconductivity in doped honeycomb-like materials or ultracold atoms in optical traps.

  19. Ab initio quantum Monte Carlo calculations of spin superexchange in cuprates: the benchmarking case of Ca2CuO3

    SciTech Connect

    Foyevtsova, Kateryna; Krogel, Jaron T; Kim, Jeongnim; Kent, Paul R; Dagotto, Elbio R; Reboredo, Fernando A

    2014-01-01

    In view of the continuous theoretical efforts aimed at an accurate microscopic description of the strongly correlated transition metal oxides and related materials, we show that with continuum quantum Monte Carlo (QMC) calculations it is possible to obtain the value of the spin superexchange coupling constant of a copper oxide in a quantitatively excellent agreement with experiment. The variational nature of the QMC total energy allows us to identify the best trial wave function out of the available pool of wave functions, which makes the approach essentially free from adjustable parameters and thus truly ab initio. The present results on magnetic interactions suggest that QMC is capable of accurately describing ground state properties of strongly correlated materials.

  20. The isotropic nuclear magnetic shielding constants of acetone in supercritical water: a sequential Monte Carlo/quantum mechanics study including solute polarization.

    PubMed

    Fonseca, Tertius L; Coutinho, Kaline; Canuto, Sylvio

    2008-07-21

    The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7+/-0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm.

  1. Monte Carlo simulation of a quantum noise limited Čerenkov detector based on air-spaced light guiding taper for megavoltage x-ray imaging

    SciTech Connect

    Teymurazyan, A.; Rowlands, J. A.; Pang, G.

    2014-04-15

    Purpose: Electronic Portal Imaging Devices (EPIDs) have been widely used in radiation therapy and are still needed on linear accelerators (Linacs) equipped with kilovoltage cone beam CT (kV-CBCT) or MRI systems. Our aim is to develop a new high quantum efficiency (QE) Čerenkov Portal Imaging Device (CPID) that is quantum noise limited at dose levels corresponding to a single Linac pulse. Methods: Recently a new concept of CPID for MV x-ray imaging in radiation therapy was introduced. It relies on Čerenkov effect for x-ray detection. The proposed design consisted of a matrix of optical fibers aligned with the incident x-rays and coupled to an active matrix flat panel imager (AMFPI) for image readout. A weakness of such design is that too few Čerenkov light photons reach the AMFPI for each incident x-ray and an AMFPI with an avalanche gain is required in order to overcome the readout noise for portal imaging application. In this work the authors propose to replace the optical fibers in the CPID with light guides without a cladding layer that are suspended in air. The air between the light guides takes on the role of the cladding layer found in a regular optical fiber. Since air has a significantly lower refractive index (∼1 versus 1.38 in a typical cladding layer), a much superior light collection efficiency is achieved. Results: A Monte Carlo simulation of the new design has been conducted to investigate its feasibility. Detector quantities such as quantum efficiency (QE), spatial resolution (MTF), and frequency dependent detective quantum efficiency (DQE) have been evaluated. The detector signal and the quantum noise have been compared to the readout noise. Conclusions: Our studies show that the modified new CPID has a QE and DQE more than an order of magnitude greater than that of current clinical systems and yet a spatial resolution similar to that of current low-QE flat-panel based EPIDs. Furthermore it was demonstrated that the new CPID does not require an

  2. Tests on novel pseudo-potentials generated from diffusion Monte Carlo data.

    NASA Astrophysics Data System (ADS)

    Reboredo, Fernando; Hood, Randolph; Bajdich, Michal

    2012-02-01

    Since Dmitri Mendeleev developed a table in 1869 to illustrate recurring ("periodic") trends of the elements, it has been understood that most chemical and physical properties can be described by taking into account the outer most electrons of the atoms. These valence electrons are mainly responsible for the chemical bond. In many ab-initio approaches only valence electrons are taken into account and a pseudopotential is used to mimic the response of the core electrons. Typically an all-electron calculation is used to generate a pseudopotential that is used either within density functional theory or quantum chemistry approaches. In this talk we explain and demonstrate a new method to generate pseudopotentials directly from all-electron many-body diffusion Monte Carlo (DMC) calculations and discuss the results of of the transferability of these pseudopotentials. The advantages of incorporating the exchange and correlation directly from DMC into the pseudopotential are also discussed.

  3. Quantum Monte Carlo study of hard-core bosons in a pyrochlore lattice with six-site ring-exchange interactions

    NASA Astrophysics Data System (ADS)

    Tieman, Catherine; Rousseau, Valery

    Highly frustrated quantum systems on lattices can exhibit a wide variety of phases. In addition to the usual Mott insulating and superfluid phases, these systems can also produce some so-called ``exotic phases'', such as super-solid and valence-bond-solid phases. An example of particularly frustrated lattice is the pyrochlore structure, which is formed by corner-sharing tetrahedrons. Many real materials adopt this structure, for instance the crystal Cd2 Re2O7 , which exhibits superconducting properties. However, the complex structure of these materials combined with the complexity of the dominant interactions that describe them makes their analytical study difficult. Also, approximate methods, such as mean-field theory, fail to give a correct description of these systems. In this work, we report on the first exact quantum Monte Carlo study of a model of hard-core bosons in a pyrochlore lattice with six-site ring-exchange interactions, using the Stochastic Green Function (SGF) algorithm. We analyze the superfluid density and the structure factor as functions of the filling and ring-exchange interaction strength, and we map out the ground state phase diagram.

  4. Combined Monte Carlo and quantum mechanics study of the hydration of the guanine-cytosine base pair.

    PubMed

    Coutinho, Kaline; Ludwig, Valdemir; Canuto, Sylvio

    2004-06-01

    We present a computer simulation study of the hydration of the guanine-cytosine (GC) hydrogen-bonded complex. Using first principles density-functional theory, with gradient-corrected exchange-correlation and Monte Carlo simulation, we include thermal contribution, structural effects, solvent polarization, and the water-water and water-GC hydrogen bond interaction to show that the GC interaction in an aqueous environment is weakened to about 70% of the value obtained for an isolated complex. We also analyze in detail the preferred hydration sites of the GC pair and show that on the average it makes around five hydrogen bonds with water.

  5. Quantum Monte Carlo Study of the Ground-State Properties of a Fermi Gas in the BCS-BEC Crossover

    SciTech Connect

    Giorgini, S.; Astrakharchik, G. E.; Boronat, J.; Casulleras, J.

    2006-11-07

    The ground-state properties of a two-component Fermi gas with attractive short-range interactions are calculated using the fixed-node diffusion Monte Carlo method. The interaction strength is varied over a wide range by tuning the value of the s-wave scattering length of the two-body potential. We calculate the ground-state energy per particle and we characterize the equation of state of the system. Off-diagonal long-range order is investigated through the asymptotic behavior of the two-body density matrix. The condensate fraction of pairs is calculated in the unitary limit and on both sides of the BCS-BEC crossover.

  6. Magnetic and pairing properties of a two-orbital model for the pnictide superconductors: a quantum Monte Carlo study.

    PubMed

    Liu, Guang-Kun; Huang, Zhong-Bing; Wang, Yong-Jun

    2014-08-13

    Using the constrained-path Monte Carlo method, a two-orbital model for the pnictide superconductors is studied at half filling and in both the electron- and hole-doped cases. At half filling, a stable (π, 0)/(0, π) magnetic order is explicitly observed and the system tends to be in an orthomagnetic order rather than the striped antiferromagnetic order on increasing the Coulomb repulsion U. In the electron-doped case, the (π, 0)/(0, π) magnetic order is enhanced upon doping and suppressed eventually and a s(±) pairing state dominates all the possible nearest-neighbour-bond pairings. Whereas in the hole-doped case, the magnetic order is straightforwardly suppressed and two nearly degenerate A(1g) and B(1g) intraband pairings become the dominant ones. PMID:25029986

  7. Quantum Monte Carlo for the x-ray absorption spectrum of pyrrole at the nitrogen K-edge

    SciTech Connect

    Zubarev, Dmitry Yu.; Austin, Brian M.; Lester, William A. Jr.

    2012-04-14

    Fixed-node diffusion Monte Carlo (FNDMC) is used to simulate the x-ray absorption spectrum of a gas-phase pyrrole molecule at the nitrogen K-edge. Trial wave functions for core-excited states are constructed from ground-state Kohn-Sham determinants substituted with singly occupied natural orbitals from configuration interaction with single excitations calculations of the five lowest valence-excited triplet states. The FNDMC ionization potential (IP) is found to lie within 0.3 eV of the experimental value of 406.1 {+-} 0.1 eV. The transition energies to anti-bonding virtual orbitals match the experimental spectrum after alignment of IP values and agree with the existing assignments.

  8. Electronic states of Al and Al{sub 2} using quantum Monte Carlo with an effective core potential

    SciTech Connect

    Greeff, C.W.; Lester, W.A. Jr.; Hammond, B.L.

    1996-02-01

    The diffusion Monte Carlo method is applied in conjunction with an ab initio effective core potential to compute energies of some neutral and charged states of Al and Al{sub 2}. The computed ionization potentials, electron affinities and dissociation energies differ from measured values by at most a few hundredths of eV. The computed dissociation energy of Al{sub 2} agrees with the most extensive CI calculations. It appears that our dissociation energy for Al{sup {minus}}{sub 2} is the most accurate to date. The quality of the results indicates that the use of the pseudopotential is not an important limitation on the accuracy of these calculations. Variational wavefunctions with Boys-Handy correlation functions are found to give more than 70{percent} of the correlation energy with 8 optimized parameters. These optimized trial functions are used together with numerical integration to localize the pseudopotential. {copyright} {ital 1996 American Institute of Physics.}

  9. Porphyrins as Corrosion Inhibitors for N80 Steel in 3.5% NaCl Solution: Electrochemical, Quantum Chemical, QSAR and Monte Carlo Simulations Studies.

    PubMed

    Singh, Ambrish; Lin, Yuanhua; Quraishi, Mumtaz A; Olasunkanmi, Lukman O; Fayemi, Omolola E; Sasikumar, Yesudass; Ramaganthan, Baskar; Bahadur, Indra; Obot, Ime B; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

    2015-08-18

    The inhibition of the corrosion of N80 steel in 3.5 wt. % NaCl solution saturated with CO2 by four porphyrins, namely 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphyrin (HPTB), 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphyrin (T4PP), 4,4',4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrakis(benzoic acid) (THP) and 5,10,15,20-tetraphenyl-21H,23H-porphyrin (TPP) was studied using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, scanning electrochemical microscopy (SECM) and scanning electron microscopy (SEM) techniques. The results showed that the inhibition efficiency, η% increases with increasing concentration of the inhibitors. The EIS results revealed that the N80 steel surface with adsorbed porphyrins exhibited non-ideal capacitive behaviour with reduced charge transfer activity. Potentiodynamic polarization measurements indicated that the studied porphyrins acted as mixed type inhibitors. The SECM results confirmed the adsorption of the porphyrins on N80 steel thereby forming a relatively insulated surface. The SEM also confirmed the formation of protective films of the porphyrins on N80 steel surface thereby protecting the surface from direct acid attack. Quantum chemical calculations, quantitative structure activity relationship (QSAR) were also carried out on the studied porphyrins and the results showed that the corrosion inhibition performances of the porphyrins could be related to their EHOMO, ELUMO, ω, and μ values. Monte Carlo simulation studies showed that THP has the highest adsorption energy, while T4PP has the least adsorption energy in agreement with the values of σ from quantum chemical calculations.

  10. Valence-bond crystal in the extended kagome spin-(1)/(2) quantum Heisenberg antiferromagnet: A variational Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Iqbal, Yasir; Becca, Federico; Poilblanc, Didier

    2011-03-01

    The highly frustrated spin-(1)/(2) quantum Heisenberg model with both nearest (J1) and next-nearest (J2) neighbor exchange interactions is revisited by using an extended variational space of projected wave functions that are optimized with state-of-the-art methods. Competition between modulated valence-bond crystals (VBCs) proposed in the literature and the Dirac spin liquid (DSL) is investigated. We find that the addition of a small ferromagnetic next-nearest-neighbor exchange coupling |J2|>0.09J1 leads to stabilization of a 36-site unit cell VBC, although the DSL remains a local minimum of the variational parameter landscape. This implies that the VBC is not trivially connected to the DSL; instead it possesses a nontrivial flux pattern and large dimerization.

  11. Solvent effects on the absorption spectrum and first hyperpolarizability of keto-enol tautomeric forms of anil derivatives: A Monte Carlo/quantum mechanics study.

    PubMed

    Adriano Junior, L; Fonseca, T L; Castro, M A

    2016-06-21

    Theoretical results for the absorption spectrum and electric properties of the enol and keto tautomeric forms of anil derivatives in the gas-phase and in solution are presented. The electronic properties in chloroform, acetonitrile, methanol, and water were determined by carrying out sequential Monte Carlo simulations and quantum mechanics calculations based on the time dependent density functional theory and on the second-order Møller-Plesset perturbation theory method. The results illustrate the role played by electrostatic interactions in the electronic properties of anil derivatives in a liquid environment. There is a significant increase of the dipole moment in solution (20%-100%) relative to the gas-phase value. Solvent effects are mild for the absorption spectrum and linear polarizability but they can be particularly important for first hyperpolarizability. A large first hyperpolarizability contrast between the enol and keto forms is observed when absorption spectra present intense lowest-energy absorption bands. Dynamic results for the first hyperpolarizability are in qualitative agreement with the available experimental results.

  12. Many-body ab initio diffusion quantum Monte Carlo applied to the strongly correlated oxide NiO

    SciTech Connect

    Mitra, Chandrima; Krogel, Jaron T.; Santana, Juan A.; Reboredo, Fernando A.

    2015-10-28

    We present a many-body diffusion quantum Monte Carlo (DMC) study of the bulk and defect properties of NiO. We find excellent agreement with experimental values, within 0.3%, 0.6%, and 3.5% for the lattice constant, cohesive energy, and bulk modulus, respectively. The quasiparticle bandgap was also computed, and the DMC result of 4.72 (0.17) eV compares well with the experimental value of 4.3 eV. Furthermore, DMC calculations of excited states at the L, Z, and the gamma point of the Brillouin zone reveal a flat upper valence band for NiO, in good agreement with Angle Resolved Photoemission Spectroscopy results. To study defect properties, we evaluated the formation energies of the neutral and charged vacancies of oxygen and nickel in NiO. A formation energy of 7.2 (0.15) eV was found for the oxygen vacancy under oxygen rich conditions. For the Ni vacancy, we obtained a formation energy of 3.2 (0.15) eV under Ni rich conditions. Lastly, these results confirm that NiO occurs as a p-type material with the dominant intrinsic vacancy defect being Ni vacancy. (C) 2015 AIP Publishing LLC.

  13. Using quantum Monte Carlo for the interaction of water with carbon and BN based substrates and assessing exchange-correlation functionals

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine; Alfe, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    The interaction of water with the pure surfaces, graphene and hexagonal boron nitride (h- BN), has received a lot of attention because of interesting phenomena exhibited by these systems and their promising potential applications in clean energy, water purification, hydrogen storage, and bio-sensing. BN doped graphene can also now be made, opening the way to carefully designed hybrid materials. However, much of the fundamental mechanisms regarding the interaction between these surfaces and water is still not well understood. We use quantum Monte Carlo to establish accurate benchmarks for water on a number of carbonaceous and BN based substrates, including 2-dimensional periodic surfaces, for which van der Waals interactions play a key role. The benchmarks are then used to test and understand various exchange-correlation functionals in density functional theory. We find that the physisorption of water is poorly described in terms of the adsorption site and the interaction energy by a range of different classes of exchange- correlation functionals, including some that account for dispersion, and we show where these inadequacies might come from.

  14. Solvent effects on the absorption spectrum and first hyperpolarizability of keto-enol tautomeric forms of anil derivatives: A Monte Carlo/quantum mechanics study

    NASA Astrophysics Data System (ADS)

    Adriano Junior, L.; Fonseca, T. L.; Castro, M. A.

    2016-06-01

    Theoretical results for the absorption spectrum and electric properties of the enol and keto tautomeric forms of anil derivatives in the gas-phase and in solution are presented. The electronic properties in chloroform, acetonitrile, methanol, and water were determined by carrying out sequential Monte Carlo simulations and quantum mechanics calculations based on the time dependent density functional theory and on the second-order Møller-Plesset perturbation theory method. The results illustrate the role played by electrostatic interactions in the electronic properties of anil derivatives in a liquid environment. There is a significant increase of the dipole moment in solution (20%-100%) relative to the gas-phase value. Solvent effects are mild for the absorption spectrum and linear polarizability but they can be particularly important for first hyperpolarizability. A large first hyperpolarizability contrast between the enol and keto forms is observed when absorption spectra present intense lowest-energy absorption bands. Dynamic results for the first hyperpolarizability are in qualitative agreement with the available experimental results.

  15. The Numerical Comparison of Magnetic Susceptibility and Heat Capacity of TMNIN with the Result of a Quantum Monte Carlo Method for the Haldane System

    NASA Astrophysics Data System (ADS)

    Ito, Masakazu; Mito, Masaki; Deguchi, Hiroyuki; Takeda, Kazuyoshi

    1994-03-01

    The measurements of magnetic heat capacity and susceptibility of one-dimensional S=1 antiferromagnet (CH3)4NNi(NO2)3 (TMNIN) have been carried out in order to make comparison with the theoretical results of a quantum Monte Carlo method for the Haldane system. The results for the heat capacity, which show a broad maximum around 10 K, are well reproduced by the theory with the interaction J/k B=-12.0±1.0 K in the temperature range T>0.2\\mid J\\mid S(S+1)/k_B. The low temperature heat capacity exhibits an exponential decay with gap energy Δ/k B=5.3±0.2 K, which gives {\\mitΔ}=0.44\\mid J\\mid , in contrast to the linear dependence on temperature as in the case for half integer spin. The residual magnetic entropy below 0.7 K is estimated to be 0.07% of Nk B ln 3, which denies the possibility of three-dimensional ordering of the spin system at lower temperatures. The observed susceptibility also agrees with the theory with J/k B=-10.9 K and g=2.02 in the whole temperature region, when we take the effect from the finite length of the chains into consideration.

  16. Binding and Diffusion of Lithium in Graphite: Quantum Monte-Carlo benchmarks and validation of van der Waals density functional methods

    NASA Astrophysics Data System (ADS)

    Kent, Paul; Ganesh, Panchapakesan; Yoon, Mina; Kim, Jeongnim; Reboredo, Fernando

    2013-03-01

    Benchmark diffusion quantum monte-carlo (DMC) studies of the adsorption and diffusion of atomic lithium in graphite are compared with density functional theory (DFT) calculations using several van der Waals methods. The charge transfer is captured adequately with conventional local density functionals. At fixed geometries, these yield surprisingly accurate energetics. In unconstrained geometries, van der Waals corrections are required to correctly reproduce graphite and lithium binding. We find that the empirical method of Grimme et al. only gives correct diffusion barriers when the Li polarizability is reduced to nearly zero, consistent with the charge transfer in the solid-state environment. The Tkatchenko-Scheffler scheme captures the polarizability reduction, yielding accurate results at low computational cost. The self-consistent vdw-DF2 functional yields the best overall results but at increased cost. Slight differences in barrier heights remain with all the DFT approaches compared to the DMC. These results establish a hierarchy of modeling approaches for the lithium-carbon system. Partially supported by the Fluid Interface Reactions, Structures and Transport Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

  17. Quantum Monte Carlo calculations of electromagnetic transitions in $^8$Be with meson-exchange currents derived from chiral effective field theory

    SciTech Connect

    Pastore, S.; Wiringa, Robert B.; Pieper, Steven C.; Schiavilla, Rocco

    2014-08-01

    We report quantum Monte Carlo calculations of electromagnetic transitions in $^8$Be. The realistic Argonne $v_{18}$ two-nucleon and Illinois-7 three-nucleon potentials are used to generate the ground state and nine excited states, with energies that are in excellent agreement with experiment. A dozen $M1$ and eight $E2$ transition matrix elements between these states are then evaluated. The $E2$ matrix elements are computed only in impulse approximation, with those transitions from broad resonant states requiring special treatment. The $M1$ matrix elements include two-body meson-exchange currents derived from chiral effective field theory, which typically contribute 20--30\\% of the total expectation value. Many of the transitions are between isospin-mixed states; the calculations are performed for isospin-pure states and then combined with the empirical mixing coefficients to compare to experiment. In general, we find that transitions between states that have the same dominant spatial symmetry are in decent agreement with experiment, but those transitions between different spatial symmetries are often significantly underpredicted.

  18. Part i: Lie-Backlund Theory and Linearization of Differential Equations. Part II: Monte Carlo Simulations of 1-D Quantum Spin Models.

    NASA Astrophysics Data System (ADS)

    Cullen, John J.

    Part I begins with an account of groups of Lie -Back-lund (L-B) tangent transformations; it is then shown that L-B symmetry operators depending on integrals (nonlocal variables), such as discussed by Konopelchenko and Mokhnachev (1979), are related by change of variables to the L-B operators which involve no more than derivatives. A general method is set down for transforming a given L-B operator into a new one, by any invertible transformation depending on (. . ., D(,x)('-1) u, u, u(,x), . . .). It is shown that once a given differential equation admits a L-B operator, there is in general a very large number of related ("secondary") equations which admit the same operator. The L-B Theory involving nonlocal variables is used to characterize group theoretically the linearization both of the Burgers equation, u(,t) + uu(,x) - u(,xx) = 0, and of the o.d.e. u(,xx) + (omega)('2)(x)u + Ku('-3) = 0. Secondary equations are found to play an important role in understanding the group theoretical background to the linearization of differential equations. Part II deals with Monte Carlo simulations of the l-d quantum Heisenberg and XY-models, using an approach suggested by Suzuki (1976). The simulation is actually carried out on a 2-d, m x N, Isinglike system, equivalent to the original N-spin quantum system when m (--->) (INFIN). The results for m (LESSTHEQ) 10 and kT/(VBAR)J(VBAR) (GREATERTHEQ) .0125 are good enough to show that the method is generally applicable to quantum spin models; however some difficulties caused by singular bonding in the classical lattice (Wiesler 1982) and by the generation of unwanted states have to be taken into account in practice. The finite-size scaling method of Fisher and Ferdinard is adapted for use near T = 0 in the ferromagnetic Heisenberg model; applied to the simulation data it shows that the low temperature susceptibiltiy behaves at T('-(gamma)), where (gamma) = 1.32 (+OR-) 10%. Also, simple and potentially useful finite-size scaling

  19. Comparison of the completely renormalized equation-of-motion coupled-cluster and Quantum Monte Carlo results for the low-lying electronic states of methylene

    NASA Astrophysics Data System (ADS)

    Gour, Jeffrey R.; Piecuch, Piotr; Włoch, Marta

    2010-10-01

    The left-eigenstate completely renormalized (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as CR-EOMCC(2,3) [M. Włoch et al., Mol. Phys. 104, 2149 (2006); P. Piecuch et al., Int. J. Quantum Chem. 109, 3268 (2009)], and the companion ground-state CR-CC(2,3) methodology [P. Piecuch and M. Włoch, J. Chem. Phys. 123, 224105 (2005); P. Piecuch et al., Chem. Phys. Lett. 418, 467 (2006)] are used to determine the total electronic and adiabatic excitation energies corresponding to the ground and lowest three excited states of methylene. The emphasis is on comparing the CR-CC(2,3)/CR-EOMCC(2,3) results obtained with the large correlation-consistent basis sets of the aug-cc-pCV xZ (x = T, Q, 5) quality and the corresponding complete basis set (CBS) limits with the recently published variational and diffusion Quantum Monte Carlo (QMC) data [P. Zimmerman et al., J. Chem. Phys. 131, 124103 (2009)]. It is demonstrated that the CBS CR-CC(2,3)/CR-EOMCC(2,3) results are in very good agreement with the best QMC, i.e. diffusion MC (DMC) data, with errors in the total and adiabatic excitation energies of all calculated states on the order of a few millihartree and less than 0.1 eV, respectively, even for the challenging, strongly multi-reference C 1 A 1 state for which the basic EOMCC approach with singles and doubles completely fails. The agreement between the CBS CR-CC(2,3)/CR-EOMCC(2,3) and variational MC (VMC) results for the total energies is not as good as in the DMC case, but the excitation energies resulting from the CBS CR-CC(2,3)/CR-EOMCC(2,3) and VMC calculations agree very well.

  20. Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz

    NASA Astrophysics Data System (ADS)

    Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco; Sorella, Sandro; Casula, Michele

    2015-06-01

    We study the ionization energy, electron affinity, and the π → π∗ (1La) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the 1La excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral 1La excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.

  1. Vertical and adiabatic excitations in anthracene from quantum Monte Carlo: Constrained energy minimization for structural and electronic excited-state properties in the JAGP ansatz

    SciTech Connect

    Dupuy, Nicolas; Bouaouli, Samira; Mauri, Francesco Casula, Michele; Sorella, Sandro

    2015-06-07

    We study the ionization energy, electron affinity, and the π → π{sup ∗} ({sup 1}L{sub a}) excitation energy of the anthracene molecule, by means of variational quantum Monte Carlo (QMC) methods based on a Jastrow correlated antisymmetrized geminal power (JAGP) wave function, developed on molecular orbitals (MOs). The MO-based JAGP ansatz allows one to rigorously treat electron transitions, such as the HOMO → LUMO one, which underlies the {sup 1}L{sub a} excited state. We present a QMC optimization scheme able to preserve the rank of the antisymmetrized geminal power matrix, thanks to a constrained minimization with projectors built upon symmetry selected MOs. We show that this approach leads to stable energy minimization and geometry relaxation of both ground and excited states, performed consistently within the correlated QMC framework. Geometry optimization of excited states is needed to make a reliable and direct comparison with experimental adiabatic excitation energies. This is particularly important in π-conjugated and polycyclic aromatic hydrocarbons, where there is a strong interplay between low-lying energy excitations and structural modifications, playing a functional role in many photochemical processes. Anthracene is an ideal benchmark to test these effects. Its geometry relaxation energies upon electron excitation are of up to 0.3 eV in the neutral {sup 1}L{sub a} excited state, while they are of the order of 0.1 eV in electron addition and removal processes. Significant modifications of the ground state bond length alternation are revealed in the QMC excited state geometry optimizations. Our QMC study yields benchmark results for both geometries and energies, with values below chemical accuracy if compared to experiments, once zero point energy effects are taken into account.

  2. Equations of state and phase transitions in (Mg,Fe)SiO3 perovskite and post-perovskites, position of the phase boundary and its double crossing, by Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Cohen, R. E.; Lin, Y.

    2015-12-01

    We have performed quantum Monte Carlo (QMC) simulations and density functional theory calculations to study the equations of state and phase transitions in (Mg,Fe)SiO3 perovskite (Pv, bridgmanite) and post-perovskite (PPv) .[1] The ground-state energies were derived using quantum QMC simulations and the temperature-dependent Helmholtz free energies were calculated within the quasiharmonic approximation and density functional perturbation theory. Quantum Monte Carlo (QMC) within Diffusion Monte Carlo (DMC) is a stochastic numerical solution of Schrödinger's equation within the fixed many-particle nodes obtained, in our case, from a determinant of DFT orbitals. Agreement with experiments is improved over DFT alone. Furthermore, we obtain statistical error bounds on the results, rather than the unconstrained errors of DFT. The Pv-PPv phase boundary calculated from our QMC equations of state is also consistent with experiments, and better than previous DFT computations. In order to understand the H-phase reported in (Mg,Fe)SiO3 [2], we have performed evolutionary structure searching for FeSiO3.[3] We find a new structure type which may be consistent with the experimental observations, but is a lower pressure, less dense, phase. We have built a thermodynamic model for (Mg,Fe)SiO3 perovskite as a function of P and T, and will discuss implications for the location of the phase boundary in D'' and its double crossing [4]. This work is supported by NSF and the ERC Advanced Grant ToMCaT. [1] Y. Lin, R. E. Cohen, S. Stackhouse, K. P. Driver, B. Militzer, L. Shulenburger, and J. Kim, Phys. Rev. B 90 (2014). [2] L. Zhang et al., Science 344, 877 (2014). [3] R. E. Cohen and Y. Lin, Phys. Rev. B 90 (2014). [4] J.W. Hernlund, C. Thomas and P.J. Tackley, Nature 434, 882 (2005).

  3. Self-healing diffusion quantum Monte Carlo algorithms: methods for direct reduction of the fermion sign error in electronic structure calculations

    SciTech Connect

    Reboredo, F A; Hood, R Q; Kent, P C

    2009-01-06

    We develop a formalism and present an algorithm for optimization of the trial wave-function used in fixed-node diffusion quantum Monte Carlo (DMC) methods. The formalism is based on the DMC mixed estimator of the ground state probability density. We take advantage of a basic property of the walker configuration distribution generated in a DMC calculation, to (i) project-out a multi-determinant expansion of the fixed node ground state wave function and (ii) to define a cost function that relates the interacting-ground-state-fixed-node and the non-interacting trial wave functions. We show that (a) locally smoothing out the kink of the fixed-node ground-state wave function at the node generates a new trial wave function with better nodal structure and (b) we argue that the noise in the fixed-node wave function resulting from finite sampling plays a beneficial role, allowing the nodes to adjust towards the ones of the exact many-body ground state in a simulated annealing-like process. Based on these principles, we propose a method to improve both single determinant and multi-determinant expansions of the trial wave function. The method can be generalized to other wave function forms such as pfaffians. We test the method in a model system where benchmark configuration interaction calculations can be performed and most components of the Hamiltonian are evaluated analytically. Comparing the DMC calculations with the exact solutions, we find that the trial wave function is systematically improved. The overlap of the optimized trial wave function and the exact ground state converges to 100% even starting from wave functions orthogonal to the exact ground state. Similarly, the DMC total energy and density converges to the exact solutions for the model. In the optimization process we find an optimal non-interacting nodal potential of density-functional-like form whose existence was predicted in a previous publication [Phys. Rev. B 77 245110 (2008)]. Tests of the method are

  4. Spin Density Distribution in Open-Shell Transition Metal Systems: A Comparative Post-Hartree-Fock, Density Functional Theory, and Quantum Monte Carlo Study of the CuCl2 Molecule.

    PubMed

    Caffarel, Michel; Giner, Emmanuel; Scemama, Anthony; Ramírez-Solís, Alejandro

    2014-12-01

    We present a comparative study of the spatial distribution of the spin density of the ground state of CuCl2 using Density Functional Theory (DFT), quantum Monte Carlo (QMC), and post-Hartree-Fock wave function theory (WFT). A number of studies have shown that an accurate description of the electronic structure of the lowest-lying states of this molecule is particularly challenging due to the interplay between the strong dynamical correlation effects in the 3d shell and the delocalization of the 3d hole over the chlorine atoms. More generally, this problem is representative of the difficulties encountered when studying open-shell metal-containing molecular systems. Here, it is shown that qualitatively different results for the spin density distribution are obtained from the various quantum-mechanical approaches. At the DFT level, the spin density distribution is found to be very dependent on the functional employed. At the QMC level, Fixed-Node Diffusion Monte Carlo (FN-DMC) results are strongly dependent on the nodal structure of the trial wave function. Regarding wave function methods, most approaches not including a very high amount of dynamic correlation effects lead to a much too high localization of the spin density on the copper atom, in sharp contrast with DFT. To shed some light on these conflicting results Full CI-type (FCI) calculations using the 6-31G basis set and based on a selection process of the most important determinants, the so-called CIPSI approach (Configuration Interaction with Perturbative Selection done Iteratively) are performed. Quite remarkably, it is found that for this 63-electron molecule and a full CI space including about 10(18) determinants, the FCI limit can almost be reached. Putting all results together, a natural and coherent picture for the spin distribution is proposed. PMID:26583212

  5. Spin Density Distribution in Open-Shell Transition Metal Systems: A Comparative Post-Hartree-Fock, Density Functional Theory, and Quantum Monte Carlo Study of the CuCl2 Molecule.

    PubMed

    Caffarel, Michel; Giner, Emmanuel; Scemama, Anthony; Ramírez-Solís, Alejandro

    2014-12-01

    We present a comparative study of the spatial distribution of the spin density of the ground state of CuCl2 using Density Functional Theory (DFT), quantum Monte Carlo (QMC), and post-Hartree-Fock wave function theory (WFT). A number of studies have shown that an accurate description of the electronic structure of the lowest-lying states of this molecule is particularly challenging due to the interplay between the strong dynamical correlation effects in the 3d shell and the delocalization of the 3d hole over the chlorine atoms. More generally, this problem is representative of the difficulties encountered when studying open-shell metal-containing molecular systems. Here, it is shown that qualitatively different results for the spin density distribution are obtained from the various quantum-mechanical approaches. At the DFT level, the spin density distribution is found to be very dependent on the functional employed. At the QMC level, Fixed-Node Diffusion Monte Carlo (FN-DMC) results are strongly dependent on the nodal structure of the trial wave function. Regarding wave function methods, most approaches not including a very high amount of dynamic correlation effects lead to a much too high localization of the spin density on the copper atom, in sharp contrast with DFT. To shed some light on these conflicting results Full CI-type (FCI) calculations using the 6-31G basis set and based on a selection process of the most important determinants, the so-called CIPSI approach (Configuration Interaction with Perturbative Selection done Iteratively) are performed. Quite remarkably, it is found that for this 63-electron molecule and a full CI space including about 10(18) determinants, the FCI limit can almost be reached. Putting all results together, a natural and coherent picture for the spin distribution is proposed.

  6. Calculation of all-electron wavefunction of hemoprotein cytochrome c by density functional theory

    NASA Astrophysics Data System (ADS)

    Sato, Fumitoshi; Yoshihiro, Tamotsu; Era, Makoto; Kashiwagi, Hiroshi

    2001-06-01

    An all-electron wavefunction of horse heart d 6-low-spin ferrocytochrome c (ferrocyt. c) was calculated by our Gaussian-based density functional theory (DFT) molecular orbital (MO) program, ProteinDF with a workstation cluster. It may be the first full-scale DFT calculation of a metalloprotein, and the numbers of orbitals and auxiliary functions are 9600 and 17 578, respectively. We show that the highest occupied MO (HOMO) derives from 3d orbitals of heme Fe and is unexpectedly delocalized while preserving the essential atomic character, which will give room for consideration of the electron transfer processes between proteins. The potential of MO calculations on larger proteins is also discussed with the computational data of cytochrome c (cyt. c).

  7. Large-scale All-electron Density Functional Theory Calculations using Enriched Finite Element Method

    NASA Astrophysics Data System (ADS)

    Kanungo, Bikash; Gavini, Vikram

    We present a computationally efficient method to perform large-scale all-electron density functional theory calculations by enriching the Lagrange polynomial basis in classical finite element (FE) discretization with atom-centered numerical basis functions, which are obtained from the solutions of the Kohn-Sham (KS) problem for single atoms. We term these atom-centered numerical basis functions as enrichment functions. The integrals involved in the construction of the discrete KS Hamiltonian and overlap matrix are computed using an adaptive quadrature grid based on gradients in the enrichment functions. Further, we propose an efficient scheme to invert the overlap matrix by exploiting its LDL factorization and employing spectral finite elements along with Gauss-Lobatto quadrature rules. Finally, we use a Chebyshev polynomial based acceleration technique to compute the occupied eigenspace in each self-consistent iteration. We demonstrate the accuracy, efficiency and scalability of the proposed method on various metallic and insulating benchmark systems, with systems ranging in the order of 10,000 electrons. We observe a 50-100 fold reduction in the overall computational time when compared to classical FE calculations while being commensurate with the desired chemical accuracy. We acknowledge the support of NSF (Grant No. 1053145) and ARO (Grant No. W911NF-15-1-0158) in conducting this work.

  8. Predicting Pt-195 NMR chemical shift using new relativistic all-electron basis set.

    PubMed

    Paschoal, D; Guerra, C Fonseca; de Oliveira, M A L; Ramalho, T C; Dos Santos, H F

    2016-10-01

    Predicting NMR properties is a valuable tool to assist the experimentalists in the characterization of molecular structure. For heavy metals, such as Pt-195, only a few computational protocols are available. In the present contribution, all-electron Gaussian basis sets, suitable to calculate the Pt-195 NMR chemical shift, are presented for Pt and all elements commonly found as Pt-ligands. The new basis sets identified as NMR-DKH were partially contracted as a triple-zeta doubly polarized scheme with all coefficients obtained from a Douglas-Kroll-Hess (DKH) second-order scalar relativistic calculation. The Pt-195 chemical shift was predicted through empirical models fitted to reproduce experimental data for a set of 183 Pt(II) complexes which NMR sign ranges from -1000 to -6000 ppm. Furthermore, the models were validated using a new set of 75 Pt(II) complexes, not included in the descriptive set. The models were constructed using non-relativistic Hamiltonian at density functional theory (DFT-PBEPBE) level with NMR-DKH basis set for all atoms. For the best model, the mean absolute deviation (MAD) and the mean relative deviation (MRD) were 150 ppm and 6%, respectively, for the validation set (75 Pt-complexes) and 168 ppm (MAD) and 5% (MRD) for all 258 Pt(II) complexes. These results were comparable with relativistic DFT calculation, 200 ppm (MAD) and 6% (MRD). © 2016 Wiley Periodicals, Inc. PMID:27510431

  9. Predicting Pt-195 NMR chemical shift using new relativistic all-electron basis set.

    PubMed

    Paschoal, D; Guerra, C Fonseca; de Oliveira, M A L; Ramalho, T C; Dos Santos, H F

    2016-10-01

    Predicting NMR properties is a valuable tool to assist the experimentalists in the characterization of molecular structure. For heavy metals, such as Pt-195, only a few computational protocols are available. In the present contribution, all-electron Gaussian basis sets, suitable to calculate the Pt-195 NMR chemical shift, are presented for Pt and all elements commonly found as Pt-ligands. The new basis sets identified as NMR-DKH were partially contracted as a triple-zeta doubly polarized scheme with all coefficients obtained from a Douglas-Kroll-Hess (DKH) second-order scalar relativistic calculation. The Pt-195 chemical shift was predicted through empirical models fitted to reproduce experimental data for a set of 183 Pt(II) complexes which NMR sign ranges from -1000 to -6000 ppm. Furthermore, the models were validated using a new set of 75 Pt(II) complexes, not included in the descriptive set. The models were constructed using non-relativistic Hamiltonian at density functional theory (DFT-PBEPBE) level with NMR-DKH basis set for all atoms. For the best model, the mean absolute deviation (MAD) and the mean relative deviation (MRD) were 150 ppm and 6%, respectively, for the validation set (75 Pt-complexes) and 168 ppm (MAD) and 5% (MRD) for all 258 Pt(II) complexes. These results were comparable with relativistic DFT calculation, 200 ppm (MAD) and 6% (MRD). © 2016 Wiley Periodicals, Inc.

  10. Norm-conserving pseudopotentials with chemical accuracy compared to all-electron calculations

    NASA Astrophysics Data System (ADS)

    Willand, Alex; Kvashnin, Yaroslav O.; Genovese, Luigi; Vázquez-Mayagoitia, Álvaro; Deb, Arpan Krishna; Sadeghi, Ali; Deutsch, Thierry; Goedecker, Stefan

    2013-03-01

    By adding a nonlinear core correction to the well established dual space Gaussian type pseudopotentials for the chemical elements up to the third period, we construct improved pseudopotentials for the Perdew-Burke-Ernzerhof [J. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996), 10.1103/PhysRevLett.77.3865] functional and demonstrate that they exhibit excellent accuracy. Our benchmarks for the G2-1 test set show average atomization energy errors of only half a kcal/mol. The pseudopotentials also remain highly reliable for high pressure phases of crystalline solids. When supplemented by empirical dispersion corrections [S. Grimme, J. Comput. Chem. 27, 1787 (2006), 10.1002/jcc.20495; S. Grimme, J. Antony, S. Ehrlich, and H. Krieg, J. Chem. Phys. 132, 154104 (2010), 10.1063/1.3382344] the average error in the interaction energy between molecules is also about half a kcal/mol. The accuracy that can be obtained by these pseudopotentials in combination with a systematic basis set is well superior to the accuracy that can be obtained by commonly used medium size Gaussian basis sets in all-electron calculations.

  11. All-electron Kohn–Sham density functional theory on hierarchic finite element spaces

    SciTech Connect

    Schauer, Volker; Linder, Christian

    2013-10-01

    In this work, a real space formulation of the Kohn–Sham equations is developed, making use of the hierarchy of finite element spaces from different polynomial order. The focus is laid on all-electron calculations, having the highest requirement onto the basis set, which must be able to represent the orthogonal eigenfunctions as well as the electrostatic potential. A careful numerical analysis is performed, which points out the numerical intricacies originating from the singularity of the nuclei and the necessity for approximations in the numerical setting, with the ambition to enable solutions within a predefined accuracy. In this context the influence of counter-charges in the Poisson equation, the requirement of a finite domain size, numerical quadratures and the mesh refinement are examined as well as the representation of the electrostatic potential in a high order finite element space. The performance and accuracy of the method is demonstrated in computations on noble gases. In addition the finite element basis proves its flexibility in the calculation of the bond-length as well as the dipole moment of the carbon monoxide molecule.

  12. Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

    SciTech Connect

    Webster, R. Harrison, N. M.; Bernasconi, L.

    2015-06-07

    We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green’s function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional c{sub HF} and show that there exists one value of c{sub HF} (∼0.32) that reproduces at least semi-quantitatively the optical gap of this material.

  13. All-electronic biosensing in microfluidics: bulk and surface impedance sensing

    NASA Astrophysics Data System (ADS)

    Fraikin, Jean-Luc

    All-electronic, impedance-based sensing techniques offer promising new routes for probing nanoscale biological processes. The ease with which electrical probes can be fabricated at the nanoscale and integrated into microfluidic systems, combined with the large bandwidth afforded by radiofrequency electrical measurement, gives electrical detection significant advantages over other sensing approaches. We have developed two microfluidic devices for impedance-based biosensing. The first is a novel radiofrequency (rf) field-effect transistor which uses the electrolytic Debye layer as its active element. We demonstrate control of the nm-thick Debye layer using an external gate voltage, with gate modulation at frequencies as high 5 MHz. We use this sensor to make quantitative measurements of the electric double-layer capacitance, including determining and controlling the potential of zero charge of the electrodes, a quantity of importance for electrochemistry and impedance-based biosensing. The second device is a microfluidic analyzer for high-throughput, label-free measurement of nanoparticles suspended in a fluid. We demonstrate detection and volumetric analysis of individual synthetic nanoparticles (<100 nm dia.) with sufficient throughput to analyze >500,000 particles/second, and are able to distinguish subcomponents of a polydisperse particle mixture with diameters larger than about 30-40 nm. We also demonstrate the rapid (seconds) size and titer analysis of unlabeled bacteriophage T7 (55-65 nm dia.) in both salt solution and mouse blood plasma, using ˜ 1 muL of analyte. Surprisingly, we find that the background of naturally-occurring nanoparticles in plasma have a power-law size distribution. The scalable fabrication of these instruments, and the simple electronics required for readout make them well-suited for practical applications.

  14. Optical properties of alkali halide crystals from all-electron hybrid TD-DFT calculations

    NASA Astrophysics Data System (ADS)

    Webster, R.; Bernasconi, L.; Harrison, N. M.

    2015-06-01

    We present a study of the electronic and optical properties of a series of alkali halide crystals AX, with A = Li, Na, K, Rb and X = F, Cl, Br based on a recent implementation of hybrid-exchange time-dependent density functional theory (TD-DFT) (TD-B3LYP) in the all-electron Gaussian basis set code CRYSTAL. We examine, in particular, the impact of basis set size and quality on the prediction of the optical gap and exciton binding energy. The formation of bound excitons by photoexcitation is observed in all the studied systems and this is shown to be correlated to specific features of the Hartree-Fock exchange component of the TD-DFT response kernel. All computed optical gaps and exciton binding energies are however markedly below estimated experimental and, where available, 2-particle Green's function (GW-Bethe-Salpeter equation, GW-BSE) values. We attribute this reduced exciton binding to the incorrect asymptotics of the B3LYP exchange correlation ground state functional and of the TD-B3LYP response kernel, which lead to a large underestimation of the Coulomb interaction between the excited electron and hole wavefunctions. Considering LiF as an example, we correlate the asymptotic behaviour of the TD-B3LYP kernel to the fraction of Fock exchange admixed in the ground state functional cHF and show that there exists one value of cHF (˜0.32) that reproduces at least semi-quantitatively the optical gap of this material.

  15. Monte Carlo Benchmark

    2010-10-20

    The "Monte Carlo Benchmark" (MCB) is intended to model the computatiional performance of Monte Carlo algorithms on parallel architectures. It models the solution of a simple heuristic transport equation using a Monte Carlo technique. The MCB employs typical features of Monte Carlo algorithms such as particle creation, particle tracking, tallying particle information, and particle destruction. Particles are also traded among processors using MPI calls.

  16. Quantum Monte Carlo Computations of the (Mg1-XFeX) SiO3 Perovskite to Post-perovskite Phase Boundary

    NASA Astrophysics Data System (ADS)

    Lin, Yangzheng; Cohen, R. E.; Floris, Andrea; Shulenburger, Luke; Driver, Kevin P.

    We have computed total energies of FeSiO3 and MgSiO3[1 ] perovskite and post-perovskite using diffusion Monte Carlo with the qmcpack GPU code. In conjunction with DFT +U computations for intermediate compositions (Mg1-XFeX) SiO3 and phonons computed using density functional perturbation theory (DFPT) with the pwscf code, we have derived the chemical potentials of perovskite (Pv) and post-perovskite (PPv) (Mg1-XFeX) SiO3 and computed the binary phase diagram versus P, T, and X using a non-ideal solid solution model. The finite temperature effects were considered within quasi-harmonic approximation (QHA). Our results show that ferrous iron stabilizes PPv and lowers the Pv-PPv transition pressure, which is consistent with previous theoretical and some experimental studies. We will discuss the correlation between the Earth's D'' layer and the Pv to PPv phase boundary. Computations were performed on XSEDE machines, and on the Oak Ridge Leadership Computing Facility (OLCF) machine Titan under project CPH103geo of INCITE program E-mail: rcohen@carnegiescience.edu; This work is supported by NSF.

  17. Shell model Monte Carlo methods

    SciTech Connect

    Koonin, S.E.; Dean, D.J.

    1996-10-01

    We review quantum Monte Carlo methods for dealing with large shell model problems. These methods reduce the imaginary-time many-body evolution operator to a coherent superposition of one-body evolutions in fluctuating one-body fields; resultant path integral is evaluated stochastically. We first discuss the motivation, formalism, and implementation of such Shell Model Monte Carlo methods. There then follows a sampler of results and insights obtained from a number of applications. These include the ground state and thermal properties of pf-shell nuclei, thermal behavior of {gamma}-soft nuclei, and calculation of double beta-decay matrix elements. Finally, prospects for further progress in such calculations are discussed. 87 refs.

  18. Valence-bond crystal in the extended Kagomé spin- 1 / 2 quantum Heisenberg antiferromagnet: A variational Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Becca, Federico; Iqbal, Yasir; Poilblanc, Didier

    2011-03-01

    The highly-frustrated spin- 1 / 2 quantum Heisenberg model with both nearest (J1) and next-nearest (J2) neighbor exchange interactions is revisited by using an extended variational space of projected wave functions that are optimized with state-of-the-art methods. Competition between modulated valence-bond crystals (VBC) proposed in the literature and the Dirac spin liquid (DSL) is investigated. We find that the addition of a small ferromagnetic next-nearest-neighbor exchange coupling |J2 | > 0.09J1 leads to stabilization of a 36-site unit cell VBC, although the DSL remains a local minimum of the variational parameter landscape. This implies that the VBC is not trivially connected to the DSL: instead it possesses a non-trivial flux pattern and large dimerization.

  19. About the collapse of the 3.3 μm CH stretching band with ionization in polycyclic aromatic hydrocarbons: Configuration interaction and quantum Monte Carlo studies of the CH fragment

    NASA Astrophysics Data System (ADS)

    Pauzat, Françoise; Pilmé, Julien; Toulouse, Julien; Ellinger, Yves

    2010-08-01

    The puzzling difference between the IR spectra of polycyclic aromatic hydrocarbons (PAHs) and those of the corresponding positive ions (PAHs+) is a well documented fact, although the basic reason for it is far from clear. In this report, the CH fragment, in its neutral and ionized forms is taken as a case study for investigating the collapse of the CH stretching vibration with ionization. A comprehensive study of the dipole moment function around the equilibrium geometries of the fragments using large scale configuration interaction and quantum Monte Carlo methods shows very different variations with the CH distance: a marked decrease for neutral CH(Π2) and a perfect stability for ionized CH+(Σ1+). These results are consistent with strong/weak intensities of the CH vibrations in the neutral/ionized PAHs, the key point being the presence, or not, of a hole in the π shell. A topological analysis of the electronic densities shows that the collapse of the CH stretching with ionization is directly linked to the compensation between the internal charge transfer contribution and the distortion of the electronic density within the CH bond.

  20. Thermodynamic properties of Th xU 1-xO 2 (0 < x < 1) based on quantum-mechanical calculations and Monte-Carlo simulations

    NASA Astrophysics Data System (ADS)

    Shuller, Lindsay C.; Ewing, Rodney C.; Becker, Udo

    2011-05-01

    Th xU 1-xO 2+y binary compositions occur in nature, uranothorianite, and as a mixed oxide nuclear fuel. As a nuclear fuel, important properties, such as the melting point, thermal conductivity, and the thermal expansion coefficient change as a function of composition. Additionally, for direct disposal of Th xU 1-xO 2, the chemical durability changes as a function of composition, with the dissolution rate decreasing with increasing thoria content. UO 2 and ThO 2 have the same isometric structure, and the ionic radii of 8-fold coordinated U 4+ and Th 4+ are similar (1.14 nm and 1.19 nm, respectively). Thus, this binary is expected to form a complete solid solution. However, atomic-scale measurements or simulations of cation ordering and the associated thermodynamic properties of the Th xU 1-xO 2 system have yet to be determined. A combination of density-functional theory, Monte-Carlo methods, and thermodynamic integration are used to calculate thermodynamic properties of the Th xU 1-xO 2 binary (Δ H mix, Δ G mix, Δ S mix, phase diagram). The Gibbs free energy of mixing (Δ G mix) shows a miscibility gap at equilibration temperatures below 1000 K (e.g., E exsoln = 0.13 kJ/(mol cations) at 750 K). Such a miscibility gap may indicate possible exsolution (i.e., phase separation upon cooling). A unique approach to evaluate the likelihood and kinetics of forming interfaces between U-rich and Th-rich has been chosen that compares the energy gain of forming separate phases with estimated energy losses of forming necessary interfaces. The result of such an approach is that the thermodynamic gain of phase separation does not overcome the increase in interface energy between exsolution lamellae for thin exsolution lamellae (10 Å). Lamella formation becomes energetically favorable with a reduction of the interface area and, thus, an increase in lamella thickness to >45 Å. However, this increase in lamellae thickness may be diffusion limited. Monte-Carlo simulations converge

  1. Multi-electron systems in strong magnetic fields II: A fixed-phase diffusion quantum Monte Carlo application based on trial functions from a Hartree-Fock-Roothaan method

    NASA Astrophysics Data System (ADS)

    Boblest, S.; Meyer, D.; Wunner, G.

    2014-11-01

    We present a quantum Monte Carlo application for the computation of energy eigenvalues for atoms and ions in strong magnetic fields. The required guiding wave functions are obtained with the Hartree-Fock-Roothaan code described in the accompanying publication (Schimeczek and Wunner, 2014). Our method yields highly accurate results for the binding energies of symmetry subspace ground states and at the same time provides a means for quantifying the quality of the results obtained with the above-mentioned Hartree-Fock-Roothaan method. Catalogue identifier: AETV_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AETV_v1_0.html Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 72 284 No. of bytes in distributed program, including test data, etc.: 604 948 Distribution format: tar.gz Programming language: C++. Computer: Cluster of 1-˜500 HP Compaq dc5750. Operating system: Linux. Has the code been vectorized or parallelized?: Yes. Code includes MPI directives. RAM: 500 MB per node Classification: 2.1. External routines: Boost::Serialization, Boost::MPI, LAPACK BLAS Nature of problem: Quantitative modelings of features observed in the X-ray spectra of isolated neutron stars are hampered by the lack of sufficiently large and accurate databases for atoms and ions up to the last fusion product iron, at high magnetic field strengths. The predominant amount of line data in the literature has been calculated with Hartree-Fock methods, which are intrinsically restricted in precision. Our code is intended to provide a powerful tool for calculating very accurate energy values from, and thereby improving the quality of, existing Hartree-Fock results. Solution method: The Fixed-phase quantum Monte Carlo method is used in combination with guiding functions obtained in Hartree

  2. Coupled Electron-Ion Monte Carlo calculations of atomic hydrogen

    NASA Astrophysics Data System (ADS)

    Holzmann, Markus; Pierleoni, Carlo; Ceperley, David M.

    2005-07-01

    We present a new Monte Carlo method which couples Path Integral for finite temperature protons with Quantum Monte Carlo for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. This method fills the gap between high temperature electron-proton Path Integral and ground state Diffusion Monte Carlo methods. Our data exhibit more structure and higher melting temperatures of the proton crystal than Car-Parrinello Molecular Dynamics results using LDA. We further discuss the quantum motion of the protons and the zero temperature limit.

  3. 31 CFR 370.35 - Does the Bureau of the Public Debt accept all electronically signed transaction requests?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 31 Money and Finance: Treasury 2 2010-07-01 2010-07-01 false Does the Bureau of the Public Debt accept all electronically signed transaction requests? 370.35 Section 370.35 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) FISCAL SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF...

  4. Monte Carlo Example Programs

    2006-05-09

    The Monte Carlo example programs VARHATOM and DMCATOM are two small, simple FORTRAN programs that illustrate the use of the Monte Carlo Mathematical technique for calculating the ground state energy of the hydrogen atom.

  5. Combining the Complete Active Space Self-Consistent Field Method and the Full Configuration Interaction Quantum Monte Carlo within a Super-CI Framework, with Application to Challenging Metal-Porphyrins.

    PubMed

    Li Manni, Giovanni; Smart, Simon D; Alavi, Ali

    2016-03-01

    A novel stochastic Complete Active Space Self-Consistent Field (CASSCF) method has been developed and implemented in the Molcas software package. A two-step procedure is used, in which the CAS configuration interaction secular equations are solved stochastically with the Full Configuration Interaction Quantum Monte Carlo (FCIQMC) approach, while orbital rotations are performed using an approximated form of the Super-CI method. This new method does not suffer from the strong combinatorial limitations of standard MCSCF implementations using direct schemes and can handle active spaces well in excess of those accessible to traditional CASSCF approaches. The density matrix formulation of the Super-CI method makes this step independent of the size of the CI expansion, depending exclusively on one- and two-body density matrices with indices restricted to the relatively small number of active orbitals. No sigma vectors need to be stored in memory for the FCIQMC eigensolver--a substantial gain in comparison to implementations using the Davidson method, which require three or more vectors of the size of the CI expansion. Further, no orbital Hessian is computed, circumventing limitations on basis set expansions. Like the parent FCIQMC method, the present technique is scalable on massively parallel architectures. We present in this report the method and its application to the free-base porphyrin, Mg(II) porphyrin, and Fe(II) porphyrin. In the present study, active spaces up to 32 electrons and 29 orbitals in orbital expansions containing up to 916 contracted functions are treated with modest computational resources. Results are quite promising even without accounting for the correlation outside the active space. The systems here presented clearly demonstrate that large CASSCF calculations are possible via FCIQMC-CASSCF without limitations on basis set size.

  6. Singlet-triplet energy splitting between 1D and 3D (1s2 2s nd), n = 3, 4, 5, and 6, Rydberg states of the beryllium atom (9Be) calculated with all-electron explicitly correlated Gaussian functions

    NASA Astrophysics Data System (ADS)

    Sharkey, Keeper L.; Bubin, Sergiy; Adamowicz, Ludwik

    2014-11-01

    Accurate variational nonrelativistic quantum-mechanical calculations are performed for the five lowest 1D and four lowest 3D states of the 9Be isotope of the beryllium atom. All-electron explicitly correlated Gaussian (ECG) functions are used in the calculations and their nonlinear parameters are optimized with the aid of the analytical energy gradient determined with respect to these parameters. The effect of the finite nuclear mass is directly included in the Hamiltonian used in the calculations. The singlet-triplet energy gaps between the corresponding 1D and 3D states, are reported.

  7. Monte Carlo fundamentals

    SciTech Connect

    Brown, F.B.; Sutton, T.M.

    1996-02-01

    This report is composed of the lecture notes from the first half of a 32-hour graduate-level course on Monte Carlo methods offered at KAPL. These notes, prepared by two of the principle developers of KAPL`s RACER Monte Carlo code, cover the fundamental theory, concepts, and practices for Monte Carlo analysis. In particular, a thorough grounding in the basic fundamentals of Monte Carlo methods is presented, including random number generation, random sampling, the Monte Carlo approach to solving transport problems, computational geometry, collision physics, tallies, and eigenvalue calculations. Furthermore, modern computational algorithms for vector and parallel approaches to Monte Carlo calculations are covered in detail, including fundamental parallel and vector concepts, the event-based algorithm, master/slave schemes, parallel scaling laws, and portability issues.

  8. Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Bardenet, Rémi

    2013-07-01

    Bayesian inference often requires integrating some function with respect to a posterior distribution. Monte Carlo methods are sampling algorithms that allow to compute these integrals numerically when they are not analytically tractable. We review here the basic principles and the most common Monte Carlo algorithms, among which rejection sampling, importance sampling and Monte Carlo Markov chain (MCMC) methods. We give intuition on the theoretical justification of the algorithms as well as practical advice, trying to relate both. We discuss the application of Monte Carlo in experimental physics, and point to landmarks in the literature for the curious reader.

  9. All-electron double zeta basis sets for the lanthanides: Application in atomic and molecular property calculations

    NASA Astrophysics Data System (ADS)

    Jorge, F. E.; Martins, L. S. C.; Franco, M. L.

    2016-01-01

    Segmented all-electron basis sets of valence double zeta quality plus polarization functions (DZP) for the elements from Ce to Lu are generated to be used with the non-relativistic and Douglas-Kroll-Hess (DKH) Hamiltonians. At the B3LYP level, the DZP-DKH atomic ionization energies and equilibrium bond lengths and atomization energies of the lanthanide trifluorides are evaluated and compared with benchmark theoretical and experimental data reported in the literature. In general, this compact size set shows to have a regular, efficient, and reliable performance. It can be particularly useful in molecular property calculations that require explicit treatment of the core electrons.

  10. Frozen core potential scheme with a relativistic electronic Hamiltonian: Theoretical connection between the model potential and all-electron treatments

    NASA Astrophysics Data System (ADS)

    Seino, Junji; Tarumi, Moto; Nakai, Hiromi

    2014-01-01

    This Letter proposes an accurate scheme using frozen core orbitals, called the frozen core potential (FCP) method, to theoretically connect model potential calculations to all-electron (AE) ones. The present scheme is based on the Huzinaga-Cantu equation combined with spin-free relativistic Douglas-Kroll-Hess Hamiltonians. The local unitary transformation scheme for efficiently constructing the Hamiltonian produces a seamless extension to the FCP method in a relativistic framework. Numerical applications to coinage diatomic molecules illustrate the high accuracy of this FCP method, as compared to AE calculations. Furthermore, the efficiency of the FCP method is also confirmed by these calculations.

  11. Quantum Monte Carlo methods for nuclei.

    SciTech Connect

    Wiringa, R. B.; Physics

    2008-01-01

    A major goal in nuclear physics is to understand how nuclear binding, structure, and reactions can be described from the underlying interactions between individual nucleons. We want to compute the properties of an A-nucleon system as an A-body problem with free-space nuclear interactions that describe nucleon-nucleon (NN) scattering and the two-nucleon bound-state. Properties of interest for a given nucleus include the ground-state binding energy, excitation spectrum, one- and two-nucleon density and momentum distributions, electromagnetic moments and transitions. They also wish to describe the interactions of nuclei with electrons, neutrinos, pions, nucleons, and other nuclei. Such calculations can provide a standard of comparison to test whether sub-nucleonic effects, such as explicit quark degrees of freedom, must be invoked to explain an observed phenomenon. they can also be used to evaluate nuclear matrix elements needed for some test of the standard model, and to predict reaction rates that are difficult or impossible to measure in the laboratory. For example, all the astrophysical reactions that contribute to the Big Bang or to solar energy production should be amenable to such ab initio calculations. To achieve this goal, they must both determine reasonable Hamiltonians to be used and devise reliable many-body methods to evaluate them. Significant progress has been made in the past decade on both fronts, with the development of a number of potential models that accurately reproduce NN elastic scattering data, and a variety of advanced many-body methods. In practice, to reproduce experimental energies and transitions, it appears necessary to add many-nucleon forces to the Hamiltonian and electroweak charge and current operators beyond the basic single-nucleon terms. While testing their interactions and currents against experiment, it is also important to test the many-body methods against each other to ensure that any approximations made are not biasing the results.

  12. Monte Carlo methods and applications in nuclear physics

    SciTech Connect

    Carlson, J.

    1990-01-01

    Monte Carlo methods for studying few- and many-body quantum systems are introduced, with special emphasis given to their applications in nuclear physics. Variational and Green's function Monte Carlo methods are presented in some detail. The status of calculations of light nuclei is reviewed, including discussions of the three-nucleon-interaction, charge and magnetic form factors, the coulomb sum rule, and studies of low-energy radiative transitions. 58 refs., 12 figs.

  13. Fragmented Molecular Orbital with Diffusion Monte Carlo for large molecular systems

    NASA Astrophysics Data System (ADS)

    Benali, Anouar; Pruitt, Spencer R.; Fedorov, Dmitri G.

    Performing accurate quantum mechanics (QM) calculations on larger and larger systems, while maintaining a high level of accuracy is an ongoing effort in many ab initio fields. Many different attempts have been made to develop highly scalable and accurate methods. The fragment molecular orbital (FMO) method is an ab initio method capable of taking advantage of modern supercomputers, such as the Blue Gene Q system Mira at the Argonne National Laboratory Leadership Computing Facility (ALCF). FMO is based on dividing molecules into fragments and performing ab initio calculations on fragments, their dimers and, optionally, trimers. This decomposition makes it possible to perform QM calculations of real size biological molecules. In contrast to many other fragment-based methods, the effect of the environment is rigorously accounted for by computing the electrostatic potential (ESP) due to remaining fragments that are not explicitly included in a given monomer, dimer, or trimer calculation. The use of highly accurate levels of theory, such as Diffusion Monte Carlo (DMC-QMC), in conjunction with FMO allows for the goal of highly scalable and accurate all electron calculations demonstrated in this study, on a variety of relevant systems (H2O)[3-6] and protein using GAMESS and QMCPACK.

  14. MORSE Monte Carlo code

    SciTech Connect

    Cramer, S.N.

    1984-01-01

    The MORSE code is a large general-use multigroup Monte Carlo code system. Although no claims can be made regarding its superiority in either theoretical details or Monte Carlo techniques, MORSE has been, since its inception at ORNL in the late 1960s, the most widely used Monte Carlo radiation transport code. The principal reason for this popularity is that MORSE is relatively easy to use, independent of any installation or distribution center, and it can be easily customized to fit almost any specific need. Features of the MORSE code are described.

  15. Validity of virial theorem in all-electron mixed basis density functional, Hartree-Fock, and GW calculations.

    PubMed

    Kuwahara, Riichi; Tadokoro, Yoichi; Ohno, Kaoru

    2014-08-28

    In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree-Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is in excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.

  16. All-electron first-principles GW+Bethe-Salpeter calculation for optical absorption spectra of sodium clusters

    SciTech Connect

    Noguchi, Yoshifumi; Ohno, Kaoru

    2010-04-15

    The optical absorption spectra of sodium clusters (Na{sub 2n}, n{<=} 4) are calculated by using an all-electron first-principles GW+Bethe-Salpeter method with the mixed-basis approach within the Tamm-Dancoff approximation. In these small systems, the excitonic effect strongly affects the optical properties due to the confinement of exciton in the small system size. The present state-of-the-art method treats the electron-hole two-particle Green's function by incorporating the ladder diagrams up to the infinite order and therefore takes into account the excitonic effect in a good approximation. We check the accuracy of the present method by comparing the resulting spectra with experiments. In addition, the effect of delocalization in particular in the lowest unoccupied molecular orbital in the GW quasiparticle wave function is also discussed by rediagonalizing the Dyson equation.

  17. Validity of virial theorem in all-electron mixed basis density functional, Hartree–Fock, and GW calculations

    SciTech Connect

    Kuwahara, Riichi; Tadokoro, Yoichi; Ohno, Kaoru

    2014-08-28

    In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree–Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is in excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA.

  18. All-electron formalism for total energy strain derivatives and stress tensor components for numeric atom-centered orbitals

    NASA Astrophysics Data System (ADS)

    Knuth, Franz; Carbogno, Christian; Atalla, Viktor; Blum, Volker; Scheffler, Matthias

    2015-05-01

    We derive and implement the strain derivatives of the total energy of solids, i.e., the analytic stress tensor components, in an all-electron, numeric atom-centered orbital based density-functional formalism. We account for contributions that arise in the semi-local approximation (LDA/GGA) as well as in the generalized Kohn-Sham case, in which a fraction of exact exchange (hybrid functionals) is included. In this work, we discuss the details of the implementation including the numerical corrections for sparse integrations grids which allow to produce accurate results. We validate the implementation for a variety of test cases by comparing to strain derivatives performed via finite differences. Additionally, we include the detailed definition of the overlapping atom-centered integration formalism used in this work to obtain total energies and their derivatives.

  19. All-electron segmented contraction basis sets of triple zeta valence quality for the fifth-row elements

    NASA Astrophysics Data System (ADS)

    Martins, L. S. C.; Jorge, F. E.; Machado, S. F.

    2015-11-01

    All-electron contracted Gaussian basis set of triple zeta valence quality plus polarisation functions (TZP) for the elements Cs, Ba, La, and from Hf to Rn is presented. Douglas-Kroll-Hess (DKH) basis set for fifth-row elements is also reported. We have recontracted the original TZP basis set, i.e., the values of the contraction coefficients are re-optimised using the second-order DKH Hamiltonian. By addition of diffuse functions (s, p, d, f, and g symmetries), which are optimised for the anion ground states, an augmented TZP basis set is constructed. Using the B3LYP hybrid functional, the performance of the TZP-DKH basis set is assessed for predicting atomic ionisation energy as well as spectroscopy constants of some compounds. Despite its compact size, this set demonstrates consistent, efficient, and reliable performance and will be especially useful in calculations of molecular properties that require explicit treatment of the core electrons.

  20. Exact Dynamics via Poisson Process: a unifying Monte Carlo paradigm

    NASA Astrophysics Data System (ADS)

    Gubernatis, James

    2014-03-01

    A common computational task is solving a set of ordinary differential equations (o.d.e.'s). A little known theorem says that the solution of any set of o.d.e.'s is exactly solved by the expectation value over a set of arbitary Poisson processes of a particular function of the elements of the matrix that defines the o.d.e.'s. The theorem thus provides a new starting point to develop real and imaginary-time continous-time solvers for quantum Monte Carlo algorithms, and several simple observations enable various quantum Monte Carlo techniques and variance reduction methods to transfer to a new context. I will state the theorem, note a transformation to a very simple computational scheme, and illustrate the use of some techniques from the directed-loop algorithm in context of the wavefunction Monte Carlo method that is used to solve the Lindblad master equation for the dynamics of open quantum systems. I will end by noting that as the theorem does not depend on the source of the o.d.e.'s coming from quantum mechanics, it also enables the transfer of continuous-time methods from quantum Monte Carlo to the simulation of various classical equations of motion heretofore only solved deterministically.

  1. Symbolic implicit Monte Carlo

    SciTech Connect

    Brooks, E.D. III )

    1989-08-01

    We introduce a new implicit Monte Carlo technique for solving time dependent radiation transport problems involving spontaneous emission. In the usual implicit Monte Carlo procedure an effective scattering term in dictated by the requirement of self-consistency between the transport and implicitly differenced atomic populations equations. The effective scattering term, a source of inefficiency for optically thick problems, becomes an impasse for problems with gain where its sign is negative. In our new technique the effective scattering term does not occur and the excecution time for the Monte Carlo portion of the algorithm is independent of opacity. We compare the performance and accuracy of the new symbolic implicit Monte Carlo technique to the usual effective scattering technique for the time dependent description of a two-level system in slab geometry. We also examine the possibility of effectively exploiting multiprocessors on the algorithm, obtaining supercomputer performance using shared memory multiprocessors based on cheap commodity microprocessor technology. {copyright} 1989 Academic Press, Inc.

  2. Efficient Parallel All-Electron Four-Component Dirac-Kohn-Sham Program Using a Distributed Matrix Approach II.

    PubMed

    Storchi, Loriano; Rampino, Sergio; Belpassi, Leonardo; Tarantelli, Francesco; Quiney, Harry M

    2013-12-10

    We propose a new complete memory-distributed algorithm, which significantly improves the parallel implementation of the all-electron four-component Dirac-Kohn-Sham (DKS) module of BERTHA (J. Chem. Theory Comput. 2010, 6, 384). We devised an original procedure for mapping the DKS matrix between an efficient integral-driven distribution, guided by the structure of specific G-spinor basis sets and by density fitting algorithms, and the two-dimensional block-cyclic distribution scheme required by the ScaLAPACK library employed for the linear algebra operations. This implementation, because of the efficiency in the memory distribution, represents a leap forward in the applicability of the DKS procedure to arbitrarily large molecular systems and its porting on last-generation massively parallel systems. The performance of the code is illustrated by some test calculations on several gold clusters of increasing size. The DKS self-consistent procedure has been explicitly converged for two representative clusters, namely Au20 and Au34, for which the density of electronic states is reported and discussed. The largest gold cluster uses more than 39k basis functions and DKS matrices of the order of 23 GB. PMID:26592273

  3. A divide and conquer real-space approach for all-electron molecular electrostatic potentials and interaction energies.

    PubMed

    Losilla, S A; Sundholm, D

    2012-06-01

    A computational scheme to perform accurate numerical calculations of electrostatic potentials and interaction energies for molecular systems has been developed and implemented. Molecular electron and energy densities are divided into overlapping atom-centered atomic contributions and a three-dimensional molecular remainder. The steep nuclear cusps are included in the atom-centered functions making the three-dimensional remainder smooth enough to be accurately represented with a tractable amount of grid points. The one-dimensional radial functions of the atom-centered contributions as well as the three-dimensional remainder are expanded using finite element functions. The electrostatic potential is calculated by integrating the Coulomb potential for each separate density contribution, using our tensorial finite element method for the three-dimensional remainder. We also provide algorithms to compute accurate electron-electron and electron-nuclear interactions numerically using the proposed partitioning. The methods have been tested on all-electron densities of 18 reasonable large molecules containing elements up to Zn. The accuracy of the calculated Coulomb interaction energies is in the range of 10(-3) to 10(-6) E(h) when using an equidistant grid with a step length of 0.05 a(0).

  4. Validity of virial theorem in all-electron mixed basis density functional, Hartree-Fock, and GW calculations.

    PubMed

    Kuwahara, Riichi; Tadokoro, Yoichi; Ohno, Kaoru

    2014-08-28

    In this paper, we calculate kinetic and potential energy contributions to the electronic ground-state total energy of several isolated atoms (He, Be, Ne, Mg, Ar, and Ca) by using the local density approximation (LDA) in density functional theory, the Hartree-Fock approximation (HFA), and the self-consistent GW approximation (GWA). To this end, we have implemented self-consistent HFA and GWA routines in our all-electron mixed basis code, TOMBO. We confirm that virial theorem is fairly well satisfied in all of these approximations, although the resulting eigenvalue of the highest occupied molecular orbital level, i.e., the negative of the ionization potential, is in excellent agreement only in the case of the GWA. We find that the wave function of the lowest unoccupied molecular orbital level of noble gas atoms is a resonating virtual bound state, and that of the GWA spreads wider than that of the LDA and thinner than that of the HFA. PMID:25173006

  5. Real-space electronic structure calculations with full-potential all-electron precision for transition metals

    NASA Astrophysics Data System (ADS)

    Ono, Tomoya; Heide, Marcus; Atodiresei, Nicolae; Baumeister, Paul; Tsukamoto, Shigeru; Blügel, Stefan

    2010-11-01

    We have developed an efficient computational scheme utilizing the real-space finite-difference formalism and the projector augmented-wave (PAW) method to perform precise first-principles electronic-structure simulations based on the density-functional theory for systems containing transition metals with a modest computational effort. By combining the advantages of the time-saving double-grid technique and the Fourier-filtering procedure for the projectors of pseudopotentials, we can overcome the egg box effect in the computations even for first-row elements and transition metals, which is a problem of the real-space finite-difference formalism. In order to demonstrate the potential power in terms of precision and applicability of the present scheme, we have carried out simulations to examine several bulk properties and structural energy differences between different bulk phases of transition metals and have obtained excellent agreement with the results of other precise first-principles methods such as a plane-wave-based PAW method and an all-electron full-potential linearized augmented plane-wave (FLAPW) method.

  6. All-electronic droplet generation on-chip with real-time feedback control for EWOD digital microfluidics.

    PubMed

    Gong, Jian; Kim, Chang-Jin C J

    2008-06-01

    Electrowetting-on-dielectric (EWOD) actuation enables digital (or droplet) microfluidics where small packets of liquids are manipulated on a two-dimensional surface. Due to its mechanical simplicity and low energy consumption, EWOD holds particular promise for portable systems. To improve volume precision of the droplets, which is desired for quantitative applications such as biochemical assays, existing practices would require near-perfect device fabrication and operation conditions unless the droplets are generated under feedback control by an extra pump setup off of the chip. In this paper, we develop an all-electronic (i.e., no ancillary pumping) real-time feedback control of on-chip droplet generation. A fast voltage modulation, capacitance sensing, and discrete-time PID feedback controller are integrated on the operating electronic board. A significant improvement is obtained in the droplet volume uniformity, compared with an open loop control as well as the previous feedback control employing an external pump. Furthermore, this new capability empowers users to prescribe the droplet volume even below the previously considered minimum, allowing, for example, 1 : x (x < 1) mixing, in comparison to the previously considered n : m mixing (i.e., n and m unit droplets).

  7. ALL-ELECTRONIC DROPLET GENERATION ON-CHIP WITH REAL-TIME FEEDBACK CONTROL FOR EWOD DIGITIAL MICROFLUIDICS

    PubMed Central

    Gong, Jian; Kim, Chang-Jin “CJ”

    2009-01-01

    Electrowetting-on-dielectric (EWOD) actuation enables digital (or droplet) microfluidics where small packets of liquids are manipulated on a two-dimensional surface. Due to its mechanical simplicity and low energy consumption, EWOD holds particular promise for portable systems. To improve volume precision of the droplets, which is desired for quantitative applications such as biochemical assays, existing practices would require near-perfect device fabricaion and operation conditions unless the droplets are generated under feedback control by an extra pump setup off of the chip. In this paper, we develop an all-electronic (i.e., no ancillary pumping) real-time feedback control of on-chip droplet generation. A fast voltage modulation, capacitance sensing, and discrete-time PID feedback controller are integrated on the operating electronic board. A significant improvement is obtained in the droplet volume uniformity, compared with an open loop control as well as the previous feedback control employing an external pump. Furthermore, this new capability empowers users to prescribe the droplet volume even below the previously considered minimum, allowing, for example, 1:x (x < 1) mixing, in comparison to the previously considered n:m mixing (i.e., n and m unit droplets). PMID:18497909

  8. Advancing Efficient All-Electron Electronic Structure Methods Based on Numeric Atom-Centered Orbitals for Energy Related Materials

    NASA Astrophysics Data System (ADS)

    Blum, Volker

    This talk describes recent advances of a general, efficient, accurate all-electron electronic theory approach based on numeric atom-centered orbitals; emphasis is placed on developments related to materials for energy conversion and their discovery. For total energies and electron band structures, we show that the overall accuracy is on par with the best benchmark quality codes for materials, but scalable to large system sizes (1,000s of atoms) and amenable to both periodic and non-periodic simulations. A recent localized resolution-of-identity approach for the Coulomb operator enables O (N) hybrid functional based descriptions of the electronic structure of non-periodic and periodic systems, shown for supercell sizes up to 1,000 atoms; the same approach yields accurate results for many-body perturbation theory as well. For molecular systems, we also show how many-body perturbation theory for charged and neutral quasiparticle excitation energies can be efficiently yet accurately applied using basis sets of computationally manageable size. Finally, the talk highlights applications to the electronic structure of hybrid organic-inorganic perovskite materials, as well as to graphene-based substrates for possible future transition metal compound based electrocatalyst materials. All methods described here are part of the FHI-aims code. VB gratefully acknowledges contributions by numerous collaborators at Duke University, Fritz Haber Institute Berlin, TU Munich, USTC Hefei, Aalto University, and many others around the globe.

  9. Vectorized Monte Carlo

    SciTech Connect

    Brown, F.B.

    1981-01-01

    Examination of the global algorithms and local kernels of conventional general-purpose Monte Carlo codes shows that multigroup Monte Carlo methods have sufficient structure to permit efficient vectorization. A structured multigroup Monte Carlo algorithm for vector computers is developed in which many particle events are treated at once on a cell-by-cell basis. Vectorization of kernels for tracking and variance reduction is described, and a new method for discrete sampling is developed to facilitate the vectorization of collision analysis. To demonstrate the potential of the new method, a vectorized Monte Carlo code for multigroup radiation transport analysis was developed. This code incorporates many features of conventional general-purpose production codes, including general geometry, splitting and Russian roulette, survival biasing, variance estimation via batching, a number of cutoffs, and generalized tallies of collision, tracklength, and surface crossing estimators with response functions. Predictions of vectorized performance characteristics for the CYBER-205 were made using emulated coding and a dynamic model of vector instruction timing. Computation rates were examined for a variety of test problems to determine sensitivities to batch size and vector lengths. Significant speedups are predicted for even a few hundred particles per batch, and asymptotic speedups by about 40 over equivalent Amdahl 470V/8 scalar codes arepredicted for a few thousand particles per batch. The principal conclusion is that vectorization of a general-purpose multigroup Monte Carlo code is well worth the significant effort required for stylized coding and major algorithmic changes.

  10. exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory

    NASA Astrophysics Data System (ADS)

    Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian; Nabok, Dmitrii; Pavone, Pasquale; Rigamonti, Santiago; Sagmeister, Stephan; Werner, Ute; Draxl, Claudia

    2014-09-01

    Linearized augmented planewave methods are known as the most precise numerical schemes for solving the Kohn-Sham equations of density-functional theory (DFT). In this review, we describe how this method is realized in the all-electron full-potential computer package, exciting. We emphasize the variety of different related basis sets, subsumed as (linearized) augmented planewave plus local orbital methods, discussing their pros and cons and we show that extremely high accuracy (microhartrees) can be achieved if the basis is chosen carefully. As the name of the code suggests, exciting is not restricted to ground-state calculations, but has a major focus on excited-state properties. It includes time-dependent DFT in the linear-response regime with various static and dynamical exchange-correlation kernels. These are preferably used to compute optical and electron-loss spectra for metals, molecules and semiconductors with weak electron-hole interactions. exciting makes use of many-body perturbation theory for charged and neutral excitations. To obtain the quasi-particle band structure, the GW approach is implemented in the single-shot approximation, known as G0W0. Optical absorption spectra for valence and core excitations are handled by the solution of the Bethe-Salpeter equation, which allows for the description of strongly bound excitons. Besides these aspects concerning methodology, we demonstrate the broad range of possible applications by prototypical examples, comprising elastic properties, phonons, thermal-expansion coefficients, dielectric tensors and loss functions, magneto-optical Kerr effect, core-level spectra and more.

  11. Exciting: a full-potential all-electron package implementing density-functional theory and many-body perturbation theory.

    PubMed

    Gulans, Andris; Kontur, Stefan; Meisenbichler, Christian; Nabok, Dmitrii; Pavone, Pasquale; Rigamonti, Santiago; Sagmeister, Stephan; Werner, Ute; Draxl, Claudia

    2014-09-10

    Linearized augmented planewave methods are known as the most precise numerical schemes for solving the Kohn-Sham equations of density-functional theory (DFT). In this review, we describe how this method is realized in the all-electron full-potential computer package, exciting. We emphasize the variety of different related basis sets, subsumed as (linearized) augmented planewave plus local orbital methods, discussing their pros and cons and we show that extremely high accuracy (microhartrees) can be achieved if the basis is chosen carefully. As the name of the code suggests, exciting is not restricted to ground-state calculations, but has a major focus on excited-state properties. It includes time-dependent DFT in the linear-response regime with various static and dynamical exchange-correlation kernels. These are preferably used to compute optical and electron-loss spectra for metals, molecules and semiconductors with weak electron-hole interactions. exciting makes use of many-body perturbation theory for charged and neutral excitations. To obtain the quasi-particle band structure, the GW approach is implemented in the single-shot approximation, known as G(0)W(0). Optical absorption spectra for valence and core excitations are handled by the solution of the Bethe-Salpeter equation, which allows for the description of strongly bound excitons. Besides these aspects concerning methodology, we demonstrate the broad range of possible applications by prototypical examples, comprising elastic properties, phonons, thermal-expansion coefficients, dielectric tensors and loss functions, magneto-optical Kerr effect, core-level spectra and more. PMID:25135665

  12. Monte Carlo algorithm for free energy calculation.

    PubMed

    Bi, Sheng; Tong, Ning-Hua

    2015-07-01

    We propose a Monte Carlo algorithm for the free energy calculation based on configuration space sampling. An upward or downward temperature scan can be used to produce F(T). We implement this algorithm for the Ising model on a square lattice and triangular lattice. Comparison with the exact free energy shows an excellent agreement. We analyze the properties of this algorithm and compare it with the Wang-Landau algorithm, which samples in energy space. This method is applicable to general classical statistical models. The possibility of extending it to quantum systems is discussed.

  13. Monte Carlo neutrino oscillations

    SciTech Connect

    Kneller, James P.; McLaughlin, Gail C.

    2006-03-01

    We demonstrate that the effects of matter upon neutrino propagation may be recast as the scattering of the initial neutrino wave function. Exchanging the differential, Schrodinger equation for an integral equation for the scattering matrix S permits a Monte Carlo method for the computation of S that removes many of the numerical difficulties associated with direct integration techniques.

  14. Baseball Monte Carlo Style.

    ERIC Educational Resources Information Center

    Houser, Larry L.

    1981-01-01

    Monte Carlo methods are used to simulate activities in baseball such as a team's "hot streak" and a hitter's "batting slump." Student participation in such simulations is viewed as a useful method of giving pupils a better understanding of the probability concepts involved. (MP)

  15. Path Integral Monte Carlo Methods for Fermions

    NASA Astrophysics Data System (ADS)

    Ethan, Ethan; Dubois, Jonathan; Ceperley, David

    2014-03-01

    In general, Quantum Monte Carlo methods suffer from a sign problem when simulating fermionic systems. This causes the efficiency of a simulation to decrease exponentially with the number of particles and inverse temperature. To circumvent this issue, a nodal constraint is often implemented, restricting the Monte Carlo procedure from sampling paths that cause the many-body density matrix to change sign. Unfortunately, this high-dimensional nodal surface is not a priori known unless the system is exactly solvable, resulting in uncontrolled errors. We will discuss two possible routes to extend the applicability of finite-temperatue path integral Monte Carlo. First we extend the regime where signful simulations are possible through a novel permutation sampling scheme. Afterwards, we discuss a method to variationally improve the nodal surface by minimizing a free energy during simulation. Applications of these methods will include both free and interacting electron gases, concluding with discussion concerning extension to inhomogeneous systems. Support from DOE DE-FG52-09NA29456, DE-AC52-07NA27344, LLNL LDRD 10- ERD-058, and the Lawrence Scholar program.

  16. Monte Carlo simulations of phosphate polyhedron connectivity in glasses

    SciTech Connect

    ALAM,TODD M.

    2000-01-01

    Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

  17. Monte Carlo Simulations of Phosphate Polyhedron Connectivity in Glasses

    SciTech Connect

    ALAM,TODD M.

    1999-12-21

    Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

  18. Monte Carlo fluorescence microtomography

    NASA Astrophysics Data System (ADS)

    Cong, Alexander X.; Hofmann, Matthias C.; Cong, Wenxiang; Xu, Yong; Wang, Ge

    2011-07-01

    Fluorescence microscopy allows real-time monitoring of optical molecular probes for disease characterization, drug development, and tissue regeneration. However, when a biological sample is thicker than 1 mm, intense scattering of light would significantly degrade the spatial resolution of fluorescence microscopy. In this paper, we develop a fluorescence microtomography technique that utilizes the Monte Carlo method to image fluorescence reporters in thick biological samples. This approach is based on an l0-regularized tomography model and provides an excellent solution. Our studies on biomimetic tissue scaffolds have demonstrated that the proposed approach is capable of localizing and quantifying the distribution of optical molecular probe accurately and reliably.

  19. Monte Carlo simulation in statistical physics: an introduction

    NASA Astrophysics Data System (ADS)

    Binder, K., Heermann, D. W.

    Monte Carlo Simulation in Statistical Physics deals with the computer simulation of many-body systems in condensed-matter physics and related fields of physics, chemistry and beyond, to traffic flows, stock market fluctuations, etc.). Using random numbers generated by a computer, probability distributions are calculated, allowing the estimation of the thermodynamic properties of various systems. This book describes the theoretical background to several variants of these Monte Carlo methods and gives a systematic presentation from which newcomers can learn to perform such simulations and to analyze their results. This fourth edition has been updated and a new chapter on Monte Carlo simulation of quantum-mechanical problems has been added. To help students in their work a special web server has been installed to host programs and discussion groups (http://wwwcp.tphys.uni-heidelberg.de). Prof. Binder was the winner of the Berni J. Alder CECAM Award for Computational Physics 2001.

  20. Monte Carlo Study of Real Time Dynamics on the Lattice

    NASA Astrophysics Data System (ADS)

    Alexandru, Andrei; Başar, Gökçe; Bedaque, Paulo F.; Vartak, Sohan; Warrington, Neill C.

    2016-08-01

    Monte Carlo studies involving real time dynamics are severely restricted by the sign problem that emerges from a highly oscillatory phase of the path integral. In this Letter, we present a new method to compute real time quantities on the lattice using the Schwinger-Keldysh formalism via Monte Carlo simulations. The key idea is to deform the path integration domain to a complex manifold where the phase oscillations are mild and the sign problem is manageable. We use the previously introduced "contraction algorithm" to create a Markov chain on this alternative manifold. We substantiate our approach by analyzing the quantum mechanical anharmonic oscillator. Our results are in agreement with the exact ones obtained by diagonalization of the Hamiltonian. The method we introduce is generic and, in principle, applicable to quantum field theory albeit very slow. We discuss some possible improvements that should speed up the algorithm.

  1. Experimental signatures of quantum annealing

    NASA Astrophysics Data System (ADS)

    Boixo, Sergio

    2013-03-01

    Quantum annealing is a general strategy for solving optimization problems with the aid of quantum adiabatic evolution. How effective is rapid decoherence in precluding quantum effects in a quantum annealing experiment, and will engineered quantum annealing devices effectively perform classical thermalization when coupled to a decohering thermal environment? Using the D-Wave machine, we report experimental results for a simple problem which takes advantage of the fact that for quantum annealing the measurement statistics are determined by the energy spectrum along the quantum evolution, while in classical thermalization they are determined by the spectrum of the final Hamiltonian only. We establish an experimental signature which is consistent with quantum annealing, and at the same time inconsistent with classical thermalization, in spite of a decoherence timescale which is orders of magnitude shorter than the adiabatic evolution time. For larger and more difficult problems, we compare the measurements statistics of the D-Wave machine to large-scale numerical simulations of simulated annealing and simulated quantum annealing, implemented through classical and quantum Monte Carlo simulations. For our test cases the statistics of the machine are - within calibration uncertainties - indistinguishable from a simulated quantum annealer with suitably chosen parameters, but significantly different from a classical annealer. Work in collaboration with T. Albash, N. Chancellor, S. Isakov, D. Lidar, T. Roennow, F. Spedalieri, M. Troyer and Z. Wang.

  2. Frost in Charitum Montes

    NASA Technical Reports Server (NTRS)

    2003-01-01

    MGS MOC Release No. MOC2-387, 10 June 2003

    This is a Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) wide angle view of the Charitum Montes, south of Argyre Planitia, in early June 2003. The seasonal south polar frost cap, composed of carbon dioxide, has been retreating southward through this area since spring began a month ago. The bright features toward the bottom of this picture are surfaces covered by frost. The picture is located near 57oS, 43oW. North is at the top, south is at the bottom. Sunlight illuminates the scene from the upper left. The area shown is about 217 km (135 miles) wide.

  3. MCMini: Monte Carlo on GPGPU

    SciTech Connect

    Marcus, Ryan C.

    2012-07-25

    MCMini is a proof of concept that demonstrates the possibility for Monte Carlo neutron transport using OpenCL with a focus on performance. This implementation, written in C, shows that tracing particles and calculating reactions on a 3D mesh can be done in a highly scalable fashion. These results demonstrate a potential path forward for MCNP or other Monte Carlo codes.

  4. Fermion-induced quantum critical points: beyond Landau criterion

    NASA Astrophysics Data System (ADS)

    Yao, Hong; Li, Zi-Xiang; Jiang, Yi-Fan; Jian, Shao-Kai

    According to Landau criterion, phase transitions must be first-order when cubic terms of order parameters in the Landau-Ginzburg free energy are allowed by symmetry. Here, from both renormalization group analysis and sign-problem-free quantum Monte Carlo simulations, we show that second-order quantum phase transitions can occur at such putatively-first-order quantum phase transitions in strongly-interacting Dirac semimetals in two spatial dimensions. Such type of Landau-criterion-violating quantum critical points are induced by massless fermionic modes at the quantum phase transitions. We call them ``fermion-induced quantum critical points''. From Majorana-quantum-Monte-Carlo simulations and renormalization analysis, we find that the critical exponentials at the kekule valence-bond-solid transition of the Dirac fermions on the honeycomb lattice are highly-nonclassical. We also discuss experimental signatures of the kekule quantum critical point which may be realized in graphene-like systems.

  5. Quantum computing

    PubMed Central

    Li, Shu-Shen; Long, Gui-Lu; Bai, Feng-Shan; Feng, Song-Lin; Zheng, Hou-Zhi

    2001-01-01

    Quantum computing is a quickly growing research field. This article introduces the basic concepts of quantum computing, recent developments in quantum searching, and decoherence in a possible quantum dot realization. PMID:11562459

  6. Auxiliary Field Diffusion Monte Carlo Calculation of Nuclei with A{<=}40 with Tensor Interactions

    SciTech Connect

    Gandolfi, S.; Pederiva, F.

    2007-07-13

    We calculate the ground-state energy of {sup 4}He, {sup 8}He, {sup 16}O, and {sup 40}Ca using the auxiliary field diffusion Monte Carlo method in the fixed-phase approximation and the Argonne v{sub 6}{sup '} interaction which includes a tensor force. Comparison of our light nuclei results to those of Green's function Monte Carlo calculations shows the accuracy of our method for both open and closed-shell nuclei. We also apply it to {sup 16}O and {sup 40}Ca to show that quantum Monte Carlo methods are now applicable to larger nuclei.

  7. Coupled Electron-Ion Monte Carlo Calculations of Dense Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Pierleoni, Carlo; Ceperley, David M.; Holzmann, Markus

    2004-09-01

    We present an efficient new Monte Carlo method which couples path integrals for finite temperature protons with quantum Monte Carlo calculations for ground state electrons, and we apply it to metallic hydrogen for pressures beyond molecular dissociation. We report data for the equation of state for temperatures across the melting of the proton crystal. Our data exhibit more structure and higher melting temperatures of the proton crystal than do Car-Parrinello molecular dynamics results. This method fills the gap between high temperature electron-proton path integral and ground state diffusion Monte Carlo methods and should have wide applicability.

  8. Mathematical foundation of quantum annealing

    SciTech Connect

    Morita, Satoshi; Nishimori, Hidetoshi

    2008-12-15

    Quantum annealing is a generic name of quantum algorithms that use quantum-mechanical fluctuations to search for the solution of an optimization problem. It shares the basic idea with quantum adiabatic evolution studied actively in quantum computation. The present paper reviews the mathematical and theoretical foundations of quantum annealing. In particular, theorems are presented for convergence conditions of quantum annealing to the target optimal state after an infinite-time evolution following the Schroedinger or stochastic (Monte Carlo) dynamics. It is proved that the same asymptotic behavior of the control parameter guarantees convergence for both the Schroedinger dynamics and the stochastic dynamics in spite of the essential difference of these two types of dynamics. Also described are the prescriptions to reduce errors in the final approximate solution obtained after a long but finite dynamical evolution of quantum annealing. It is shown there that we can reduce errors significantly by an ingenious choice of annealing schedule (time dependence of the control parameter) without compromising computational complexity qualitatively. A review is given on the derivation of the convergence condition for classical simulated annealing from the view point of quantum adiabaticity using a classical-quantum mapping.

  9. Wormhole Hamiltonian Monte Carlo

    PubMed Central

    Lan, Shiwei; Streets, Jeffrey; Shahbaba, Babak

    2015-01-01

    In machine learning and statistics, probabilistic inference involving multimodal distributions is quite difficult. This is especially true in high dimensional problems, where most existing algorithms cannot easily move from one mode to another. To address this issue, we propose a novel Bayesian inference approach based on Markov Chain Monte Carlo. Our method can effectively sample from multimodal distributions, especially when the dimension is high and the modes are isolated. To this end, it exploits and modifies the Riemannian geometric properties of the target distribution to create wormholes connecting modes in order to facilitate moving between them. Further, our proposed method uses the regeneration technique in order to adapt the algorithm by identifying new modes and updating the network of wormholes without affecting the stationary distribution. To find new modes, as opposed to redis-covering those previously identified, we employ a novel mode searching algorithm that explores a residual energy function obtained by subtracting an approximate Gaussian mixture density (based on previously discovered modes) from the target density function. PMID:25861551

  10. A wavelet-based Projector Augmented-Wave (PAW) method: Reaching frozen-core all-electron precision with a systematic, adaptive and localized wavelet basis set

    NASA Astrophysics Data System (ADS)

    Rangel, T.; Caliste, D.; Genovese, L.; Torrent, M.

    2016-11-01

    We present a Projector Augmented-Wave (PAW) method based on a wavelet basis set. We implemented our wavelet-PAW method as a PAW library in the ABINIT package [http://www.abinit.org] and into BigDFT [http://www.bigdft.org]. We test our implementation in prototypical systems to illustrate the potential usage of our code. By using the wavelet-PAW method, we can simulate charged and special boundary condition systems with frozen-core all-electron precision. Furthermore, our work paves the way to large-scale and potentially order- N simulations within a PAW method.

  11. Path-integral Monte Carlo method for Rényi entanglement entropies.

    PubMed

    Herdman, C M; Inglis, Stephen; Roy, P-N; Melko, R G; Del Maestro, A

    2014-07-01

    We introduce a quantum Monte Carlo algorithm to measure the Rényi entanglement entropies in systems of interacting bosons in the continuum. This approach is based on a path-integral ground state method that can be applied to interacting itinerant bosons in any spatial dimension with direct relevance to experimental systems of quantum fluids. We demonstrate how it may be used to compute spatial mode entanglement, particle partitioned entanglement, and the entanglement of particles, providing insights into quantum correlations generated by fluctuations, indistinguishability, and interactions. We present proof-of-principle calculations and benchmark against an exactly soluble model of interacting bosons in one spatial dimension. As this algorithm retains the fundamental polynomial scaling of quantum Monte Carlo when applied to sign-problem-free models, future applications should allow for the study of entanglement entropy in large-scale many-body systems of interacting bosons.

  12. Isotropic Monte Carlo Grain Growth

    2013-04-25

    IMCGG performs Monte Carlo simulations of normal grain growth in metals on a hexagonal grid in two dimensions with periodic boundary conditions. This may be performed with either an isotropic or a misorientation - and incliantion-dependent grain boundary energy.

  13. Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Auletta, Gennaro; Fortunato, Mauro; Parisi, Giorgio

    2014-01-01

    Introduction; Part I. Basic Features of Quantum Mechanics: 1. From classical mechanics to quantum mechanics; 2. Quantum observable and states; 3. Quantum dynamics; 4. Examples of quantum dynamics; 5. Density matrix; Part II. More Advanced Topics: 6. Angular momentum and spin; 7. Identical particles; 8. Symmetries and conservation laws; 9. The measurement problem; Part III. Matter and Light: 10. Perturbations and approximation methods; 11. Hydrogen and helium atoms; 12. Hydrogen molecular ion; 13. Quantum optics; Part IV. Quantum Information: State and Correlations: 14. Quantum theory of open systems; 15. State measurement in quantum mechanics; 16. Entanglement: non-separability; 17. Entanglement: quantum information; References; Index.

  14. How localized is ``local?'' Efficiency vs. accuracy of O(N) domain decomposition in local orbital based all-electron electronic structure theory

    NASA Astrophysics Data System (ADS)

    Havu, Vile; Blum, Volker; Scheffler, Matthias

    2007-03-01

    Numeric atom-centered local orbitals (NAO) are efficient basis sets for all-electron electronic structure theory. The locality of NAO's can be exploited to render (in principle) all operations of the self-consistency cycle O(N). This is straightforward for 3D integrals using domain decomposition into spatially close subsets of integration points, enabling critical computational savings that are effective from ˜tens of atoms (no significant overhead for smaller systems) and make large systems (100s of atoms) computationally feasible. Using a new all-electron NAO-based code,^1 we investigate the quantitative impact of exploiting this locality on two distinct classes of systems: Large light-element molecules [Alanine-based polypeptide chains (Ala)n], and compact transition metal clusters. Strict NAO locality is achieved by imposing a cutoff potential with an onset radius rc, and exploited by appropriately shaped integration domains (subsets of integration points). Conventional tight rc<= 3å have no measurable accuracy impact in (Ala)n, but introduce inaccuracies of 20-30 meV/atom in Cun. The domain shape impacts the computational effort by only 10-20 % for reasonable rc. ^1 V. Blum, R. Gehrke, P. Havu, V. Havu, M. Scheffler, The FHI Ab Initio Molecular Simulations (aims) Project, Fritz-Haber-Institut, Berlin (2006).

  15. Discrete Diffusion Monte Carlo for grey Implicit Monte Carlo simulations.

    SciTech Connect

    Densmore, J. D.; Urbatsch, T. J.; Evans, T. M.; Buksas, M. W.

    2005-01-01

    Discrete Diffusion Monte Carlo (DDMC) is a hybrid transport-diffusion method for Monte Carlo simulations in diffusive media. In DDMC, particles take discrete steps between spatial cells according to a discretized diffusion equation. Thus, DDMC produces accurate solutions while increasing the efficiency of the Monte Carlo calculation. In this paper, we extend previously developed DDMC techniques in several ways that improve the accuracy and utility of DDMC for grey Implicit Monte Carlo calculations. First, we employ a diffusion equation that is discretized in space but is continuous time. Not only is this methodology theoretically more accurate than temporally discretized DDMC techniques, but it also has the benefit that a particle's time is always known. Thus, there is no ambiguity regarding what time to assign a particle that leaves an optically thick region (where DDMC is used) and begins transporting by standard Monte Carlo in an optically thin region. In addition, we treat particles incident on an optically thick region using the asymptotic diffusion-limit boundary condition. This interface technique can produce accurate solutions even if the incident particles are distributed anisotropically in angle. Finally, we develop a method for estimating radiation momentum deposition during the DDMC simulation. With a set of numerical examples, we demonstrate the accuracy and efficiency of our improved DDMC method.

  16. Materials Frontiers to Empower Quantum Computing

    SciTech Connect

    Taylor, Antoinette Jane; Sarrao, John Louis; Richardson, Christopher

    2015-06-11

    This is an exciting time at the nexus of quantum computing and materials research. The materials frontiers described in this report represent a significant advance in electronic materials and our understanding of the interactions between the local material and a manufactured quantum state. Simultaneously, directed efforts to solve materials issues related to quantum computing provide an opportunity to control and probe the fundamental arrangement of matter that will impact all electronic materials. An opportunity exists to extend our understanding of materials functionality from electronic-grade to quantum-grade by achieving a predictive understanding of noise and decoherence in qubits and their origins in materials defects and environmental coupling. Realizing this vision systematically and predictively will be transformative for quantum computing and will represent a qualitative step forward in materials prediction and control.

  17. Observations on variational and projector Monte Carlo methods.

    PubMed

    Umrigar, C J

    2015-10-28

    Variational Monte Carlo and various projector Monte Carlo (PMC) methods are presented in a unified manner. Similarities and differences between the methods and choices made in designing the methods are discussed. Both methods where the Monte Carlo walk is performed in a discrete space and methods where it is performed in a continuous space are considered. It is pointed out that the usual prescription for importance sampling may not be advantageous depending on the particular quantum Monte Carlo method used and the observables of interest, so alternate prescriptions are presented. The nature of the sign problem is discussed for various versions of PMC methods. A prescription for an exact PMC method in real space, i.e., a method that does not make a fixed-node or similar approximation and does not have a finite basis error, is presented. This method is likely to be practical for systems with a small number of electrons. Approximate PMC methods that are applicable to larger systems and go beyond the fixed-node approximation are also discussed. PMID:26520496

  18. Observations on variational and projector Monte Carlo methods

    NASA Astrophysics Data System (ADS)

    Umrigar, C. J.

    2015-10-01

    Variational Monte Carlo and various projector Monte Carlo (PMC) methods are presented in a unified manner. Similarities and differences between the methods and choices made in designing the methods are discussed. Both methods where the Monte Carlo walk is performed in a discrete space and methods where it is performed in a continuous space are considered. It is pointed out that the usual prescription for importance sampling may not be advantageous depending on the particular quantum Monte Carlo method used and the observables of interest, so alternate prescriptions are presented. The nature of the sign problem is discussed for various versions of PMC methods. A prescription for an exact PMC method in real space, i.e., a method that does not make a fixed-node or similar approximation and does not have a finite basis error, is presented. This method is likely to be practical for systems with a small number of electrons. Approximate PMC methods that are applicable to larger systems and go beyond the fixed-node approximation are also discussed.

  19. Observations on variational and projector Monte Carlo methods

    SciTech Connect

    Umrigar, C. J.

    2015-10-28

    Variational Monte Carlo and various projector Monte Carlo (PMC) methods are presented in a unified manner. Similarities and differences between the methods and choices made in designing the methods are discussed. Both methods where the Monte Carlo walk is performed in a discrete space and methods where it is performed in a continuous space are considered. It is pointed out that the usual prescription for importance sampling may not be advantageous depending on the particular quantum Monte Carlo method used and the observables of interest, so alternate prescriptions are presented. The nature of the sign problem is discussed for various versions of PMC methods. A prescription for an exact PMC method in real space, i.e., a method that does not make a fixed-node or similar approximation and does not have a finite basis error, is presented. This method is likely to be practical for systems with a small number of electrons. Approximate PMC methods that are applicable to larger systems and go beyond the fixed-node approximation are also discussed.

  20. Quantum memory Quantum memory

    NASA Astrophysics Data System (ADS)

    Le Gouët, Jean-Louis; Moiseev, Sergey

    2012-06-01

    Interaction of quantum radiation with multi-particle ensembles has sparked off intense research efforts during the past decade. Emblematic of this field is the quantum memory scheme, where a quantum state of light is mapped onto an ensemble of atoms and then recovered in its original shape. While opening new access to the basics of light-atom interaction, quantum memory also appears as a key element for information processing applications, such as linear optics quantum computation and long-distance quantum communication via quantum repeaters. Not surprisingly, it is far from trivial to practically recover a stored quantum state of light and, although impressive progress has already been accomplished, researchers are still struggling to reach this ambitious objective. This special issue provides an account of the state-of-the-art in a fast-moving research area that makes physicists, engineers and chemists work together at the forefront of their discipline, involving quantum fields and atoms in different media, magnetic resonance techniques and material science. Various strategies have been considered to store and retrieve quantum light. The explored designs belong to three main—while still overlapping—classes. In architectures derived from photon echo, information is mapped over the spectral components of inhomogeneously broadened absorption bands, such as those encountered in rare earth ion doped crystals and atomic gases in external gradient magnetic field. Protocols based on electromagnetic induced transparency also rely on resonant excitation and are ideally suited to the homogeneous absorption lines offered by laser cooled atomic clouds or ion Coulomb crystals. Finally off-resonance approaches are illustrated by Faraday and Raman processes. Coupling with an optical cavity may enhance the storage process, even for negligibly small atom number. Multiple scattering is also proposed as a way to enlarge the quantum interaction distance of light with matter. The

  1. 4-Component correlated all-electron study on Eka-actinium Fluoride (E121F) including Gaunt interaction: Accurate analytical form, bonding and influence on rovibrational spectra

    NASA Astrophysics Data System (ADS)

    Amador, Davi H. T.; de Oliveira, Heibbe C. B.; Sambrano, Julio R.; Gargano, Ricardo; de Macedo, Luiz Guilherme M.

    2016-10-01

    A prolapse-free basis set for Eka-Actinium (E121, Z = 121), numerical atomic calculations on E121, spectroscopic constants and accurate analytical form for the potential energy curve of diatomic E121F obtained at 4-component all-electron CCSD(T) level including Gaunt interaction are presented. The results show a strong and polarized bond (≈181 kcal/mol in strength) between E121 and F, the outermost frontier molecular orbitals from E121F should be fairly similar to the ones from AcF and there is no evidence of break of periodic trends. Moreover, the Gaunt interaction, although small, is expected to influence considerably the overall rovibrational spectra.

  2. All-electron molecular Dirac-Hartree-Fock calculations: Properties of the group IV monoxides GeO, SnO and PbO

    NASA Technical Reports Server (NTRS)

    Dyall, Kenneth G.

    1991-01-01

    Dirac-Hartree-Fock calculations have been carried out on the ground states of the group IV monoxides GeO, SnO and PbO. Geometries, dipole moments and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate the results are compared with the experimental data and previous calculations. Spin-orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass-velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides, and confirm the conclusions drawn on the basis of the hydride calculations.

  3. Estimation of beryllium ground state energy by Monte Carlo simulation

    SciTech Connect

    Kabir, K. M. Ariful; Halder, Amal

    2015-05-15

    Quantum Monte Carlo method represent a powerful and broadly applicable computational tool for finding very accurate solution of the stationary Schrödinger equation for atoms, molecules, solids and a variety of model systems. Using variational Monte Carlo method we have calculated the ground state energy of the Beryllium atom. Our calculation are based on using a modified four parameters trial wave function which leads to good result comparing with the few parameters trial wave functions presented before. Based on random Numbers we can generate a large sample of electron locations to estimate the ground state energy of Beryllium. Our calculation gives good estimation for the ground state energy of the Beryllium atom comparing with the corresponding exact data.

  4. Nuclear pairing within a configuration-space Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Lingle, Mark; Volya, Alexander

    2015-06-01

    Pairing correlations in nuclei play a decisive role in determining nuclear drip lines, binding energies, and many collective properties. In this work a new configuration-space Monte Carlo (CSMC) method for treating nuclear pairing correlations is developed, implemented, and demonstrated. In CSMC the Hamiltonian matrix is stochastically generated in Krylov subspace, resulting in the Monte Carlo version of Lanczos-like diagonalization. The advantages of this approach over other techniques are discussed; the absence of the fermionic sign problem, probabilistic interpretation of quantum-mechanical amplitudes, and ability to handle truly large-scale problems with defined precision and error control are noteworthy merits of CSMC. The features of our CSMC approach are shown using models and realistic examples. Special attention is given to difficult limits: situations with nonconstant pairing strengths, cases with nearly degenerate excited states, limits when pairing correlations in finite systems are weak, and problems when the relevant configuration space is large.

  5. Quantum Communication

    NASA Astrophysics Data System (ADS)

    Weinfurter, Harald; Zeilinger, Anton

    Quantum entanglement lies at the heart of the new field of quantum communication and computation. For a long time, entanglement was seen just as one of those fancy features which make quantum mechanics so counterintuitive. But recently, quantum information theory has shown the tremendous importance of quantum correlations for the formulation of new methods of information transfer and for algorithms exploiting the capabilities of quantum computers.This chapter describes the first experimental realizations of quantum communication schemes using entangled photon pairs. We show how to make communication secure against eavesdropping using entanglement-based quantum cryptography, how to increase the information capacity of a quantum channel by quantum dense coding and, finally, how to communicate quantum information itself in the process of quantum teleportation.

  6. Proton Upset Monte Carlo Simulation

    NASA Technical Reports Server (NTRS)

    O'Neill, Patrick M.; Kouba, Coy K.; Foster, Charles C.

    2009-01-01

    The Proton Upset Monte Carlo Simulation (PROPSET) program calculates the frequency of on-orbit upsets in computer chips (for given orbits such as Low Earth Orbit, Lunar Orbit, and the like) from proton bombardment based on the results of heavy ion testing alone. The software simulates the bombardment of modern microelectronic components (computer chips) with high-energy (.200 MeV) protons. The nuclear interaction of the proton with the silicon of the chip is modeled and nuclear fragments from this interaction are tracked using Monte Carlo techniques to produce statistically accurate predictions.

  7. Stochastic solution to quantum dynamics

    NASA Technical Reports Server (NTRS)

    John, Sarah; Wilson, John W.

    1994-01-01

    The quantum Liouville equation in the Wigner representation is solved numerically by using Monte Carlo methods. For incremental time steps, the propagation is implemented as a classical evolution in phase space modified by a quantum correction. The correction, which is a momentum jump function, is simulated in the quasi-classical approximation via a stochastic process. The technique, which is developed and validated in two- and three- dimensional momentum space, extends an earlier one-dimensional work. Also, by developing a new algorithm, the application to bound state motion in an anharmonic quartic potential shows better agreement with exact solutions in two-dimensional phase space.

  8. Mineralogy of Libya Montes, Mars

    NASA Astrophysics Data System (ADS)

    Perry, K. A.; Bishop, J. L.; McKeown, N. K.

    2009-12-01

    Observations by CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) have revealed a range of minerals in Libya Montes including olivine, pyroxene, and phyllosilicate [1]. Here we extend our spectral analyses of CRISM images in Libya Montes to identify carbonates. We have also performed detailed characterization of the spectral signature of the phyllosilicate- and carbonate-bearing outcrops in order to constrain the types of phyllosilicates and carbonates present. Phyllosilicate-bearing rocks in Libya Montes have spectral bands at 1.42, 2.30 and 2.39 µm, consistent with Fe- and Mg- bearing smectites. The mixture of Fe and Mg in Libya Montes may be within the clay mineral structure or within the CRISM pixel. Because the pixels have 18 meter/pixel spatial resolution, it is possible that the bands observed are due to the mixing of nontronite and saponite rather than a smectite with both Fe and Mg. Carbonates found in Libya Montes are similar to those found in Nili Fossae [2]. The carbonates have bands centered at 2.30 and 2.52 µm. Libya Montes carbonates most closely resemble the Mg-carbonate, magnesite. Olivine spectra are seen throughout Libya Montes, characterized by a positive slope from 1.2-1.8 µm. Large outcrops of olivine are relatively rare on Mars [3]. This implies that fresh bedrock has been recently exposed because olivine weathers readily compared to pyroxene and feldspar. Pyroxene in Libya Montes resembles an Fe-bearing orthopyroxene with a broad band centered at 1.82 µm. The lowermost unit identified in Libya Montes is a clay-bearing unit. Overlying this is a carbonate-bearing unit with a clear unit division visible in at least one CRISM image. An olivine-bearing unit unconformably overlies these two units and may represent a drape related to the Isidis impact, as suggested for Nili Fossae [2]. However, it appears that the carbonate in Libya Montes is an integral portion of the rock underlying the olivine-bearing unit rather than an

  9. Communication: Water on hexagonal boron nitride from diffusion Monte Carlo

    NASA Astrophysics Data System (ADS)

    Al-Hamdani, Yasmine S.; Ma, Ming; Alfè, Dario; von Lilienfeld, O. Anatole; Michaelides, Angelos

    2015-05-01

    Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of -84 ± 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT.

  10. Communication: Water on hexagonal boron nitride from diffusion Monte Carlo.

    PubMed

    Al-Hamdani, Yasmine S; Ma, Ming; Alfè, Dario; von Lilienfeld, O Anatole; Michaelides, Angelos

    2015-05-14

    Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of -84 ± 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT. PMID:25978876

  11. Communication: Water on hexagonal boron nitride from diffusion Monte Carlo

    SciTech Connect

    Al-Hamdani, Yasmine S.; Ma, Ming; Michaelides, Angelos; Alfè, Dario; Lilienfeld, O. Anatole von

    2015-05-14

    Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of −84 ± 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT.

  12. Quantum simulation

    NASA Astrophysics Data System (ADS)

    Georgescu, I. M.; Ashhab, S.; Nori, Franco

    2014-01-01

    Simulating quantum mechanics is known to be a difficult computational problem, especially when dealing with large systems. However, this difficulty may be overcome by using some controllable quantum system to study another less controllable or accessible quantum system, i.e., quantum simulation. Quantum simulation promises to have applications in the study of many problems in, e.g., condensed-matter physics, high-energy physics, atomic physics, quantum chemistry, and cosmology. Quantum simulation could be implemented using quantum computers, but also with simpler, analog devices that would require less control, and therefore, would be easier to construct. A number of quantum systems such as neutral atoms, ions, polar molecules, electrons in semiconductors, superconducting circuits, nuclear spins, and photons have been proposed as quantum simulators. This review outlines the main theoretical and experimental aspects of quantum simulation and emphasizes some of the challenges and promises of this fast-growing field.

  13. Heats of Segregation of BCC Metals Using Ab Initio and Quantum Approximate Methods

    NASA Technical Reports Server (NTRS)

    Good, Brian; Chaka, Anne; Bozzolo, Guillermo

    2003-01-01

    Many multicomponent alloys exhibit surface segregation, in which the composition at or near a surface may be substantially different from that of the bulk. A number of phenomenological explanations for this tendency have been suggested, involving, among other things, differences among the components' surface energies, molar volumes, and heats of solution. From a theoretical standpoint, the complexity of the problem has precluded a simple, unified explanation, thus preventing the development of computational tools that would enable the identification of the driving mechanisms for segregation. In that context, we investigate the problem of surface segregation in a variety of bcc metal alloys by computing dilute-limit heats of segregation using both the quantum-approximate energy method of Bozzolo, Ferrante and Smith (BFS), and all-electron density functional theory. In addition, the composition dependence of the heats of segregation is investigated using a BFS-based Monte Carlo procedure, and, for selected cases of interest, density functional calculations. Results are discussed in the context of a simple picture that describes segregation behavior as the result of a competition between size mismatch and alloying effects

  14. Multilevel sequential Monte Carlo samplers

    DOE PAGES

    Beskos, Alexandros; Jasra, Ajay; Law, Kody; Tempone, Raul; Zhou, Yan

    2016-08-24

    Here, we study the approximation of expectations w.r.t. probability distributions associated to the solution of partial differential equations (PDEs); this scenario appears routinely in Bayesian inverse problems. In practice, one often has to solve the associated PDE numerically, using, for instance finite element methods and leading to a discretisation bias, with the step-size level hL. In addition, the expectation cannot be computed analytically and one often resorts to Monte Carlo methods. In the context of this problem, it is known that the introduction of the multilevel Monte Carlo (MLMC) method can reduce the amount of computational effort to estimate expectations, for a given level of error. This is achieved via a telescoping identity associated to a Monte Carlo approximation of a sequence of probability distributions with discretisation levelsmore » $${\\infty}$$ >h0>h1 ...>hL. In many practical problems of interest, one cannot achieve an i.i.d. sampling of the associated sequence of probability distributions. A sequential Monte Carlo (SMC) version of the MLMC method is introduced to deal with this problem. In conclusion, it is shown that under appropriate assumptions, the attractive property of a reduction of the amount of computational effort to estimate expectations, for a given level of error, can be maintained within the SMC context.« less

  15. Monte Carlo calculations of nuclei

    SciTech Connect

    Pieper, S.C.

    1997-10-01

    Nuclear many-body calculations have the complication of strong spin- and isospin-dependent potentials. In these lectures the author discusses the variational and Green`s function Monte Carlo techniques that have been developed to address this complication, and presents a few results.

  16. Bold Diagrammatic Monte Carlo Method Applied to Fermionized Frustrated Spins

    NASA Astrophysics Data System (ADS)

    Kulagin, S. A.; Prokof'ev, N.; Starykh, O. A.; Svistunov, B.; Varney, C. N.

    2013-02-01

    We demonstrate, by considering the triangular lattice spin-1/2 Heisenberg model, that Monte Carlo sampling of skeleton Feynman diagrams within the fermionization framework offers a universal first-principles tool for strongly correlated lattice quantum systems. We observe the fermionic sign blessing—cancellation of higher order diagrams leading to a finite convergence radius of the series. We calculate the magnetic susceptibility of the triangular-lattice quantum antiferromagnet in the correlated paramagnet regime and reveal a surprisingly accurate microscopic correspondence with its classical counterpart at all accessible temperatures. The extrapolation of the observed relation to zero temperature suggests the absence of the magnetic order in the ground state. We critically examine the implications of this unusual scenario.

  17. Cluster size dependence of double ionization energy spectra of spin-polarized aluminum and sodium clusters: All-electron spin-polarized GW+T -matrix method

    NASA Astrophysics Data System (ADS)

    Noguchi, Yoshifumi; Ohno, Kaoru; Solovyev, Igor; Sasaki, Taizo

    2010-04-01

    The double ionization energy (DIE) spectra are calculated for the spin-polarized aluminum and sodium clusters by means of the all-electron spin-polarized GW+T -matrix method based on the many-body perturbation theory. Our method using the one- and two-particle Green’s functions enables us to determine the whole spectra at once in a single calculation. The smaller is the size of the cluster, the larger the difference between the minimal double ionization energy and the twice of the ionization potential. This is because the strong Coulomb repulsion between two holes becomes dominant in small confined geometry. Due to Pauli’s exclusion principle, the parallel spin DIE is close to or smaller than the antiparallel spin DIE except for Na4 that has well-separated highest and second highest occupied molecular-orbital levels calculated by the spin-dependent GW calculation. In this paper, we compare the results calculated for aluminum and sodium clusters and discuss the spin-polarized effect and the cluster size dependence of the resulting spectra in detail.

  18. Monte Carlo simulation of a quantized universe.

    NASA Astrophysics Data System (ADS)

    Berger, Beverly K.

    1988-08-01

    A Monte Carlo simulation method which yields groundstate wave functions for multielectron atoms is applied to quantized cosmological models. In quantum mechanics, the propagator for the Schrödinger equation reduces to the absolute value squared of the groundstate wave function in the limit of infinite Euclidean time. The wave function of the universe as the solution to the Wheeler-DeWitt equation may be regarded as the zero energy mode of a Schrödinger equation in coordinate time. The simulation evaluates the path integral formulation of the propagator by constructing a large number of paths and computing their contribution to the path integral using the Metropolis algorithm to drive the paths toward a global minimum in the path energy. The result agrees with a solution to the Wheeler-DeWitt equation which has the characteristics of a nodeless groundstate wave function. Oscillatory behavior cannot be reproduced although the simulation results may be physically reasonable. The primary advantage of the simulations is that they may easily be extended to cosmologies with many degrees of freedom. Examples with one, two, and three degrees of freedom (d.f.) are presented.

  19. Monte Carlo Experiments: Design and Implementation.

    ERIC Educational Resources Information Center

    Paxton, Pamela; Curran, Patrick J.; Bollen, Kenneth A.; Kirby, Jim; Chen, Feinian

    2001-01-01

    Illustrates the design and planning of Monte Carlo simulations, presenting nine steps in planning and performing a Monte Carlo analysis from developing a theoretically derived question of interest through summarizing the results. Uses a Monte Carlo simulation to illustrate many of the relevant points. (SLD)

  20. Monte Carlo Simulation for Perusal and Practice.

    ERIC Educational Resources Information Center

    Brooks, Gordon P.; Barcikowski, Robert S.; Robey, Randall R.

    The meaningful investigation of many problems in statistics can be solved through Monte Carlo methods. Monte Carlo studies can help solve problems that are mathematically intractable through the analysis of random samples from populations whose characteristics are known to the researcher. Using Monte Carlo simulation, the values of a statistic are…

  1. Quantum ontologies

    SciTech Connect

    Stapp, H.P.

    1988-12-01

    Quantum ontologies are conceptions of the constitution of the universe that are compatible with quantum theory. The ontological orientation is contrasted to the pragmatic orientation of science, and reasons are given for considering quantum ontologies both within science, and in broader contexts. The principal quantum ontologies are described and evaluated. Invited paper at conference: Bell's Theorem, Quantum Theory, and Conceptions of the Universe, George Mason University, October 20-21, 1988. 16 refs.

  2. Quantum Monte Carlo simulation of the dissipative granular array

    NASA Astrophysics Data System (ADS)

    Matsumoto, Munehisa; Troyer, Matthias

    2007-03-01

    We develop a new cluster algorithm for the dissipative granular arrays and apply it to the one-dimensional (1D) array. The problem in the simulation of the dissipative granular array arises from the competition between the phase difference terms and the on-site charging energy terms in the action. We divide these two kinds of terms into on-site terms and inter-site terms. A cluster update for the latter is combined with the Metropolis method for the former, being in the same spirit as was done for the resistively-shunted Josephson-junction array [1]. The on-site charging energy is calculated for the 1D array and its dependence on the strength of dissipation is discussed in comparison to several theoretical predictions [2]. [1] P. Werner and M. Troyer: Phys. Rev. Lett. 95 (2005) 060201. [2] K. B. Efetov and A. Tschersich: Europhys. Lett. 59 (2002) 114; A. Altland, L.I. Glazman, A. Kamenev: Phys. Rev. Lett 92 (2004) 026801.

  3. Quantum Computer Games: Quantum Minesweeper

    ERIC Educational Resources Information Center

    Gordon, Michal; Gordon, Goren

    2010-01-01

    The computer game of quantum minesweeper is introduced as a quantum extension of the well-known classical minesweeper. Its main objective is to teach the unique concepts of quantum mechanics in a fun way. Quantum minesweeper demonstrates the effects of superposition, entanglement and their non-local characteristics. While in the classical…

  4. A Wigner Monte Carlo approach to density functional theory

    SciTech Connect

    Sellier, J.M. Dimov, I.

    2014-08-01

    In order to simulate quantum N-body systems, stationary and time-dependent density functional theories rely on the capacity of calculating the single-electron wave-functions of a system from which one obtains the total electron density (Kohn–Sham systems). In this paper, we introduce the use of the Wigner Monte Carlo method in ab-initio calculations. This approach allows time-dependent simulations of chemical systems in the presence of reflective and absorbing boundary conditions. It also enables an intuitive comprehension of chemical systems in terms of the Wigner formalism based on the concept of phase-space. Finally, being based on a Monte Carlo method, it scales very well on parallel machines paving the way towards the time-dependent simulation of very complex molecules. A validation is performed by studying the electron distribution of three different systems, a Lithium atom, a Boron atom and a hydrogenic molecule. For the sake of simplicity, we start from initial conditions not too far from equilibrium and show that the systems reach a stationary regime, as expected (despite no restriction is imposed in the choice of the initial conditions). We also show a good agreement with the standard density functional theory for the hydrogenic molecule. These results demonstrate that the combination of the Wigner Monte Carlo method and Kohn–Sham systems provides a reliable computational tool which could, eventually, be applied to more sophisticated problems.

  5. Monte Carlo methods in ICF

    SciTech Connect

    Zimmerman, G.B.

    1997-06-24

    Monte Carlo methods appropriate to simulate the transport of x-rays, neutrons, ion and electrons in Inertial Confinement Fusion targets are described and analyzed. The Implicit Monte Carlo method of x-ray transport handles symmetry within indirect drive ICF hohlraums well, but can be improved 50X in efficiency by angular biasing the x-rays towards the fuel capsule. Accurate simulation of thermonuclear burns nd burn diagnostics involves detailed particle source spectra, charged particle ranges, inflight reaction kinematics, corrections for bulk and thermal Doppler effects and variance reduction to obtain adequate statistics for rare events. It is found that the effects of angular Coulomb scattering must be included in models of charged particle transport through heterogeneous materials.

  6. Improved Full Configuration Interaction Monte Carlo for the Hubbard Model

    NASA Astrophysics Data System (ADS)

    Changlani, Hitesh; Holmes, Adam; Petruzielo, Frank; Chan, Garnet; Henley, C. L.; Umrigar, C. J.

    2012-02-01

    We consider the recently proposed full configuration interaction quantum Monte Carlo (FCI-QMC) method and its ``initiator'' extension, both of which promise to ameliorate the sign problem by utilizing the cancellation of positive and negative walkers in the Hilbert space of Slater determinants. While the method has been primarily used for quantum chemistry by A.Alavi and his co-workers [1,2], its application to lattice models in solid state physics has not been tested. We propose an improvement in the form of choosing a basis to make the wavefunction more localized in Fock space, which potentially also reduces the sign problem. We perform calculations on the 4x4 and 8x8 Hubbard models in real and momentum space and in a basis motivated by the reduced density matrix of a 2x2 real space patch obtained from the exact diagonalization of a larger system in which it is embedded. We discuss our results for a range of fillings and U/t and compare them with previous Auxiliary Field QMC and Fixed Node Green's Function Monte Carlo calculations. [4pt] [1] George Booth, Alex Thom, Ali Alavi, J Chem Phys, 131, 050106,(2009)[0pt] [2] D Cleland, GH Booth, Ali Alavi, J Chem Phys 132, 041103, (2010)

  7. Path integral Monte Carlo on a lattice. II. Bound states

    NASA Astrophysics Data System (ADS)

    O'Callaghan, Mark; Miller, Bruce N.

    2016-07-01

    The equilibrium properties of a single quantum particle (qp) interacting with a classical gas for a wide range of temperatures that explore the system's behavior in the classical as well as in the quantum regime is investigated. Both the qp and the atoms are restricted to sites on a one-dimensional lattice. A path integral formalism developed within the context of the canonical ensemble is utilized, where the qp is represented by a closed, variable-step random walk on the lattice. Monte Carlo methods are employed to determine the system's properties. To test the usefulness of the path integral formalism, the Metropolis algorithm is employed to determine the equilibrium properties of the qp in the context of a square well potential, forcing the qp to occupy bound states. We consider a one-dimensional square well potential where all atoms on the lattice are occupied with one atom with an on-site potential except for a contiguous set of sites of various lengths centered at the middle of the lattice. Comparison of the potential energy, the energy fluctuations, and the correlation function are made between the results of the Monte Carlo simulations and the numerical calculations.

  8. Path integral Monte Carlo on a lattice. II. Bound states.

    PubMed

    O'Callaghan, Mark; Miller, Bruce N

    2016-07-01

    The equilibrium properties of a single quantum particle (qp) interacting with a classical gas for a wide range of temperatures that explore the system's behavior in the classical as well as in the quantum regime is investigated. Both the qp and the atoms are restricted to sites on a one-dimensional lattice. A path integral formalism developed within the context of the canonical ensemble is utilized, where the qp is represented by a closed, variable-step random walk on the lattice. Monte Carlo methods are employed to determine the system's properties. To test the usefulness of the path integral formalism, the Metropolis algorithm is employed to determine the equilibrium properties of the qp in the context of a square well potential, forcing the qp to occupy bound states. We consider a one-dimensional square well potential where all atoms on the lattice are occupied with one atom with an on-site potential except for a contiguous set of sites of various lengths centered at the middle of the lattice. Comparison of the potential energy, the energy fluctuations, and the correlation function are made between the results of the Monte Carlo simulations and the numerical calculations. PMID:27575090

  9. Quantum memristors

    PubMed Central

    Pfeiffer, P.; Egusquiza, I. L.; Di Ventra, M.; Sanz, M.; Solano, E.

    2016-01-01

    Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantum regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. The proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems. PMID:27381511

  10. Quantum memristors.

    PubMed

    Pfeiffer, P; Egusquiza, I L; Di Ventra, M; Sanz, M; Solano, E

    2016-01-01

    Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantum regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. The proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems. PMID:27381511

  11. Quantum memristors.

    PubMed

    Pfeiffer, P; Egusquiza, I L; Di Ventra, M; Sanz, M; Solano, E

    2016-07-06

    Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantum regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. The proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems.

  12. Quantum memristors

    NASA Astrophysics Data System (ADS)

    Pfeiffer, P.; Egusquiza, I. L.; di Ventra, M.; Sanz, M.; Solano, E.

    2016-07-01

    Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantum regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. The proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems.

  13. The D0 Monte Carlo

    SciTech Connect

    Womersley, J. . Dept. of Physics)

    1992-10-01

    The D0 detector at the Fermilab Tevatron began its first data taking run in May 1992. For analysis of the expected 25 pb[sup [minus]1] data sample, roughly half a million simulated events will be needed. The GEANT-based Monte Carlo program used to generate these events is described, together with comparisons to test beam data. Some novel techniques used to speed up execution and simplify geometrical input are described.

  14. A fixed-node Diffusion Monte Carlo study of the 1,2,3-tridehydrobenzene triradical

    SciTech Connect

    Koziol, Lucas; Morales, Miguel M.

    2014-06-14

    The electronic structure of 1,2,3-tridehydrobenzene was investigated using quantum Monte Carlo methods. The radical contains two low-lying electronic states that are nearly degenerate adiabatically (within 2 kcal/mol separation), according to previous coupled cluster calculations. We performed Diffusion Monte Carlo (DMC) calculations starting from Multi-Reference Configuration Interaction (MRCI) trial wavefunctions, with a complete active space (CAS) containing 9 electrons in 9 orbitals, CAS(9,9). Our converged DMC results are in close agreement with the best coupled-cluster results, and further strengthen the assignment of a {sup 2}A{sub 1} ground state.

  15. Quantum Teardrops

    NASA Astrophysics Data System (ADS)

    Brzeziński, Tomasz; Fairfax, Simon A.

    2012-11-01

    Algebras of functions on quantum weighted projective spaces are introduced, and the structure of quantum weighted projective lines or quantum teardrops is described in detail. In particular the presentation of the coordinate algebra of the quantum teardrop in terms of generators and relations and classification of irreducible *-representations are derived. The algebras are then analysed from the point of view of Hopf-Galois theory or the theory of quantum principal bundles. Fredholm modules and associated traces are constructed. C*-algebras of continuous functions on quantum weighted projective lines are described and their K-groups computed.

  16. Quantum phase transition of the transverse-field quantum Ising model on scale-free networks.

    PubMed

    Yi, Hangmo

    2015-01-01

    I investigate the quantum phase transition of the transverse-field quantum Ising model in which nearest neighbors are defined according to the connectivity of scale-free networks. Using a continuous-time quantum Monte Carlo simulation method and the finite-size scaling analysis, I identify the quantum critical point and study its scaling characteristics. For the degree exponent λ=6, I obtain results that are consistent with the mean-field theory. For λ=4.5 and 4, however, the results suggest that the quantum critical point belongs to a non-mean-field universality class. Further simulations indicate that the quantum critical point remains mean-field-like if λ>5, but it continuously deviates from the mean-field theory as λ becomes smaller.

  17. Quantum Darwinism

    SciTech Connect

    Zurek, Wojciech H

    2008-01-01

    Quantum Darwinism - proliferation, in the environment, of multiple records of selected states of the system (its information-theoretic progeny) - explains how quantum fragility of individual state can lead to classical robustness of their multitude.

  18. Quantum memristors

    DOE PAGES

    Pfeiffer, P.; Egusquiza, I. L.; Di Ventra, M.; Sanz, M.; Solano, E.

    2016-07-06

    Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantummore » regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. As a result, the proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems.« less

  19. Quantum criticality

    NASA Astrophysics Data System (ADS)

    Coleman, Piers; Schofield, Andrew J.

    2005-01-01

    As we mark the centenary of Albert Einstein's seminal contribution to both quantum mechanics and special relativity, we approach another anniversary - that of Einstein's foundation of the quantum theory of solids. But 100 years on, the same experimental measurement that puzzled Einstein and his contemporaries is forcing us to question our understanding of how quantum matter transforms at ultra-low temperatures.

  20. Present status of vectorized Monte Carlo

    SciTech Connect

    Brown, F.B.

    1987-01-01

    Monte Carlo applications have traditionally been limited by the large amounts of computer time required to produce acceptably small statistical uncertainties, so the immediate benefit of vectorization is an increase in either the number of jobs completed or the number of particles processed per job, typically by one order of magnitude or more. This results directly in improved engineering design analyses, since Monte Carlo methods are used as standards for correcting more approximate methods. The relatively small number of vectorized programs is a consequence of the newness of vectorized Monte Carlo, the difficulties of nonportability, and the very large development effort required to rewrite or restructure Monte Carlo codes for vectorization. Based on the successful efforts to date, it may be concluded that Monte Carlo vectorization will spread to increasing numbers of codes and applications. The possibility of multitasking provides even further motivation for vectorizing Monte Carlo, since the step from vector to multitasked vector is relatively straightforward.

  1. Quantum frames

    NASA Astrophysics Data System (ADS)

    Brown, Matthew J.

    2014-02-01

    The framework of quantum frames can help unravel some of the interpretive difficulties i the foundation of quantum mechanics. In this paper, I begin by tracing the origins of this concept in Bohr's discussion of quantum theory and his theory of complementarity. Engaging with various interpreters and followers of Bohr, I argue that the correct account of quantum frames must be extended beyond literal space-time reference frames to frames defined by relations between a quantum system and the exosystem or external physical frame, of which measurement contexts are a particularly important example. This approach provides superior solutions to key EPR-type measurement and locality paradoxes.

  2. Quantum cheques

    NASA Astrophysics Data System (ADS)

    Moulick, Subhayan Roy; Panigrahi, Prasanta K.

    2016-06-01

    We propose the idea of a quantum cheque scheme, a cryptographic protocol in which any legitimate client of a trusted bank can issue a cheque, that cannot be counterfeited or altered in anyway, and can be verified by a bank or any of its branches. We formally define a quantum cheque and present the first unconditionally secure quantum cheque scheme and show it to be secure against any no-signalling adversary. The proposed quantum cheque scheme can been perceived as the quantum analog of Electronic Data Interchange, as an alternate for current e-Payment Gateways.

  3. Quantum Darwinism

    NASA Astrophysics Data System (ADS)

    Zurek, Wojciech Hubert

    2009-03-01

    Quantum Darwinism describes the proliferation, in the environment, of multiple records of selected states of a quantum system. It explains how the quantum fragility of a state of a single quantum system can lead to the classical robustness of states in their correlated multitude; shows how effective `wave-packet collapse' arises as a result of the proliferation throughout the environment of imprints of the state of the system; and provides a framework for the derivation of Born's rule, which relates the probabilities of detecting states to their amplitudes. Taken together, these three advances mark considerable progress towards settling the quantum measurement problem.

  4. Quantum Cryptography

    NASA Astrophysics Data System (ADS)

    Fehr, Serge

    2010-05-01

    Quantum cryptography makes use of the quantum-mechanical behavior of nature for the design and analysis of cryptographic schemes. Optimally (but not always), quantum cryptography allows for the design of cryptographic schemes whose security is guaranteed solely by the laws of nature. This is in sharp contrast to standard cryptographic schemes, which can be broken in principle, i.e., when given sufficient computing power. From a theory point of view, quantum cryptography offers a beautiful interplay between the mathematics of adversarial behavior and quantum information theory. In this review article, we discuss the traditional application of quantum cryptography, quantum key distribution (QKD), from a modern perspective, and we discuss some recent developments in the context of quantum two-party cooperation (2PC). QKD allows two distant parties to communicate in a provably-secure way in the presence of an outside eavesdropper, whereas 2PC is concerned with protecting information against possibly malicious insiders. We show the basic idea of constructing quantum cryptographic schemes, but we also show some connections to quantum information theory as needed for the rigorous security analyses, and we discuss some of the relevant quantum-information-theoretic results.

  5. Quantum Optics

    NASA Astrophysics Data System (ADS)

    Orvil Scully, Marlan; Zubairy, Muhammad Suhail

    1997-09-01

    Quantum optics has witnessed significant theoretical and experimental developments in recent years. This book provides an in-depth and wide-ranging introduction to the subject, emphasizing throughout the basic principles and their applications. The book begins by developing the basic tools of quantum optics, and goes on to show the application of these tools in a variety of quantum optical systems, including lasing without inversion, squeezed states, and atom optics. The final four chapters discuss quantum optical tests of the foundations of quantum mechanics, and particular aspects of measurement theory. Assuming only a background of standard quantum mechanics and electromagnetic theory, and containing many problems and references, this book will be invaluable to graduate students of quantum optics, as well as to researchers in this field.

  6. Uncertainty Propagation with Fast Monte Carlo Techniques

    NASA Astrophysics Data System (ADS)

    Rochman, D.; van der Marck, S. C.; Koning, A. J.; Sjöstrand, H.; Zwermann, W.

    2014-04-01

    Two new and faster Monte Carlo methods for the propagation of nuclear data uncertainties in Monte Carlo nuclear simulations are presented (the "Fast TMC" and "Fast GRS" methods). They are addressing the main drawback of the original Total Monte Carlo method (TMC), namely the necessary large time multiplication factor compared to a single calculation. With these new methods, Monte Carlo simulations can now be accompanied with uncertainty propagation (other than statistical), with small additional calculation time. The new methods are presented and compared with the TMC methods for criticality benchmarks.

  7. Monte Carlo Study of Real Time Dynamics on the Lattice.

    PubMed

    Alexandru, Andrei; Başar, Gökçe; Bedaque, Paulo F; Vartak, Sohan; Warrington, Neill C

    2016-08-19

    Monte Carlo studies involving real time dynamics are severely restricted by the sign problem that emerges from a highly oscillatory phase of the path integral. In this Letter, we present a new method to compute real time quantities on the lattice using the Schwinger-Keldysh formalism via Monte Carlo simulations. The key idea is to deform the path integration domain to a complex manifold where the phase oscillations are mild and the sign problem is manageable. We use the previously introduced "contraction algorithm" to create a Markov chain on this alternative manifold. We substantiate our approach by analyzing the quantum mechanical anharmonic oscillator. Our results are in agreement with the exact ones obtained by diagonalization of the Hamiltonian. The method we introduce is generic and, in principle, applicable to quantum field theory albeit very slow. We discuss some possible improvements that should speed up the algorithm. PMID:27588844

  8. Multidimensional stochastic approximation Monte Carlo.

    PubMed

    Zablotskiy, Sergey V; Ivanov, Victor A; Paul, Wolfgang

    2016-06-01

    Stochastic Approximation Monte Carlo (SAMC) has been established as a mathematically founded powerful flat-histogram Monte Carlo method, used to determine the density of states, g(E), of a model system. We show here how it can be generalized for the determination of multidimensional probability distributions (or equivalently densities of states) of macroscopic or mesoscopic variables defined on the space of microstates of a statistical mechanical system. This establishes this method as a systematic way for coarse graining a model system, or, in other words, for performing a renormalization group step on a model. We discuss the formulation of the Kadanoff block spin transformation and the coarse-graining procedure for polymer models in this language. We also apply it to a standard case in the literature of two-dimensional densities of states, where two competing energetic effects are present g(E_{1},E_{2}). We show when and why care has to be exercised when obtaining the microcanonical density of states g(E_{1}+E_{2}) from g(E_{1},E_{2}). PMID:27415383

  9. Multidimensional stochastic approximation Monte Carlo

    NASA Astrophysics Data System (ADS)

    Zablotskiy, Sergey V.; Ivanov, Victor A.; Paul, Wolfgang

    2016-06-01

    Stochastic Approximation Monte Carlo (SAMC) has been established as a mathematically founded powerful flat-histogram Monte Carlo method, used to determine the density of states, g (E ) , of a model system. We show here how it can be generalized for the determination of multidimensional probability distributions (or equivalently densities of states) of macroscopic or mesoscopic variables defined on the space of microstates of a statistical mechanical system. This establishes this method as a systematic way for coarse graining a model system, or, in other words, for performing a renormalization group step on a model. We discuss the formulation of the Kadanoff block spin transformation and the coarse-graining procedure for polymer models in this language. We also apply it to a standard case in the literature of two-dimensional densities of states, where two competing energetic effects are present g (E1,E2) . We show when and why care has to be exercised when obtaining the microcanonical density of states g (E1+E2) from g (E1,E2) .

  10. Monte Carlo surface flux tallies

    SciTech Connect

    Favorite, Jeffrey A

    2010-11-19

    Particle fluxes on surfaces are difficult to calculate with Monte Carlo codes because the score requires a division by the surface-crossing angle cosine, and grazing angles lead to inaccuracies. We revisit the standard practice of dividing by half of a cosine 'cutoff' for particles whose surface-crossing cosines are below the cutoff. The theory behind this approximation is sound, but the application of the theory to all possible situations does not account for two implicit assumptions: (1) the grazing band must be symmetric about 0, and (2) a single linear expansion for the angular flux must be applied in the entire grazing band. These assumptions are violated in common circumstances; for example, for separate in-going and out-going flux tallies on internal surfaces, and for out-going flux tallies on external surfaces. In some situations, dividing by two-thirds of the cosine cutoff is more appropriate. If users were able to control both the cosine cutoff and the substitute value, they could use these parameters to make accurate surface flux tallies. The procedure is demonstrated in a test problem in which Monte Carlo surface fluxes in cosine bins are converted to angular fluxes and compared with the results of a discrete ordinates calculation.

  11. Improved diffusion Monte Carlo and the Brownian fan

    NASA Astrophysics Data System (ADS)

    Weare, J.; Hairer, M.

    2012-12-01

    Diffusion Monte Carlo (DMC) is a workhorse of stochastic computing. It was invented forty years ago as the central component in a Monte Carlo technique for estimating various characteristics of quantum mechanical systems. Since then it has been used in applied in a huge number of fields, often as a central component in sequential Monte Carlo techniques (e.g. the particle filter). DMC computes averages of some underlying stochastic dynamics weighted by a functional of the path of the process. The weight functional could represent the potential term in a Feynman-Kac representation of a partial differential equation (as in quantum Monte Carlo) or it could represent the likelihood of a sequence of noisy observations of the underlying system (as in particle filtering). DMC alternates between an evolution step in which a collection of samples of the underlying system are evolved for some short time interval, and a branching step in which, according to the weight functional, some samples are copied and some samples are eliminated. Unfortunately for certain choices of the weight functional DMC fails to have a meaningful limit as one decreases the evolution time interval between branching steps. We propose a modification of the standard DMC algorithm. The new algorithm has a lower variance per workload, regardless of the regime considered. In particular, it makes it feasible to use DMC in situations where the ``naive'' generalization of the standard algorithm would be impractical, due to an exponential explosion of its variance. We numerically demonstrate the effectiveness of the new algorithm on a standard rare event simulation problem (probability of an unlikely transition in a Lennard-Jones cluster), as well as a high-frequency data assimilation problem. We then provide a detailed heuristic explanation of why, in the case of rare event simulation, the new algorithm is expected to converge to a limiting process as the underlying stepsize goes to 0. This is shown

  12. Monte Carlo simulation with aspect-ratio optimization: Anomalous anisotropic scaling in dimerized antiferromagnets

    NASA Astrophysics Data System (ADS)

    Yasuda, Shinya; Todo, Synge

    2013-12-01

    We present a method that optimizes the aspect ratio of a spatially anisotropic quantum lattice model during the quantum Monte Carlo simulation, and realizes the virtually isotropic lattice automatically. The anisotropy is removed by using the Robbins-Monro algorithm based on the correlation length in each direction. The method allows for comparing directly the value of the critical amplitude among different anisotropic models, and identifying the universality more precisely. We apply our method to the staggered dimer antiferromagnetic Heisenberg model and demonstrate that the apparent nonuniversal behavior is attributed mainly to the strong size correction of the effective aspect ratio due to the existence of the cubic interaction.

  13. Height control of self-assembled quantum dots by strain engineering during capping

    SciTech Connect

    Grossi, D. F. Koenraad, P. M.; Smereka, P.; Keizer, J. G.; Ulloa, J. M.

    2014-10-06

    Strain engineering during the capping of III-V quantum dots has been explored as a means to control the height of strained self-assembled quantum dots. Results of Kinetic Monte Carlo simulations are confronted with cross-sectional Scanning Tunnel Microscopy (STM) measurements performed on InAs quantum dots grown by molecular beam epitaxy. We studied InAs quantum dots that are capped by In{sub x}Ga{sub (1−x)}As layers of different indium compositions. Both from our realistic 3D kinetic Monte Carlo simulations and the X-STM measurements on real samples, a trend in the height of the capped quantum dot is found as a function of the lattice mismatch between the quantum dot material and the capping layer. Results obtained on additional material combinations show a generic role of the elastic energy in the control of the quantum dot morphology by strain engineering during capping.

  14. A configuration space Monte Carlo algorithm for solving the nuclear pairing problem

    NASA Astrophysics Data System (ADS)

    Lingle, Mark

    Nuclear pairing correlations using Quantum Monte Carlo are studied in this dissertation. We start by defining the nuclear pairing problem and discussing several historical methods developed to solve this problem, paying special attention to the applicability of such methods. A numerical example discussing pairing correlations in several calcium isotopes using the BCS and Exact Pairing solutions are presented. The ground state energies, correlation energies, and occupation numbers are compared to determine the applicability of each approach to realistic cases. Next we discuss some generalities related to the theory of Markov Chains and Quantum Monte Carlo in regards to nuclear structure. Finally we present our configuration space Monte Carlo algorithm starting from a discussion of a path integral approach by the authors. Some general features of the Pairing Hamiltonian that boost the effectiveness of a configuration space Monte Carlo approach are mentioned. The full details of our method are presented and special attention is paid to convergence and error control. We present a series of examples illustrating the effectiveness of our approach. These include situations with non-constant pairing strengths, limits when pairing correlations are weak, the computation of excited states, and problems when the relevant configuration space is large. We conclude with a chapter examining some of the effects of continuum states in 24O.

  15. Monte Carlo calculation of dynamical properties of the two-dimensional Hubbard model

    NASA Technical Reports Server (NTRS)

    White, S. R.; Scalapino, D. J.; Sugar, R. L.; Bickers, N. E.

    1989-01-01

    A new method is introduced for analytically continuing imaginary-time data from quantum Monte Carlo calculations to the real-frequency axis. The method is based on a least-squares-fitting procedure with constraints of positivity and smoothness on the real-frequency quantities. Results are shown for the single-particle spectral-weight function and density of states for the half-filled, two-dimensional Hubbard model.

  16. Application of Diffusion Monte Carlo to Materials Dominated by van der Waals Interactions

    SciTech Connect

    Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.; Kim, Jeongnim; von Lilienfeld, O. Anatole

    2014-06-12

    Van der Waals forces are notoriously difficult to account for from first principles. We perform extensive calculation to assess the usefulness and validity of diffusion quantum Monte Carlo when applied to van der Waals forces. We present results for noble gas solids and clusters - archetypical van der Waals dominated assemblies, as well as a relevant pi-pi stacking supramolecular complex: DNA + intercalating anti-cancer drug Ellipticine.

  17. Black hole entropy from strongly coupled gauge theory--direct confirmation by Monte Carlo simulaton

    SciTech Connect

    Takeuchi, Shingo

    2008-11-23

    We present the first Monte Carlo results for supersymmetric matrix quantum mechanics with sixteen supercharges at finite temperature. The recently proposed non-lattice simulation enables us to include the effects of fermionic matrices in a transparent and reliable manner. The internal energy nicely interpolates the weak coupling behavior obtained by the high temperature expansion, and the strong coupling behavior predicted from the dual black hole geometry. This results provide highly non-trivial evidences for the gauge/gravity duality.

  18. Quantum entanglement, quantum communication and the limits of quantum computing

    NASA Astrophysics Data System (ADS)

    Ambainis, Andris

    Quantum entanglement is a term describing the quantum correlations between different parts of a quantum system. Quantum information theory has developed sophisticated techniques to quantify and study quantum entanglement. In this thesis, we show how to apply those techniques to problems in quantum algorithms, complexity theory, communication and cryptography. The main results are: (1) quantum communication protocols that are exponentially more efficient that conventional (classical) communication protocols, (2) unconditionally secure quantum protocols for cryptographic problems, (3) a new "quantum adversary" method for proving lower bounds on quantum algorithms, (4) a study of "one clean qubit computation", a model related to the experimental implementation of quantum computers using NMR (nucleo-magnetic resonance) technology.

  19. Quantum volume

    NASA Astrophysics Data System (ADS)

    Ryabov, V. A.

    2015-08-01

    Quantum systems in a mechanical embedding, the breathing mode of a small particles, optomechanical system, etc. are far not the full list of examples in which the volume exhibits quantum behavior. Traditional consideration suggests strain in small systems as a result of a collective movement of particles, rather than the dynamics of the volume as an independent variable. The aim of this work is to show that some problem here might be essentially simplified by introducing periodic boundary conditions. At this case, the volume is considered as the independent dynamical variable driven by the internal pressure. For this purpose, the concept of quantum volume based on Schrödinger’s equation in 𝕋3 manifold is proposed. It is used to explore several 1D model systems: An ensemble of free particles under external pressure, quantum manometer and a quantum breathing mode. In particular, the influence of the pressure of free particle on quantum oscillator is determined. It is shown also that correction to the spectrum of the breathing mode due to internal degrees of freedom is determined by the off-diagonal matrix elements of the quantum stress. The new treatment not using the “force” theorem is proposed for the quantum stress tensor. In the general case of flexible quantum 3D dynamics, quantum deformations of different type might be introduced similarly to monopole mode.

  20. Monte Carlo Simulations for Radiobiology

    NASA Astrophysics Data System (ADS)

    Ackerman, Nicole; Bazalova, Magdalena; Chang, Kevin; Graves, Edward

    2012-02-01

    The relationship between tumor response and radiation is currently modeled as dose, quantified on the mm or cm scale through measurement or simulation. This does not take into account modern knowledge of cancer, including tissue heterogeneities and repair mechanisms. We perform Monte Carlo simulations utilizing Geant4 to model radiation treatment on a cellular scale. Biological measurements are correlated to simulated results, primarily the energy deposit in nuclear volumes. One application is modeling dose enhancement through the use of high-Z materials, such gold nanoparticles. The model matches in vitro data and predicts dose enhancement ratios for a variety of in vivo scenarios. This model shows promise for both treatment design and furthering our understanding of radiobiology.

  1. Structural mapping of Maxwell Montes

    NASA Technical Reports Server (NTRS)

    Keep, Myra; Hansen, Vicki L.

    1993-01-01

    Four sets of structures were mapped in the western and southern portions of Maxwell Montes. An early north-trending set of penetrative lineaments is cut by dominant, spaced ridges and paired valleys that trend northwest. To the south the ridges and valleys splay and graben form in the valleys. The spaced ridges and graben are cut by northeast-trending graben. The northwest-trending graben formed synchronously with or slightly later than the spaced ridges. Formation of the northeast-trending graben may have overlapped with that of the northwest-trending graben, but occurred in a spatially distinct area (regions of 2 deg slope). Graben formation, with northwest-southeast extension, may be related to gravity-sliding. Individually and collectively these structures are too small to support the immense topography of Maxwell, and are interpreted as parasitic features above a larger mass that supports the mountain belt.

  2. Quantum flywheel

    NASA Astrophysics Data System (ADS)

    Levy, Amikam; Diósi, Lajos; Kosloff, Ronnie

    2016-05-01

    In this work we present the concept of a quantum flywheel coupled to a quantum heat engine. The flywheel stores useful work in its energy levels, while additional power is extracted continuously from the device. Generally, the energy exchange between a quantum engine and a quantized work repository is accompanied by heat, which degrades the charging efficiency. Specifically when the quantum harmonic oscillator acts as a work repository, quantum and thermal fluctuations dominate the dynamics. Quantum monitoring and feedback control are applied to the flywheel in order to reach steady state and regulate its operation. To maximize the charging efficiency one needs a balance between the information gained by measuring the system and the information fed back to the system. The dynamics of the flywheel are described by a stochastic master equation that accounts for the engine, the external driving, the measurement, and the feedback operations.

  3. Quantum criticality.

    PubMed

    Coleman, Piers; Schofield, Andrew J

    2005-01-20

    As we mark the centenary of Albert Einstein's seminal contribution to both quantum mechanics and special relativity, we approach another anniversary--that of Einstein's foundation of the quantum theory of solids. But 100 years on, the same experimental measurement that puzzled Einstein and his contemporaries is forcing us to question our understanding of how quantum matter transforms at ultra-low temperatures. PMID:15662409

  4. Quantum seismography

    NASA Astrophysics Data System (ADS)

    Lanzagorta, Marco; Jitrik, Oliverio; Uhlmann, Jeffrey; Venegas, Salvador

    2016-05-01

    A major scientific thrust from recent years has been to try to harness quantum phenomena to increase the performance of a wide variety of information processing devices. In particular, quantum radar has emerged as an intriguing theoretical concept that could revolutionize electromagnetic standoff sensing. In this paper we will discuss how the techniques developed for quantum radar could also be used towards the design of novel seismographs able to detect small ground vibrations., We use a hypothetical earthquake warning system in order to compare quantum seismography with traditional seismographic techniques.

  5. Quantum Dots

    NASA Astrophysics Data System (ADS)

    Tartakovskii, Alexander

    2012-07-01

    Part I. Nanostructure Design and Structural Properties of Epitaxially Grown Quantum Dots and Nanowires: 1. Growth of III/V semiconductor quantum dots C. Schneider, S. Hofling and A. Forchel; 2. Single semiconductor quantum dots in nanowires: growth, optics, and devices M. E. Reimer, N. Akopian, M. Barkelid, G. Bulgarini, R. Heeres, M. Hocevar, B. J. Witek, E. Bakkers and V. Zwiller; 3. Atomic scale analysis of self-assembled quantum dots by cross-sectional scanning tunneling microscopy and atom probe tomography J. G. Keizer and P. M. Koenraad; Part II. Manipulation of Individual Quantum States in Quantum Dots Using Optical Techniques: 4. Studies of the hole spin in self-assembled quantum dots using optical techniques B. D. Gerardot and R. J. Warburton; 5. Resonance fluorescence from a single quantum dot A. N. Vamivakas, C. Matthiesen, Y. Zhao, C.-Y. Lu and M. Atature; 6. Coherent control of quantum dot excitons using ultra-fast optical techniques A. J. Ramsay and A. M. Fox; 7. Optical probing of holes in quantum dot molecules: structure, symmetry, and spin M. F. Doty and J. I. Climente; Part III. Optical Properties of Quantum Dots in Photonic Cavities and Plasmon-Coupled Dots: 8. Deterministic light-matter coupling using single quantum dots P. Senellart; 9. Quantum dots in photonic crystal cavities A. Faraon, D. Englund, I. Fushman, A. Majumdar and J. Vukovic; 10. Photon statistics in quantum dot micropillar emission M. Asmann and M. Bayer; 11. Nanoplasmonics with colloidal quantum dots V. Temnov and U. Woggon; Part IV. Quantum Dot Nano-Laboratory: Magnetic Ions and Nuclear Spins in a Dot: 12. Dynamics and optical control of an individual Mn spin in a quantum dot L. Besombes, C. Le Gall, H. Boukari and H. Mariette; 13. Optical spectroscopy of InAs/GaAs quantum dots doped with a single Mn atom O. Krebs and A. Lemaitre; 14. Nuclear spin effects in quantum dot optics B. Urbaszek, B. Eble, T. Amand and X. Marie; Part V. Electron Transport in Quantum Dots Fabricated by

  6. Vector Monte Carlo simulations on atmospheric scattering of polarization qubits.

    PubMed

    Li, Ming; Lu, Pengfei; Yu, Zhongyuan; Yan, Lei; Chen, Zhihui; Yang, Chuanghua; Luo, Xiao

    2013-03-01

    In this paper, a vector Monte Carlo (MC) method is proposed to study the influence of atmospheric scattering on polarization qubits for satellite-based quantum communication. The vector MC method utilizes a transmittance method to solve the photon free path for an inhomogeneous atmosphere and random number sampling to determine whether the type of scattering is aerosol scattering or molecule scattering. Simulations are performed for downlink and uplink. The degrees and the rotations of polarization are qualitatively and quantitatively obtained, which agree well with the measured results in the previous experiments. The results show that polarization qubits are well preserved in the downlink and uplink, while the number of received single photons is less than half of the total transmitted single photons for both links. Moreover, our vector MC method can be applied for the scattering of polarized light in other inhomogeneous random media.

  7. Monte Carlo study of double exchange interaction in manganese oxide

    SciTech Connect

    Naa, Christian Fredy; Suprijadi, Viridi, Sparisoma Djamal, Mitra; Fasquelle, Didier

    2015-09-30

    In this paper we study the magnetoresistance properties attributed by double exchange (DE) interaction in manganese oxide by Monte Carlo simulation. We construct a model based on mixed-valence Mn{sup 3+} and Mn{sup 4+} on the general system of Re{sub 2/3}Ae{sub 1/3}MnO{sub 3} in two dimensional system. The conduction mechanism is based on probability of e{sub g} electrons hopping from Mn{sup 3+} to Mn{sup 4+}. The resistivity dependence on temperature and the external magnetic field are presented and the validity with related experimental results are discussed. We use the resistivity power law to fit our data on metallic region and basic activated behavior on insulator region. On metallic region, we found our result agree well with the quantum theory of DE interaction. From general arguments, we found our simulation agree qualitatively with experimental results.

  8. Hellman-Feynman operator sampling in diffusion Monte Carlo calculations.

    PubMed

    Gaudoin, R; Pitarke, J M

    2007-09-21

    Diffusion Monte Carlo (DMC) calculations typically yield highly accurate results in solid-state and quantum-chemical calculations. However, operators that do not commute with the Hamiltonian are at best sampled correctly up to second order in the error of the underlying trial wave function once simple corrections have been applied. This error is of the same order as that for the energy in variational calculations. Operators that suffer from these problems include potential energies and the density. This Letter presents a new method, based on the Hellman-Feynman theorem, for the correct DMC sampling of all operators diagonal in real space. Our method is easy to implement in any standard DMC code.

  9. Reply to the comment on "Quantum trajectory tests of radical-pair quantum dynamics in CIDNP measurements of photosynthetic reaction centers" by G. Jeschke

    NASA Astrophysics Data System (ADS)

    Kominis, I. K.

    2016-03-01

    We recently unraveled a major inconsistency in the traditional description of radical-pair quantum dynamics by studying single-molecule quantum trajectories and comparing their prediction with Haberkorn's master equation. A comment by Jeschke claimed that the inconsistency arises because we did not properly include quantum state projections in the traditional approach. We here show that Jeschke stipulates quantum trajectories involving unphysical quantum states with negative populations. Moreover, the author's Monte Carlo simulation and its agreement with Haberkorn's master equation is a demonstration of an algebraic tautology, establishing the consistency of an unphysical master equation with circularly defined unphysical trajectories.

  10. Dissipative quantum computing with open quantum walks

    SciTech Connect

    Sinayskiy, Ilya; Petruccione, Francesco

    2014-12-04

    An open quantum walk approach to the implementation of a dissipative quantum computing scheme is presented. The formalism is demonstrated for the example of an open quantum walk implementation of a 3 qubit quantum circuit consisting of 10 gates.

  11. Quantum state transfer in double-quantum-well devices

    NASA Technical Reports Server (NTRS)

    Jakumeit, Jurgen; Tutt, Marcel; Pavlidis, Dimitris

    1994-01-01

    A Monte Carlo simulation of double-quantum-well (DQW) devices is presented in view of analyzing the quantum state transfer (QST) effect. Different structures, based on the AlGaAs/GaAs system, were simulated at 77 and 300 K and optimized in terms of electron transfer and device speed. The analysis revealed the dominant role of the impurity scattering for the QST. Different approaches were used for the optimization of QST devices and basic physical limitations were found in the electron transfer between the QWs. The maximum transfer of electrons from a high to a low mobility well was at best 20%. Negative differential resistance is hampered by the almost linear rather than threshold dependent relation of electron transfer on electric field. By optimizing the doping profile the operation frequency limit could be extended to 260 GHz.

  12. Simulated annealing versus quantum annealing

    NASA Astrophysics Data System (ADS)

    Troyer, Matthias

    Based on simulated classical annealing and simulated quantum annealing using quantum Monte Carlo (QMC) simulations I will explore the question where physical or simulated quantum annealers may outperform classical optimization algorithms. Although the stochastic dynamics of QMC simulations is not the same as the unitary dynamics of a quantum system, I will first show that for the problem of quantum tunneling between two local minima both QMC simulations and a physical system exhibit the same scaling of tunneling times with barrier height. The scaling in both cases is O (Δ2) , where Δ is the tunneling splitting. An important consequence is that QMC simulations can be used to predict the performance of a quantum annealer for tunneling through a barrier. Furthermore, by using open instead of periodic boundary conditions in imaginary time, equivalent to a projector QMC algorithm, one obtains a quadratic speedup for QMC, and achieve linear scaling in Δ. I will then address the apparent contradiction between experiments on a D-Wave 2 system that failed to see evidence of quantum speedup and previous QMC results that indicated an advantage of quantum annealing over classical annealing for spin glasses. We find that this contradiction is resolved by taking the continuous time limit in the QMC simulations which then agree with the experimentally observed behavior and show no speedup for 2D spin glasses. However, QMC simulations with large time steps gain further advantage: they ``cheat'' by ignoring what happens during a (large) time step, and can thus outperform both simulated quantum annealers and classical annealers. I will then address the question how to optimally run a simulated or physical quantum annealer. Investigating the behavior of the tails of the distribution of runtimes for very hard instances we find that adiabatically slow annealing is far from optimal. On the contrary, many repeated relatively fast annealing runs can be orders of magnitude faster for

  13. Probing loop quantum gravity with evaporating black holes.

    PubMed

    Barrau, A; Cailleteau, T; Cao, X; Diaz-Polo, J; Grain, J

    2011-12-16

    This Letter aims at showing that the observation of evaporating black holes should allow the usual Hawking behavior to be distinguished from loop quantum gravity (LQG) expectations. We present a full Monte Carlo simulation of the evaporation in LQG and statistical tests that discriminate between competing models. We conclude that contrarily to what was commonly thought, the discreteness of the area in LQG leads to characteristic features that qualify evaporating black holes as objects that could reveal quantum gravity footprints.

  14. Quantum metrology

    NASA Technical Reports Server (NTRS)

    Lee, H.; Kok, P.; Dowling, J. P.

    2002-01-01

    This paper addresses the formal equivalence between the Mach-Zehnder interferometer, the Ramsey spectroscope, and a specific quantum logical gate. Based on this equivalence we introduce the quantum Rosetta Stone, and we describe a projective measurement scheme for generating the desired correlations between the interferometric input states in order to achieve Heisenberg-limited sensitivity.

  15. Quantum microbiology.

    PubMed

    Trevors, J T; Masson, L

    2011-01-01

    During his famous 1943 lecture series at Trinity College Dublin, the reknown physicist Erwin Schrodinger discussed the failure and challenges of interpreting life by classical physics alone and that a new approach, rooted in Quantum principles, must be involved. Quantum events are simply a level of organization below the molecular level. This includes the atomic and subatomic makeup of matter in microbial metabolism and structures, as well as the organic, genetic information code of DNA and RNA. Quantum events at this time do not elucidate, for example, how specific genetic instructions were first encoded in an organic genetic code in microbial cells capable of growth and division, and its subsequent evolution over 3.6 to 4 billion years. However, due to recent technological advances, biologists and physicists are starting to demonstrate linkages between various quantum principles like quantum tunneling, entanglement and coherence in biological processes illustrating that nature has exerted some level quantum control to optimize various processes in living organisms. In this article we explore the role of quantum events in microbial processes and endeavor to show that after nearly 67 years, Schrödinger was prophetic and visionary in his view of quantum theory and its connection with some of the fundamental mechanisms of life. PMID:21368338

  16. Quantum picturalism

    NASA Astrophysics Data System (ADS)

    Coecke, Bob

    2010-01-01

    Why did it take us 50 years since the birth of the quantum mechanical formalism to discover that unknown quantum states cannot be cloned? Yet, the proof of the 'no-cloning theorem' is easy, and its consequences and potential for applications are immense. Similarly, why did it take us 60 years to discover the conceptually intriguing and easily derivable physical phenomenon of 'quantum teleportation'? We claim that the quantum mechanical formalism doesn't support our intuition, nor does it elucidate the key concepts that govern the behaviour of the entities that are subject to the laws of quantum physics. The arrays of complex numbers are kin to the arrays of 0s and 1s of the early days of computer programming practice. Using a technical term from computer science, the quantum mechanical formalism is 'low-level'. In this review we present steps towards a diagrammatic 'high-level' alternative for the Hilbert space formalism, one which appeals to our intuition. The diagrammatic language as it currently stands allows for intuitive reasoning about interacting quantum systems, and trivialises many otherwise involved and tedious computations. It clearly exposes limitations such as the no-cloning theorem, and phenomena such as quantum teleportation. As a logic, it supports 'automation': it enables a (classical) computer to reason about interacting quantum systems, prove theorems, and design protocols. It allows for a wider variety of underlying theories, and can be easily modified, having the potential to provide the required step-stone towards a deeper conceptual understanding of quantum theory, as well as its unification with other physical theories. Specific applications discussed here are purely diagrammatic proofs of several quantum computational schemes, as well as an analysis of the structural origin of quantum non-locality. The underlying mathematical foundation of this high-level diagrammatic formalism relies on so-called monoidal categories, a product of a fairly

  17. Monte Carlo simulation of high-field transport equations

    SciTech Connect

    Abdolsalami, F.

    1989-01-01

    The author has studied the importance of the intracollisional field effect in the quantum transport equation derived by Khan, Davies and Wilkins (Phys. Rev. B36, 2578(1987)) via Monte Carlo simulations. This transport equation is identical to the integral form of the Boltzmann transport equation except that the scattering-in rates contain the auxiliary function of energy width {radical}{vert bar}{alpha}{vert bar} instead of the sharp delta function of the semiclassical theory where {alpha} = {pi}{h bar}{sup 2} e/m* E {center dot} q. Here, E is the electric field, q is the phonon wave vector of m* is the effective mass. The transport equation studied corresponds to a single parabolic band of infinite width and is valid in the field dominated limit, i.e. {radical}{vert bar}{alpha}{vert bar} {much gt} h/{tau}{sub sc}, where {tau}{sup {minus}1} is the electron scattering-out rate. In his simulation, he takes the single parabolic band to be the central valley of GaAs with transition to higher valleys shut off. Electrons are assumed to scatter with polar optic and acoustic phonons with the scattering parameters chosen to simulate GaAs. The loss of intervalley scattering mechanism for high electric fields is compensated for by increasing each of the four scattering rates relative to the real values in GaAs by a factor {gamma}. The transport equation studied contains the auxilliary function which is not positive definite. Therefore, it can not represent a probability of scattering in a Monte Carlo simulation. The question whether or not intracollisional field effect is important can be resolved by replacing the nonpositive definite auxilliary function by a test positive definite function of width {radical}{vert bar}{alpha}{vert bar} and comparing the results of the Monte Carlo simulation of this quantum transport equation with those of the Boltzmann transport equation. If the results are identical, the intracollisional field effect is not important.

  18. Correlation length of the isotropic quantum Heisenberg antiferromagnet

    SciTech Connect

    Cuccoli, A.; Tognetti, V.; Vaia, R.

    1997-04-01

    The quantum Heisenberg antiferromagnet on the square lattice is known to model the magnetic interactions in the copper ion planes of many high-{ital T{sub c}} superconductors and their parent compounds. The thermodynamics of the model is approached by the {ital pure-quantum self-consistent harmonic approximation}, that reduces the quantum problem to the study of an effective classical antiferromagnetic system. The effective exchange, weakened by quantum fluctuations, enters as a temperature scale the classical-like expressions for the thermal averages, and the quantum spin correlation length is then obtained from its classical counterpart in a simple way. The theory compares very well, for any value of the spin and without need for adjustable parameters, with high temperature expansions, quantum Monte Carlo simulations, and recent neutron and nuclear quadrupole relaxation (NQR) experiments. {copyright} {ital 1997 American Institute of Physics.}

  19. Monte Carlo Shower Counter Studies

    NASA Technical Reports Server (NTRS)

    Snyder, H. David

    1991-01-01

    Activities and accomplishments related to the Monte Carlo shower counter studies are summarized. A tape of the VMS version of the GEANT software was obtained and installed on the central computer at Gallaudet University. Due to difficulties encountered in updating this VMS version, a decision was made to switch to the UNIX version of the package. This version was installed and used to generate the set of data files currently accessed by various analysis programs. The GEANT software was used to write files of data for positron and proton showers. Showers were simulated for a detector consisting of 50 alternating layers of lead and scintillator. Each file consisted of 1000 events at each of the following energies: 0.1, 0.5, 2.0, 10, 44, and 200 GeV. Data analysis activities related to clustering, chi square, and likelihood analyses are summarized. Source code for the GEANT user subprograms and data analysis programs are provided along with example data plots.

  20. Quantum Chaos

    NASA Astrophysics Data System (ADS)

    Casati, Giulio; Chirikov, Boris

    2006-11-01

    Preface; Acknowledgments; Introduction: 1. The legacy of chaos in quantum mechanics G. Casati and B. V. Chirikov; Part I. Classical Chaos and Quantum Localization: 2. Stochastic behaviour of a quantum pendulum under a periodic perturbation G. Casati, B. V. Chirikov, F. M. Izrailev and J. Ford; 3. Quantum dynamics of a nonintegrable system D. R. Grempel, R. E. Prange and S. E. Fishman; 4. Excitation of molecular rotation by periodic microwave pulses. A testing ground for Anderson localization R. Blümel, S. Fishman and U. Smilansky; 5. Localization of diffusive excitation in multi-level systems D. K. Shepelyansky; 6. Classical and quantum chaos for a kicked top F. Haake, M. Kus and R. Scharf; 7. Self-similarity in quantum dynamics L. E. Reichl and L. Haoming; 8. Time irreversibility of classically chaotic quantum dynamics K. Ikeda; 9. Effect of noise on time-dependent quantum chaos E. Ott, T. M. Antonsen Jr and J. D. Hanson; 10. Dynamical localization, dissipation and noise R. F. Graham; 11. Maximum entropy models and quantum transmission in disordered systems J.-L. Pichard and M. Sanquer; 12. Solid state 'atoms' in intense oscillating fields M. S. Sherwin; Part II. Atoms in Strong Fields: 13. Localization of classically chaotic diffusion for hydrogen atoms in microwave fields J. E. Bayfield, G. Casati, I. Guarneri and D. W. Sokol; 14. Inhibition of quantum transport due to 'scars' of unstable periodic orbits R. V. Jensen, M. M. Sanders, M. Saraceno and B. Sundaram; 15. Rubidium Rydberg atoms in strong fields G. Benson, G. Raithel and H. Walther; 16. Diamagnetic Rydberg atom: confrontation of calculated and observed spectra C.-H. Iu, G. R. Welch, M. M. Kash, D. Kleppner, D. Delande and J. C. Gay; 17. Semiclassical approximation for the quantum states of a hydrogen atom in a magnetic field near the ionization limit M. Y. Kuchiev and O. P. Sushkov; 18. The semiclassical helium atom D. Wintgen, K. Richter and G. Tanner; 19. Stretched helium: a model for quantum chaos

  1. Quantum Chaos

    NASA Astrophysics Data System (ADS)

    Casati, Giulio; Chirikov, Boris

    1995-04-01

    Preface; Acknowledgments; Introduction: 1. The legacy of chaos in quantum mechanics G. Casati and B. V. Chirikov; Part I. Classical Chaos and Quantum Localization: 2. Stochastic behaviour of a quantum pendulum under a periodic perturbation G. Casati, B. V. Chirikov, F. M. Izrailev and J. Ford; 3. Quantum dynamics of a nonintegrable system D. R. Grempel, R. E. Prange and S. E. Fishman; 4. Excitation of molecular rotation by periodic microwave pulses. A testing ground for Anderson localization R. Blümel, S. Fishman and U. Smilansky; 5. Localization of diffusive excitation in multi-level systems D. K. Shepelyansky; 6. Classical and quantum chaos for a kicked top F. Haake, M. Kus and R. Scharf; 7. Self-similarity in quantum dynamics L. E. Reichl and L. Haoming; 8. Time irreversibility of classically chaotic quantum dynamics K. Ikeda; 9. Effect of noise on time-dependent quantum chaos E. Ott, T. M. Antonsen Jr and J. D. Hanson; 10. Dynamical localization, dissipation and noise R. F. Graham; 11. Maximum entropy models and quantum transmission in disordered systems J.-L. Pichard and M. Sanquer; 12. Solid state 'atoms' in intense oscillating fields M. S. Sherwin; Part II. Atoms in Strong Fields: 13. Localization of classically chaotic diffusion for hydrogen atoms in microwave fields J. E. Bayfield, G. Casati, I. Guarneri and D. W. Sokol; 14. Inhibition of quantum transport due to 'scars' of unstable periodic orbits R. V. Jensen, M. M. Sanders, M. Saraceno and B. Sundaram; 15. Rubidium Rydberg atoms in strong fields G. Benson, G. Raithel and H. Walther; 16. Diamagnetic Rydberg atom: confrontation of calculated and observed spectra C.-H. Iu, G. R. Welch, M. M. Kash, D. Kleppner, D. Delande and J. C. Gay; 17. Semiclassical approximation for the quantum states of a hydrogen atom in a magnetic field near the ionization limit M. Y. Kuchiev and O. P. Sushkov; 18. The semiclassical helium atom D. Wintgen, K. Richter and G. Tanner; 19. Stretched helium: a model for quantum chaos

  2. Density-functional Monte-Carlo simulation of CuZn order-disorder transition

    DOE PAGES

    Khan, Suffian N.; Eisenbach, Markus

    2016-01-25

    We perform a Wang-Landau Monte Carlo simulation of a Cu0.5Zn0.5 order-disorder transition using 250 atoms and pairwise atom swaps inside a 5 x 5 x 5 BCC supercell. Each time step uses energies calculated from density functional theory (DFT) via the all-electron Korringa-Kohn- Rostoker method and self-consistent potentials. Here we find CuZn undergoes a transition from a disordered A2 to an ordered B2 structure, as observed in experiment. Our calculated transition temperature is near 870 K, comparing favorably to the known experimental peak at 750 K. We also plot the entropy, temperature, specific-heat, and short-range order as a function ofmore » internal energy.« less

  3. Quantum strategies of quantum measurements

    NASA Astrophysics Data System (ADS)

    Li, Chuan-Feng; Zhang, Yong-Sheng; Huang, Yun-Feng; Guo, Guang-Can

    2001-03-01

    In the classical Monty Hall problem, one player can always win with probability 2/3. We generalize the problem to the quantum domain and show that a fair two-party zero-sum game can be carried out if the other player is permitted to adopt quantum measurement strategy.

  4. Quantum Phase Transitions of Hard-Core Bosons on the Kagome Lattice

    NASA Astrophysics Data System (ADS)

    Isakov, S. V.; Melko, R. G.; Sengupta, K.; Wessel, S.; Kim, Yong Baek

    2006-03-01

    We study hard-core bosons with nearest-neighbor repulsion on the kagome lattice at different filling factors using quantum Monte Carlo simulations and a dual vortex theory. At half-filling, the ground state of the system is always a uniform superfluid in contrast to the case of the triangular lattice. There exists a quantum phase transition from a superfluid to a valence bond solid phase away from half-filling. The possibility of unusual quantum criticality is investigated.

  5. Quantum physics without quantum philosophy

    NASA Astrophysics Data System (ADS)

    Dürr, Detlef; Goldstein, Sheldon; Zanghì, Nino

    Quantum philosophy, a peculiar twentieth-century malady, is responsible for most of the conceptual muddle plaguing the foundations of quantum physics. When this philosophy is eschewed, one naturally arrives at Bohmian mechanics, which is what emerges from Schrödinger's equation for a nonrelativistic system of particles when we merely insist that 'particles' means particles. While distinctly non-Newtonian, Bohmian mechanics is a fully deterministic theory of particles in motion, a motion choreographed by the wave function. The quantum formalism emerges when measurement situations are analyzed according to this theory. When the quantum formalism is regarded as arising in this way, the paradoxes and perplexities so often associated with quantum theory simply evaporate.

  6. Quantum simulations of small electron-hole complexes

    SciTech Connect

    Lee, M.A.; Kalia, R.K.; Vashishta, P.D.

    1984-09-01

    The Green's Function Monte Carlo method is applied to the calculation of the binding energies of electron-hole complexes in semiconductors. The quantum simulation method allows the unambiguous determination of the ground state energy and the effects of band anisotropy on the binding energy. 22 refs., 1 fig.

  7. Fast Quantum Algorithms for Numerical Integrals and Stochastic Processes

    NASA Technical Reports Server (NTRS)

    Abrams, D.; Williams, C.

    1999-01-01

    We discuss quantum algorithms that calculate numerical integrals and descriptive statistics of stochastic processes. With either of two distinct approaches, one obtains an exponential speed increase in comparison to the fastest known classical deterministic algotithms and a quadratic speed increase incomparison to classical Monte Carlo methods.

  8. Monte Carlo Ion Transport Analysis Code.

    2009-04-15

    Version: 00 TRIPOS is a versatile Monte Carlo ion transport analysis code. It has been applied to the treatment of both surface and bulk radiation effects. The media considered is composed of multilayer polyatomic materials.

  9. Improved Monte Carlo Renormalization Group Method

    DOE R&D Accomplishments Database

    Gupta, R.; Wilson, K. G.; Umrigar, C.

    1985-01-01

    An extensive program to analyze critical systems using an Improved Monte Carlo Renormalization Group Method (IMCRG) being undertaken at LANL and Cornell is described. Here we first briefly review the method and then list some of the topics being investigated.

  10. Analytical Applications of Monte Carlo Techniques.

    ERIC Educational Resources Information Center

    Guell, Oscar A.; Holcombe, James A.

    1990-01-01

    Described are analytical applications of the theory of random processes, in particular solutions obtained by using statistical procedures known as Monte Carlo techniques. Supercomputer simulations, sampling, integration, ensemble, annealing, and explicit simulation are discussed. (CW)

  11. Monte Carlo simulation of aorta autofluorescence

    NASA Astrophysics Data System (ADS)

    Kuznetsova, A. A.; Pushkareva, A. E.

    2016-08-01

    Results of numerical simulation of autofluorescence of the aorta by the method of Monte Carlo are reported. Two states of the aorta, normal and with atherosclerotic lesions, are studied. A model of the studied tissue is developed on the basis of information about optical, morphological, and physico-chemical properties. It is shown that the data obtained by numerical Monte Carlo simulation are in good agreement with experimental results indicating adequacy of the developed model of the aorta autofluorescence.

  12. Quantum Baseball.

    ERIC Educational Resources Information Center

    Peterson, Ivars

    1989-01-01

    An analogy from the game of baseball can be used to examine the philosophy involved in statistics surrounding quantum mechanical events. The "Strong Baseball Principle" is proposed and discussed. (CW)

  13. Monte Carlo simulations on the Lefschetz thimble: Taming the sign problem

    NASA Astrophysics Data System (ADS)

    Cristoforetti, Marco; Di Renzo, Francesco; Mukherjee, Abhishek; Scorzato, Luigi

    2013-09-01

    We present the first practical Monte Carlo calculations of the recently proposed Lefschetz thimble formulation of quantum field theories. Our results provide strong evidence that the numerical sign problem that afflicts Monte Carlo calculations of models with complex actions can be softened significantly by changing the domain of integration to the Lefschetz thimble or approximations thereof. We study the interacting complex scalar field theory (relativistic Bose gas) in lattices of size up to 84 using a computationally inexpensive approximation of the Lefschetz thimble. Our results are in excellent agreement with known results. We show that—at least in the case of the relativistic Bose gas—the thimble can be systematically approached and the remaining residual phase leads to a much more tractable sign problem (if at all) than the original formulation. This is especially encouraging in view of the wide applicability—in principle—of our method to quantum field theories with a sign problem. We believe that this opens up new possibilities for accurate Monte Carlo calculations in strongly interacting systems of sizes much larger that previously possible.

  14. Transverse mode revival of a light-compensated quantum memory

    SciTech Connect

    Yang Fan; Mandel, Torsten; Lutz, Christian; Yuan Zhensheng; Pan Jianwei

    2011-06-15

    A long-lived quantum memory was developed based on light-compensated cold {sup 87}Rb atoms in a dipole trap. The lifetime of the quantum memory was improved by 40 folds, from 0.67 to 28 ms with the help of a compensation laser beam. Oscillations of the memory efficiency due to the transverse mode breathing of the singly excited spin wave have been clearly observed and clarified with a Monte Carlo simulation procedure. With detailed analysis of the decoherence processes of the spin wave in cold atomic ensembles, this experiment provides a benchmark for the further development of high-quality quantum memories.

  15. Parameter Tuning Patterns for Random Graph Coloring with Quantum Annealing

    PubMed Central

    Titiloye, Olawale; Crispin, Alan

    2012-01-01

    Quantum annealing is a combinatorial optimization technique inspired by quantum mechanics. Here we show that a spin model for the k-coloring of large dense random graphs can be field tuned so that its acceptance ratio diverges during Monte Carlo quantum annealing, until a ground state is reached. We also find that simulations exhibiting such a diverging acceptance ratio are generally more effective than those tuned to the more conventional pattern of a declining and/or stagnating acceptance ratio. This observation facilitates the discovery of solutions to several well-known benchmark k-coloring instances, some of which have been open for almost two decades. PMID:23166818

  16. Quantum Locality?

    NASA Astrophysics Data System (ADS)

    Stapp, Henry P.

    2012-05-01

    Robert Griffiths has recently addressed, within the framework of a `consistent quantum theory' that he has developed, the issue of whether, as is often claimed, quantum mechanics entails a need for faster-than-light transfers of information over long distances. He argues that the putative proofs of this property that involve hidden variables include in their premises some essentially classical-physics-type assumptions that are not entailed by the precepts of quantum mechanics. Thus whatever is proved is not a feature of quantum mechanics, but is a property of a theory that tries to combine quantum theory with quasi-classical features that go beyond what is entailed by quantum theory itself. One cannot logically prove properties of a system by establishing, instead, properties of a system modified by adding properties alien to the original system. Hence Griffiths' rejection of hidden-variable-based proofs is logically warranted. Griffiths mentions the existence of a certain alternative proof that does not involve hidden variables, and that uses only macroscopically described observable properties. He notes that he had examined in his book proofs of this general kind, and concluded that they provide no evidence for nonlocal influences. But he did not examine the particular proof that he cites. An examination of that particular proof by the method specified by his `consistent quantum theory' shows that the cited proof is valid within that restrictive version of quantum theory. An added section responds to Griffiths' reply, which cites general possibilities of ambiguities that might make what is to be proved ill-defined, and hence render the pertinent `consistent framework' ill defined. But the vagaries that he cites do not upset the proof in question, which, both by its physical formulation and by explicit identification, specify the framework to be used. Griffiths confirms the validity of the proof insofar as that pertinent framework is used. The section also shows

  17. Quantum correlations and distinguishability of quantum states

    SciTech Connect

    Spehner, Dominique

    2014-07-15

    A survey of various concepts in quantum information is given, with a main emphasis on the distinguishability of quantum states and quantum correlations. Covered topics include generalized and least square measurements, state discrimination, quantum relative entropies, the Bures distance on the set of quantum states, the quantum Fisher information, the quantum Chernoff bound, bipartite entanglement, the quantum discord, and geometrical measures of quantum correlations. The article is intended both for physicists interested not only by collections of results but also by the mathematical methods justifying them, and for mathematicians looking for an up-to-date introductory course on these subjects, which are mainly developed in the physics literature.

  18. Quantum feedback by discrete quantum nondemolition measurements: Towards on-demand generation of photon-number states

    SciTech Connect

    Dotsenko, I.; Haroche, S.; Mirrahimi, M.; Brune, M.; Raimond, J.-M.; Rouchon, P.

    2009-07-15

    We propose a quantum feedback scheme for the preparation and protection of photon-number states of light trapped in a high-Q microwave cavity. A quantum nondemolition measurement of the cavity field provides information on the photon-number distribution. The feedback loop is closed by injecting into the cavity a coherent pulse adjusted to increase the probability of the target photon number. The efficiency and reliability of the closed-loop state stabilization is assessed by quantum Monte Carlo simulations. We show that, in realistic experimental conditions, the Fock states are efficiently produced and protected against decoherence.

  19. Quantum Mechanics

    NASA Astrophysics Data System (ADS)

    Mandl, F.

    1992-07-01

    The Manchester Physics Series General Editors: D. J. Sandiford; F. Mandl; A. C. Phillips Department of Physics and Astronomy, University of Manchester Properties of Matter B. H. Flowers and E. Mendoza Optics Second Edition F. G. Smith and J. H. Thomson Statistical Physics Second Edition F. Mandl Electromagnetism Second Edition I. S. Grant and W. R. Phillips Statistics R. J. Barlow Solid State Physics Second Edition J. R. Hook and H. E. Hall Quantum Mechanics F. Mandl Particle Physics Second Edition B. R. Martin and G. Shaw The Physics of Stars Second Edition A. C. Phillips Computing for Scientists R. J. Barlow and A. R. Barnett Quantum Mechanics aims to teach those parts of the subject which every physicist should know. The object is to display the inherent structure of quantum mechanics, concentrating on general principles and on methods of wide applicability without taking them to their full generality. This book will equip students to follow quantum-mechanical arguments in books and scientific papers, and to cope with simple cases. To bring the subject to life, the theory is applied to the all-important field of atomic physics. No prior knowledge of quantum mechanics is assumed. However, it would help most readers to have met some elementary wave mechanics before. Primarily written for students, it should also be of interest to experimental research workers who require a good grasp of quantum mechanics without the full formalism needed by the professional theorist. Quantum Mechanics features: A flow diagram allowing topics to be studied in different orders or omitted altogether. Optional "starred" and highlighted sections containing more advanced and specialized material for the more ambitious reader. Sets of problems at the end of each chapter to help student understanding. Hints and solutions to the problems are given at the end of the book.

  20. MONTE-CARLO Simulations ``QUANTUM''-``NOISE'' POWER-SPECTRUM 0 =(F =ma) =0 Uniform-Velocity Pareto/Red/Beethoven-Law VS 0 ≠(F =ma) ≠0 Uniform-Acceleration/Deceleration/Bremsstrahlung Archimedes-(Euclid-Descartes)-Zipf/Pink/Flicker/Bach-Law UNIVERSALITY INEVITABILITY!!!

    NASA Astrophysics Data System (ADS)

    Louis, T. T. L.; Siegel, Edward Carl-Ludwig; Young, Frederic; Smith, Adolph

    2013-03-01

    Dynamics vs usual by-rote kinematics treatment/lack of understanding, via Siegel[AIP Shock-Physics Confs. Chicago(2011); Seattle(2013)] simple classical-mechanics/dynamics simple-insights]-Panofsky-Phillips[E&M (1960s)],of Monte Carlo[Kaplan et.al.[PRL 107, 201601 (11)]:'''Noise', Sign-Problems & Statistics'']-simulations' {Hamersley-Handscombe, Monte Carlo Methods, Methuen(64-75)}``noises'' power-spectra{SEMINAL Montroll [(60s-80s)}-Boccara[ ``Modeling'' ``Complex''-Sys.(02)-ch.-8/p.-311]-West et.al.[Physics of Fractal-Operators, Springer(00)]-Shlesinger-Lindenberg-Handel-van Vliet-Jonscher-Ngai-...-Siegel[Schrodinger Symp., Imperial-College (1987);Copenhagen-Onterp. 50-Yrs. After Como-Lect.,Symp.Fdns.Mod.Phys., Joensu(87)]}, in the light of Siegel[MRS Fall-Mtgs. Boston: Symp. Fractals(89)-5-papers!!!; Symp. Scaling(90); Symp.Transport in Geometric-Constraints(90)] power-law decay algebraicity vs. white/flat/functionless [analogous to Fokker-Planck-eqn. two-terms Dichotomy, relatively: static/non-diffusive vs diffusive!!!] but dimensionality-dependence: first-odd-integer Z vs. first-even-integer Z: 2-D bulk-region -area - dominated constant