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Sample records for accurate quantum monte

  1. Quantum Monte Carlo: Faster, More Reliable, And More Accurate

    NASA Astrophysics Data System (ADS)

    Anderson, Amos Gerald

    2010-06-01

    The Schrodinger Equation has been available for about 83 years, but today, we still strain to apply it accurately to molecules of interest. The difficulty is not theoretical in nature, but practical, since we're held back by lack of sufficient computing power. Consequently, effort is applied to find acceptable approximations to facilitate real time solutions. In the meantime, computer technology has begun rapidly advancing and changing the way we think about efficient algorithms. For those who can reorganize their formulas to take advantage of these changes and thereby lift some approximations, incredible new opportunities await. Over the last decade, we've seen the emergence of a new kind of computer processor, the graphics card. Designed to accelerate computer games by optimizing quantity instead of quality in processor, they have become of sufficient quality to be useful to some scientists. In this thesis, we explore the first known use of a graphics card to computational chemistry by rewriting our Quantum Monte Carlo software into the requisite "data parallel" formalism. We find that notwithstanding precision considerations, we are able to speed up our software by about a factor of 6. The success of a Quantum Monte Carlo calculation depends on more than just processing power. It also requires the scientist to carefully design the trial wavefunction used to guide simulated electrons. We have studied the use of Generalized Valence Bond wavefunctions to simply, and yet effectively, captured the essential static correlation in atoms and molecules. Furthermore, we have developed significantly improved two particle correlation functions, designed with both flexibility and simplicity considerations, representing an effective and reliable way to add the necessary dynamic correlation. Lastly, we present our method for stabilizing the statistical nature of the calculation, by manipulating configuration weights, thus facilitating efficient and robust calculations. Our

  2. 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.

  3. Tin phase transition in terapascal pressure range described accurately with Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Nazarov, Roman; Hood, Randolph; Morales, Miguel

    The accurate prediction of phase transitions is one of the most important research areas in modern materials science. The main workhorse for such calculations, Density functional theory (DFT), employs different forms of approximate exchange-correlation functionals which may lead to overstabilization of one phase compared to another, therefore, predict incorrectly phase transition pressures. A recent example of such deficiency has been demonstrated in Sn: no bcc to hcp phase transition has been observed in Sn when dynamically compressed to 1.2 TPa while DFT predicts a transition to occur at 0.16-0.2 TPa. To overcome the limitations of DFT, we have employed diffusion quantum Monte Carlo (DMC) method which treats the many body electron problem directly. In order to get highly accurate results we systematically assess the effect of controllable approximations of DMC such as fixed node approximation, finite-size effects and the use of pseudopotentials. Based on metrologically accurate DMC equation of states we construct the pressure-temperature phase diagram and demonstrate its good agreement with experiment in contrast to DFT calculations.

  4. Accurate quantum chemical calculations

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1989-01-01

    An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.

  5. 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.

  6. 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.

  7. 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.

  8. Accurate Evaluation of Quantum Integrals

    NASA Technical Reports Server (NTRS)

    Galant, D. C.; Goorvitch, D.; Witteborn, Fred C. (Technical Monitor)

    1995-01-01

    Combining an appropriate finite difference method with Richardson's extrapolation results in a simple, highly accurate numerical method for solving a Schrodinger's equation. Important results are that error estimates are provided, and that one can extrapolate expectation values rather than the wavefunctions to obtain highly accurate expectation values. We discuss the eigenvalues, the error growth in repeated Richardson's extrapolation, and show that the expectation values calculated on a crude mesh can be extrapolated to obtain expectation values of high accuracy.

  9. Electronic structure quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Mitas, Lubos

    2009-04-01

    Quantum Monte Carlo (QMC) is an advanced simulation methodology for studies of manybody quantum systems. The QMC approaches combine analytical insights with stochastic computational techniques for efficient solution of several classes of important many-body problems such as the stationary Schrödinger equation. QMC methods of various flavors have been applied to a great variety of systems spanning continuous and lattice quantum models, molecular and condensed systems, BEC-BCS ultracold condensates, nuclei, etc. In this review, we focus on the electronic structure QMC, i.e., methods relevant for systems described by the electron-ion Hamiltonians. Some of the key QMC achievements include direct treatment of electron correlation, accuracy in predicting energy differences and favorable scaling in the system size. Calculations of atoms, molecules, clusters and solids have demonstrated QMC applicability to real systems with hundreds of electrons while providing 90-95% of the correlation energy and energy differences typically within a few percent of experiments. Advances in accuracy beyond these limits are hampered by the so-called fixed-node approximation which is used to circumvent the notorious fermion sign problem. Many-body nodes of fermion states and their properties have therefore become one of the important topics for further progress in predictive power and efficiency of QMC calculations. Some of our recent results on the wave function nodes and related nodal domain topologies will be briefly reviewed. This includes analysis of few-electron systems and descriptions of exact and approximate nodes using transformations and projections of the highly-dimensional nodal hypersurfaces into the 3D space. Studies of fermion nodes offer new insights into topological properties of eigenstates such as explicit demonstrations that generic fermionic ground states exhibit the minimal number of two nodal domains. Recently proposed trial wave functions based on Pfaffians with

  10. Quantum speedup of Monte Carlo methods.

    PubMed

    Montanaro, Ashley

    2015-09-08

    Monte Carlo methods use random sampling to estimate numerical quantities which are hard to compute deterministically. One important example is the use in statistical physics of rapidly mixing Markov chains to approximately compute partition functions. In this work, we describe a quantum algorithm which can accelerate Monte Carlo methods in a very general setting. The algorithm estimates the expected output value of an arbitrary randomized or quantum subroutine with bounded variance, achieving a near-quadratic speedup over the best possible classical algorithm. Combining the algorithm with the use of quantum walks gives a quantum speedup of the fastest known classical algorithms with rigorous performance bounds for computing partition functions, which use multiple-stage Markov chain Monte Carlo techniques. The quantum algorithm can also be used to estimate the total variation distance between probability distributions efficiently.

  11. Quantum speedup of Monte Carlo methods

    PubMed Central

    Montanaro, Ashley

    2015-01-01

    Monte Carlo methods use random sampling to estimate numerical quantities which are hard to compute deterministically. One important example is the use in statistical physics of rapidly mixing Markov chains to approximately compute partition functions. In this work, we describe a quantum algorithm which can accelerate Monte Carlo methods in a very general setting. The algorithm estimates the expected output value of an arbitrary randomized or quantum subroutine with bounded variance, achieving a near-quadratic speedup over the best possible classical algorithm. Combining the algorithm with the use of quantum walks gives a quantum speedup of the fastest known classical algorithms with rigorous performance bounds for computing partition functions, which use multiple-stage Markov chain Monte Carlo techniques. The quantum algorithm can also be used to estimate the total variation distance between probability distributions efficiently. PMID:26528079

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. Accurate Variational Description of Adiabatic Quantum Optimization

    NASA Astrophysics Data System (ADS)

    Carleo, Giuseppe; Bauer, Bela; Troyer, Matthias

    Adiabatic quantum optimization (AQO) is a quantum computing protocol where a system is driven by a time-dependent Hamiltonian. The initial Hamiltonian has an easily prepared ground-state and the final Hamiltonian encodes some desired optimization problem. An adiabatic time evolution then yields a solution to the optimization problem. Several challenges emerge in the theoretical description of this protocol: on one hand, the exact simulation of quantum dynamics is exponentially complex in the size of the optimization problem. On the other hand, approximate approaches such as tensor network states (TNS) are limited to small instances by the amount of entanglement that can be encoded. I will present here an extension of the time-dependent Variational Monte Carlo approach to problems in AQO. This approach is based on a general class of (Jastrow-Feenberg) entangled states, whose parameters are evolved in time according to a stochastic variational principle. We demonstrate this approach for optimization problems of the Ising spin-glass type. A very good accuracy is achieved when compared to exact time-dependent TNS on small instances. We then apply this approach to larger problems, and discuss the efficiency of the quantum annealing scheme in comparison with its classical counterpart.

  18. 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

  19. Quantum Monte Carlo applied to solids

    SciTech Connect

    Shulenburger, Luke; Mattsson, Thomas R.

    2013-12-01

    We apply diffusion quantum Monte Carlo to a broad set of solids, benchmarking the method by comparing bulk structural properties (equilibrium volume and bulk modulus) to experiment and density functional theory (DFT) based theories. The test set includes materials with many different types of binding including ionic, metallic, covalent, and van der Waals. We show that, on average, the accuracy is comparable to or better than that of DFT when using the new generation of functionals, including one hybrid functional and two dispersion corrected functionals. The excellent performance of quantum Monte Carlo on solids is promising for its application to heterogeneous systems and high-pressure/high-density conditions. Important to the results here is the application of a consistent procedure with regards to the several approximations that are made, such as finite-size corrections and pseudopotential approximations. This test set allows for any improvements in these methods to be judged in a systematic way.

  20. 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.

  1. Quantum Monte Carlo with directed loops.

    PubMed

    Syljuåsen, Olav F; Sandvik, Anders W

    2002-10-01

    We introduce the concept of directed loops in stochastic series expansion and path-integral quantum Monte Carlo methods. Using the detailed balance rules for directed loops, we show that it is possible to smoothly connect generally applicable simulation schemes (in which it is necessary to include backtracking processes in the loop construction) to more restricted loop algorithms that can be constructed only for a limited range of Hamiltonians (where backtracking can be avoided). The "algorithmic discontinuities" between general and special points (or regions) in parameter space can hence be eliminated. As a specific example, we consider the anisotropic S=1/2 Heisenberg antiferromagnet in an external magnetic field. We show that directed-loop simulations are very efficient for the full range of magnetic fields (zero to the saturation point) and anisotropies. In particular, for weak fields and anisotropies, the autocorrelations are significantly reduced relative to those of previous approaches. The back-tracking probability vanishes continuously as the isotropic Heisenberg point is approached. For the XY model, we show that back tracking can be avoided for all fields extending up to the saturation field. The method is hence particularly efficient in this case. We use directed-loop simulations to study the magnetization process in the two-dimensional Heisenberg model at very low temperatures. For LxL lattices with L up to 64, we utilize the step structure in the magnetization curve to extract gaps between different spin sectors. Finite-size scaling of the gaps gives an accurate estimate of the transverse susceptibility in the thermodynamic limit: chi( perpendicular )=0.0659+/-0.0002.

  2. 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.

  3. 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"…

  4. Quantum Monte Carlo calculations for light nuclei

    SciTech Connect

    Wiringa, R.B.

    1998-08-01

    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 30 different (j{sup {prime}}, 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.

  5. 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.

  6. Noncovalent Interactions by Quantum Monte Carlo.

    PubMed

    Dubecký, Matúš; Mitas, Lubos; Jurečka, Petr

    2016-05-11

    Quantum Monte Carlo (QMC) is a family of stochastic methods for solving quantum many-body problems such as the stationary Schrödinger equation. The review introduces basic notions of electronic structure QMC based on random walks in real space as well as its advances and adaptations to systems with noncovalent interactions. Specific issues such as fixed-node error cancellation, construction of trial wave functions, and efficiency considerations that allow for benchmark quality QMC energy differences are described in detail. Comprehensive overview of articles covers QMC applications to systems with noncovalent interactions over the last three decades. The current status of QMC with regard to efficiency, applicability, and usability by nonexperts together with further considerations about QMC developments, limitations, and unsolved challenges are discussed as well.

  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. Quantum Monte Carlo methods for nuclear physics

    SciTech Connect

    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-body 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.

  9. Quantum Monte Carlo methods for nuclear physics

    DOE PAGES

    Carlson, Joseph A.; Gandolfi, Stefano; Pederiva, Francesco; ...

    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

  10. Quantum Monte Carlo methods for nuclear physics

    DOE PAGES

    Carlson, J.; Gandolfi, S.; Pederiva, F.; ...

    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

  11. 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.

  12. Quantum Monte Carlo methods for nuclear physics

    NASA Astrophysics Data System (ADS)

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

    2015-07-01

    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. A coherent picture of nuclear structure and dynamics emerges based upon rather simple but realistic interactions and currents.

  13. Chemical application of diffusion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

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

    1983-10-01

    The diffusion quantum Monte Carlo (QMC) method gives a stochastic solution to the Schroedinger equation. As an example the singlet-triplet splitting of the energy of the methylene molecule CH2 is given. The QMC algorithm was implemented on the CYBER 205, first as a direct transcription of the algorithm running on our 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 is discussed. Since CH2 has only eight electrons, most of the loops in this application are fairly short. The longest inner loops run over the set of atomic basis functions. The CPU time dependence obtained versus the number of basis functions is discussed and compared with that obtained from traditional quantum chemistry codes and that obtained from traditional computer architectures. Finally, preliminary work on restructuring the algorithm to compute the separate Monte Carlo realizations in parallel is discussed.

  14. A pure-sampling quantum Monte Carlo algorithm.

    PubMed

    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.

  15. 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.

  16. Quantum Monte Carlo finite temperature electronic structure of quantum dots

    NASA Astrophysics Data System (ADS)

    Leino, Markku; Rantala, Tapio T.

    2002-08-01

    Quantum Monte Carlo methods allow a straightforward procedure for evaluation of electronic structures with a proper treatment of electronic correlations. This can be done even at finite temperatures [1]. We test the Path Integral Monte Carlo (PIMC) simulation method [2] for one and two electrons in one and three dimensional harmonic oscillator potentials and apply it in evaluation of finite temperature effects of single and coupled quantum dots. Our simulations show the correct finite temperature excited state populations including degeneracy in cases of one and three dimensional harmonic oscillators. The simulated one and two electron distributions of a single and coupled quantum dots are compared to those from experiments and other theoretical (0 K) methods [3]. Distributions are shown to agree and the finite temperature effects are discussed. Computational capacity is found to become the limiting factor in simulations with increasing accuracy. Other essential aspects of PIMC and its capability in this type of calculations are also discussed. [1] R.P. Feynman: Statistical Mechanics, Addison Wesley, 1972. [2] D.M. Ceperley, Rev.Mod.Phys. 67, 279 (1995). [3] M. Pi, A. Emperador and M. Barranco, Phys.Rev.B 63, 115316 (2001).

  17. Hybrid algorithms in quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    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.

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

    SciTech Connect

    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 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 compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.

  19. 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

  20. Monte Carlo Analysis of Quantum Transport and Fluctuations in Semiconductors.

    DTIC Science & Technology

    1986-02-18

    methods to quantum transport within the Liouville formulation. The second part concerns with fluctuations of carrier velocities and energies both in...interactions) on the transport properties. Keywords: Monte Carlo; Charge Transport; Quantum Transport ; Fluctuations; Semiconductor Physics; Master Equation...The present report contains technical matter related to the research performed on two different subjects. The first part concerns with quantum

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

    PubMed

    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(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.

  2. 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.

  3. 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.

  4. 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.

  5. Quantum Monte Carlo Calculations of Nucleon-Nucleus Scattering

    NASA Astrophysics Data System (ADS)

    Wiringa, R. B.; Nollett, Kenneth M.; Pieper, Steven C.; Brida, I.

    2009-10-01

    We report recent quantum Monte Carlo (variational and Green's function) calculations of elastic nucleon-nucleus scattering. We are adding the cases of proton-^4He, neutron-^3H and proton-^3He scattering to a previous GFMC study of neutron-^4He scattering [1]. To do this requires generalizing our methods to include long-range Coulomb forces and to treat coupled channels. The two four-body cases can be compared to other accurate four-body calculational methods such as the AGS equations and hyperspherical harmonic expansions. We will present results for the Argonne v18 interaction alone and with Urbana and Illinois three-nucleon potentials. [4pt] [1] K.M. Nollett, S. C. Pieper, R.B. Wiringa, J. Carlson, and G.M. Hale, Phys. Rev. Lett. 99, 022502 (2007)

  6. Fast and accurate calculation of dilute quantum gas using Uehling-Uhlenbeck model equation

    NASA Astrophysics Data System (ADS)

    Yano, Ryosuke

    2017-02-01

    The Uehling-Uhlenbeck (U-U) model equation is studied for the fast and accurate calculation of a dilute quantum gas. In particular, the direct simulation Monte Carlo (DSMC) method is used to solve the U-U model equation. DSMC analysis based on the U-U model equation is expected to enable the thermalization to be accurately obtained using a small number of sample particles and the dilute quantum gas dynamics to be calculated in a practical time. Finally, the applicability of DSMC analysis based on the U-U model equation to the fast and accurate calculation of a dilute quantum gas is confirmed by calculating the viscosity coefficient of a Bose gas on the basis of the Green-Kubo expression and the shock layer of a dilute Bose gas around a cylinder.

  7. Challenges for large scale ab initio Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Kent, Paul

    2015-03-01

    Ab initio Quantum Monte Carlo is an electronic structure method that is highly accurate, well suited to large scale computation, and potentially systematically improvable in accuracy. Due to increases in computer power, the method has been applied to systems where established electronic structure methods have difficulty reaching the accuracies desired to inform experiment without empiricism, a necessary step in the design of materials and a helpful step in the improvement of cheaper and less accurate methods. Recent applications include accurate phase diagrams of simple materials through to phenomena in transition metal oxides. Nevertheless there remain significant challenges to achieving a methodology that is robust and systematically improvable in practice, as well as capable of exploiting the latest generation of high-performance computers. In this talk I will describe the current state of the art, recent applications, and several significant challenges for continued improvement. Supported through the Predictive Theory and Modeling for Materials and Chemical Science program by the Office of Basic Energy Sciences (BES), Department of Energy (DOE).

  8. Quantum Monte Carlo with density matrix: potential energy curve derived properties.

    PubMed

    Bonfim, Víctor S; Borges, Nádia M; Martins, João B L; Gargano, Ricardo; Politi, José Roberto Dos S

    2017-04-01

    In this work, we used diffusion quantum Monte Carlo with density matrix (d-DMC) and variational quantum Monte Carlo (d-VMC) to determine the potential energy curve (PEC) and obtain the spectroscopic constants of H2 molecule in the ground state, in order to evaluate the capability of these methods to provide an accurate PEC description. These quantum Monte Carlo methods build with density matrix are new approaches to conventional quantum Monte Carlo methods based on wave function formed by product of α and β determinants. To investigate the robustness of d-DMC, we performed calculations with two different basis sets and analyzed the influence of the size of these sets on results. To the best of our knowledge, this is the first study that shows the dissociation energy and rotational constant obtained from d-QMC. We found that the quality of PEC described by the d-DMC is essentially coincident with the most accurate results available in the literature, regardless of the complexity of basis set employed.

  9. Quantum Monte Carlo Benchmarks Functionals for Silica Polymorphs

    NASA Astrophysics Data System (ADS)

    Driver, K. P.; Wilkins, J. W.; Hennig, R. G.; Umrigar, C. J.; Scuseria, G.; Militzer, B.; Cohen, R. E.

    2007-03-01

    For many silica polytypes, the local density approximation (LDA) does a better job than the generalized gradient approximation (GGA) in predicting structural properties and bulk moduli. However, gradient corrections to the charge density are necessary for accurate phase energy differences. Functionals that go beyond GGA may improve the accuracy of both structures and energies. For example, a meta-GGA functional, TPSS, and hybrid functionals B3LYP and HSE have shown improvement in other systems. We compare results from these functionals for structural properties, energy differences, and bulk moduli for a few high pressure phases of silica, and benchmark the results with Quantum Monte Carlo (QMC). Preliminary QMC results indicate that careful wavefunction optimization and finite size effects are of particular importance in obtaining accurate silica phase properties. Supported by DOE(DE-FG02-99ER45795), NSF (EAR-0530301, DMR-0205328), and Sandia National Laboratory. Computation at OSC and NERSC. [1]Th. Demuth et al., J. Phys.: Cond. Matter 11, 3833 (1999). [2]J. Heyd et al., J. Chem. Phys. 121, 1187 (2004). [3]E. R. Batista et al., Phys. Rev. B 74, 121102(R) (2006).

  10. Improving light propagation Monte Carlo simulations with accurate 3D modeling of skin tissue

    SciTech Connect

    Paquit, Vincent C; Price, Jeffery R; Meriaudeau, Fabrice; Tobin Jr, Kenneth William

    2008-01-01

    In this paper, we present a 3D light propagation model to simulate multispectral reflectance images of large skin surface areas. In particular, we aim to simulate more accurately the effects of various physiological properties of the skin in the case of subcutaneous vein imaging compared to existing models. Our method combines a Monte Carlo light propagation model, a realistic three-dimensional model of the skin using parametric surfaces and a vision system for data acquisition. We describe our model in detail, present results from the Monte Carlo modeling and compare our results with those obtained with a well established Monte Carlo model and with real skin reflectance images.

  11. Determining the Complexity of the Quantum Adiabatic Algorithm using Quantum Monte Carlo Simulations

    DTIC Science & Technology

    2012-12-18

    efficiently a quantum computer could solve optimization problems using the quantum adiabatic algorithm (QAA). Comparisons were made with a classical...Park, NC 27709-2211 15. SUBJECT TERMS Quantum Adiabatic Algorithm , Optimization, Monte Carlo, quantum computer, satisfiability problems, spin glass... quantum adiabatic algorithm (QAA). Comparisons were made with a classical heuristic algorithm , WalkSAT. A preliminary study was also made to see if the

  12. 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

  13. 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.

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

    PubMed

    Overy, Catherine; Booth, George H; Blunt, N S; Shepherd, James J; 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.

  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. 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.

  17. Quantum Monte Carlo simulation of topological phase transitions

    NASA Astrophysics Data System (ADS)

    Yamamoto, Arata; Kimura, Taro

    2016-12-01

    We study the electron-electron interaction effects on topological phase transitions by the ab initio quantum Monte Carlo simulation. We analyze two-dimensional class A topological insulators and three-dimensional Weyl semimetals with the long-range Coulomb interaction. The direct computation of the Chern number shows the electron-electron interaction modifies or extinguishes topological phase transitions.

  18. On a full Monte Carlo approach to quantum mechanics

    NASA Astrophysics Data System (ADS)

    Sellier, J. M.; Dimov, I.

    2016-12-01

    The Monte Carlo approach to numerical problems has shown to be remarkably efficient in performing very large computational tasks since it is an embarrassingly parallel technique. Additionally, Monte Carlo methods are well known to keep performance and accuracy with the increase of dimensionality of a given problem, a rather counterintuitive peculiarity not shared by any known deterministic method. Motivated by these very peculiar and desirable computational features, in this work we depict a full Monte Carlo approach to the problem of simulating single- and many-body quantum systems by means of signed particles. In particular we introduce a stochastic technique, based on the strategy known as importance sampling, for the computation of the Wigner kernel which, so far, has represented the main bottleneck of this method (it is equivalent to the calculation of a multi-dimensional integral, a problem in which complexity is known to grow exponentially with the dimensions of the problem). The introduction of this stochastic technique for the kernel is twofold: firstly it reduces the complexity of a quantum many-body simulation from non-linear to linear, secondly it introduces an embarassingly parallel approach to this very demanding problem. To conclude, we perform concise but indicative numerical experiments which clearly illustrate how a full Monte Carlo approach to many-body quantum systems is not only possible but also advantageous. This paves the way towards practical time-dependent, first-principle simulations of relatively large quantum systems by means of affordable computational resources.

  19. Accurately modeling Gaussian beam propagation in the context of Monte Carlo techniques

    NASA Astrophysics Data System (ADS)

    Hokr, Brett H.; Winblad, Aidan; Bixler, Joel N.; Elpers, Gabriel; Zollars, Byron; Scully, Marlan O.; Yakovlev, Vladislav V.; Thomas, Robert J.

    2016-03-01

    Monte Carlo simulations are widely considered to be the gold standard for studying the propagation of light in turbid media. However, traditional Monte Carlo methods fail to account for diffraction because they treat light as a particle. This results in converging beams focusing to a point instead of a diffraction limited spot, greatly effecting the accuracy of Monte Carlo simulations near the focal plane. Here, we present a technique capable of simulating a focusing beam in accordance to the rules of Gaussian optics, resulting in a diffraction limited focal spot. This technique can be easily implemented into any traditional Monte Carlo simulation allowing existing models to be converted to include accurate focusing geometries with minimal effort. We will present results for a focusing beam in a layered tissue model, demonstrating that for different scenarios the region of highest intensity, thus the greatest heating, can change from the surface to the focus. The ability to simulate accurate focusing geometries will greatly enhance the usefulness of Monte Carlo for countless applications, including studying laser tissue interactions in medical applications and light propagation through turbid media.

  20. Fast and accurate quantum molecular dynamics of dense plasmas across temperature regimes

    SciTech Connect

    Sjostrom, Travis; Daligault, Jerome

    2014-10-10

    Here, we develop and implement a new quantum molecular dynamics approximation that allows fast and accurate simulations of dense plasmas from cold to hot conditions. The method is based on a carefully designed orbital-free implementation of density functional theory. The results for hydrogen and aluminum are in very good agreement with Kohn-Sham (orbital-based) density functional theory and path integral Monte Carlo calculations for microscopic features such as the electron density as well as the equation of state. The present approach does not scale with temperature and hence extends to higher temperatures than is accessible in the Kohn-Sham method and lower temperatures than is accessible by path integral Monte Carlo calculations, while being significantly less computationally expensive than either of those two methods.

  1. Fast and accurate quantum molecular dynamics of dense plasmas across temperature regimes

    DOE PAGES

    Sjostrom, Travis; Daligault, Jerome

    2014-10-10

    Here, we develop and implement a new quantum molecular dynamics approximation that allows fast and accurate simulations of dense plasmas from cold to hot conditions. The method is based on a carefully designed orbital-free implementation of density functional theory. The results for hydrogen and aluminum are in very good agreement with Kohn-Sham (orbital-based) density functional theory and path integral Monte Carlo calculations for microscopic features such as the electron density as well as the equation of state. The present approach does not scale with temperature and hence extends to higher temperatures than is accessible in the Kohn-Sham method and lowermore » temperatures than is accessible by path integral Monte Carlo calculations, while being significantly less computationally expensive than either of those two methods.« less

  2. 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.

  3. Quantum Monte Carlo method applied to non-Markovian barrier transmission

    NASA Astrophysics Data System (ADS)

    Hupin, Guillaume; Lacroix, Denis

    2010-01-01

    In nuclear fusion and fission, fluctuation and dissipation arise because of the coupling of collective degrees of freedom with internal excitations. Close to the barrier, quantum, statistical, and non-Markovian effects are expected to be important. In this work, a new approach based on quantum Monte Carlo addressing this problem is presented. The exact dynamics of a system coupled to an environment is replaced by a set of stochastic evolutions of the system density. The quantum Monte Carlo method is applied to systems with quadratic potentials. In all ranges of temperature and coupling, the stochastic method matches the exact evolution, showing that non-Markovian effects can be simulated accurately. A comparison with other theories, such as Nakajima-Zwanzig or time-convolutionless, shows that only the latter can be competitive if the expansion in terms of coupling constant is made at least to fourth order. A systematic study of the inverted parabola case is made at different temperatures and coupling constants. The asymptotic passing probability is estimated by different approaches including the Markovian limit. Large differences with an exact result are seen in the latter case or when only second order in the coupling strength is considered, as is generally assumed in nuclear transport models. In contrast, if fourth order in the coupling or quantum Monte Carlo method is used, a perfect agreement is obtained.

  4. 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.

  5. Condensed Matter Applications of Quantum Monte Carlo at the Petascale

    NASA Astrophysics Data System (ADS)

    Ceperley, David

    2014-03-01

    Applications of the Quantum Monte Carlo method have a number of advantages allowing them to be useful for high performance computation. The method scales well in particle number, can treat complex systems with weak or strong correlation including disordered systems, and large thermal and zero point effects of the nuclei. The methods are adaptable to a variety of computer architectures and have multiple parallelization strategies. Most errors are under control so that increases in computer resources allow a systematic increase in accuracy. We will discuss a number of recent applications of Quantum Monte Carlo including dense hydrogen and transition metal systems and suggest future directions. Support from DOE grants DE-FG52-09NA29456, SCIDAC DE-SC0008692, the Network for Ab Initio Many-Body Methods and INCITE allocation.

  6. Exact special twist method for quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Dagrada, Mario; Karakuzu, Seher; Vildosola, Verónica Laura; Casula, Michele; Sorella, Sandro

    2016-12-01

    We present a systematic investigation of the special twist method introduced by Rajagopal et al. [Phys. Rev. B 51, 10591 (1995), 10.1103/PhysRevB.51.10591] for reducing finite-size effects in correlated calculations of periodic extended systems with Coulomb interactions and Fermi statistics. We propose a procedure for finding special twist values which, at variance with previous applications of this method, reproduce the energy of the mean-field infinite-size limit solution within an adjustable (arbitrarily small) numerical error. This choice of the special twist is shown to be the most accurate single-twist solution for curing one-body finite-size effects in correlated calculations. For these reasons we dubbed our procedure "exact special twist" (EST). EST only needs a fully converged independent-particles or mean-field calculation within the primitive cell and a simple fit to find the special twist along a specific direction in the Brillouin zone. We first assess the performances of EST in a simple correlated model such as the three-dimensional electron gas. Afterwards, we test its efficiency within ab initio quantum Monte Carlo simulations of metallic elements of increasing complexity. We show that EST displays an overall good performance in reducing finite-size errors comparable to the widely used twist average technique but at a much lower computational cost since it involves the evaluation of just one wave function. We also demonstrate that the EST method shows similar performances in the calculation of correlation functions, such as the ionic forces for structural relaxation and the pair radial distribution function in liquid hydrogen. Our conclusions point to the usefulness of EST for correlated supercell calculations; our method will be particularly relevant when the physical problem under consideration requires large periodic cells.

  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. Structural Optimization by Quantum Monte Carlo: Investigating the Low-Lying Excited States of Ethylene.

    PubMed

    Barborini, Matteo; Sorella, Sandro; Guidoni, Leonardo

    2012-04-10

    We present full structural optimizations of the ground state and of the low lying triplet state of the ethylene molecule by means of Quantum Monte Carlo methods. Using the efficient structural optimization method based on renormalization techniques and on adjoint differentiation algorithms recently proposed [Sorella, S.; Capriotti, L. J. Chem. Phys.2010, 133, 234111], we present the variational convergence of both wave function parameters and atomic positions. All of the calculations were done using an accurate and compact wave function based on Pauling's resonating valence bond representation: the Jastrow Antisymmetrized Geminal Power (JAGP). All structural and wave function parameters are optimized, including coefficients and exponents of the Gaussian primitives of the AGP and the Jastrow atomic orbitals. Bond lengths and bond angles are calculated with a statistical error of about 0.1% and are in good agreement with the available experimental data. The Variational and Diffusion Monte Carlo calculations estimate vertical and adiabatic excitation energies in the ranges 4.623(10)-4.688(5) eV and 3.001(5)-3.091(5) eV, respectively. The adiabatic gap, which is in line with other correlated quantum chemistry methods, is slightly higher than the value estimated by recent photodissociation experiments. Our results demonstrate how Quantum Monte Carlo calculations have become a promising and computationally affordable tool for the structural optimization of correlated molecular systems.

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

    SciTech Connect

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

    2016-01-07

    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 H{sub 2}O, N{sub 2}, and F{sub 2} 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.

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

    SciTech Connect

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

    2016-01-07

    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.

  11. Reptation quantum Monte Carlo algorithm for lattice Hamiltonians with a directed-update scheme.

    PubMed

    Carleo, Giuseppe; Becca, Federico; Moroni, Saverio; Baroni, Stefano

    2010-10-01

    We provide an extension to lattice systems of the reptation quantum Monte Carlo algorithm, originally devised for continuous Hamiltonians. For systems affected by the sign problem, a method to systematically improve upon the so-called fixed-node approximation is also proposed. The generality of the method, which also takes advantage of a canonical worm algorithm scheme to measure off-diagonal observables, makes it applicable to a vast variety of quantum systems and eases the study of their ground-state and excited-state properties. As a case study, we investigate the quantum dynamics of the one-dimensional Heisenberg model and we provide accurate estimates of the ground-state energy of the two-dimensional fermionic Hubbard model.

  12. Numerical system utilising a Monte Carlo calculation method for accurate dose assessment in radiation accidents.

    PubMed

    Takahashi, F; Endo, A

    2007-01-01

    A system utilising radiation transport codes has been developed to derive accurate dose distributions in a human body for radiological accidents. A suitable model is quite essential for a numerical analysis. Therefore, two tools were developed to setup a 'problem-dependent' input file, defining a radiation source and an exposed person to simulate the radiation transport in an accident with the Monte Carlo calculation codes-MCNP and MCNPX. Necessary resources are defined by a dialogue method with a generally used personal computer for both the tools. The tools prepare human body and source models described in the input file format of the employed Monte Carlo codes. The tools were validated for dose assessment in comparison with a past criticality accident and a hypothesized exposure.

  13. GORRAM: Introducing accurate operational-speed radiative transfer Monte Carlo solvers

    NASA Astrophysics Data System (ADS)

    Buras-Schnell, Robert; Schnell, Franziska; Buras, Allan

    2016-06-01

    We present a new approach for solving the radiative transfer equation in horizontally homogeneous atmospheres. The motivation was to develop a fast yet accurate radiative transfer solver to be used in operational retrieval algorithms for next generation meteorological satellites. The core component is the program GORRAM (Generator Of Really Rapid Accurate Monte-Carlo) which generates solvers individually optimized for the intended task. These solvers consist of a Monte Carlo model capable of path recycling and a representative set of photon paths. Latter is generated using the simulated annealing technique. GORRAM automatically takes advantage of limitations on the variability of the atmosphere. Due to this optimization the number of photon paths necessary for accurate results can be reduced by several orders of magnitude. For the shown example of a forward model intended for an aerosol satellite retrieval, comparison with an exact yet slow solver shows that a precision of better than 1% can be achieved with only 36 photons. The computational time is at least an order of magnitude faster than any other type of radiative transfer solver. Merely the lookup table approach often used in satellite retrieval is faster, but on the other hand suffers from limited accuracy. This makes GORRAM-generated solvers an eligible candidate as forward model in operational-speed retrieval algorithms and data assimilation applications. GORRAM also has the potential to create fast solvers of other integrable equations.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. Monte Carlo modeling provides accurate calibration factors for radionuclide activity meters.

    PubMed

    Zagni, F; Cicoria, G; Lucconi, G; Infantino, A; Lodi, F; Marengo, M

    2014-12-01

    Accurate determination of calibration factors for radionuclide activity meters is crucial for quantitative studies and in the optimization step of radiation protection, as these detectors are widespread in radiopharmacy and nuclear medicine facilities. In this work we developed the Monte Carlo model of a widely used activity meter, using the Geant4 simulation toolkit. More precisely the "PENELOPE" EM physics models were employed. The model was validated by means of several certified sources, traceable to primary activity standards, and other sources locally standardized with spectrometry measurements, plus other experimental tests. Great care was taken in order to accurately reproduce the geometrical details of the gas chamber and the activity sources, each of which is different in shape and enclosed in a unique container. Both relative calibration factors and ionization current obtained with simulations were compared against experimental measurements; further tests were carried out, such as the comparison of the relative response of the chamber for a source placed at different positions. The results showed a satisfactory level of accuracy in the energy range of interest, with the discrepancies lower than 4% for all the tested parameters. This shows that an accurate Monte Carlo modeling of this type of detector is feasible using the low-energy physics models embedded in Geant4. The obtained Monte Carlo model establishes a powerful tool for first instance determination of new calibration factors for non-standard radionuclides, for custom containers, when a reference source is not available. Moreover, the model provides an experimental setup for further research and optimization with regards to materials and geometrical details of the measuring setup, such as the ionization chamber itself or the containers configuration.

  19. Fast Monte Carlo Electron-Photon Transport Method and Application in Accurate Radiotherapy

    NASA Astrophysics Data System (ADS)

    Hao, Lijuan; Sun, Guangyao; Zheng, Huaqing; Song, Jing; Chen, Zhenping; Li, Gui

    2014-06-01

    Monte Carlo (MC) method is the most accurate computational method for dose calculation, but its wide application on clinical accurate radiotherapy is hindered due to its poor speed of converging and long computation time. In the MC dose calculation research, the main task is to speed up computation while high precision is maintained. The purpose of this paper is to enhance the calculation speed of MC method for electron-photon transport with high precision and ultimately to reduce the accurate radiotherapy dose calculation time based on normal computer to the level of several hours, which meets the requirement of clinical dose verification. Based on the existing Super Monte Carlo Simulation Program (SuperMC), developed by FDS Team, a fast MC method for electron-photon coupled transport was presented with focus on two aspects: firstly, through simplifying and optimizing the physical model of the electron-photon transport, the calculation speed was increased with slightly reduction of calculation accuracy; secondly, using a variety of MC calculation acceleration methods, for example, taking use of obtained information in previous calculations to avoid repeat simulation of particles with identical history; applying proper variance reduction techniques to accelerate MC method convergence rate, etc. The fast MC method was tested by a lot of simple physical models and clinical cases included nasopharyngeal carcinoma, peripheral lung tumor, cervical carcinoma, etc. The result shows that the fast MC method for electron-photon transport was fast enough to meet the requirement of clinical accurate radiotherapy dose verification. Later, the method will be applied to the Accurate/Advanced Radiation Therapy System ARTS as a MC dose verification module.

  20. 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.

  1. Parallelized quantum Monte Carlo algorithm with nonlocal worm updates.

    PubMed

    Masaki-Kato, Akiko; Suzuki, Takafumi; Harada, Kenji; Todo, Synge; Kawashima, Naoki

    2014-04-11

    Based on the worm algorithm in the path-integral representation, we propose a general quantum Monte Carlo algorithm suitable for parallelizing on a distributed-memory computer by domain decomposition. Of particular importance is its application to large lattice systems of bosons and spins. A large number of worms are introduced and its population is controlled by a fictitious transverse field. For a benchmark, we study the size dependence of the Bose-condensation order parameter of the hard-core Bose-Hubbard model with L×L×βt=10240×10240×16, using 3200 computing cores, which shows good parallelization efficiency.

  2. Graphics Processing Unit Accelerated Hirsch-Fye Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Moore, Conrad; Abu Asal, Sameer; Rajagoplan, Kaushik; Poliakoff, David; Caprino, Joseph; Tomko, Karen; Thakur, Bhupender; Yang, Shuxiang; Moreno, Juana; Jarrell, Mark

    2012-02-01

    In Dynamical Mean Field Theory and its cluster extensions, such as the Dynamic Cluster Algorithm, the bottleneck of the algorithm is solving the self-consistency equations with an impurity solver. Hirsch-Fye Quantum Monte Carlo is one of the most commonly used impurity and cluster solvers. This work implements optimizations of the algorithm, such as enabling large data re-use, suitable for the Graphics Processing Unit (GPU) architecture. The GPU's sheer number of concurrent parallel computations and large bandwidth to many shared memories takes advantage of the inherent parallelism in the Green function update and measurement routines, and can substantially improve the efficiency of the Hirsch-Fye impurity solver.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    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 the energies and radii of neutron drops. In particular, 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.

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

    SciTech Connect

    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 the 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.

  5. Quantum Monte Carlo Characterization of Excited States and Energy-Level Alignment of Oligomer/Quantum-Dot Interfaces

    NASA Astrophysics Data System (ADS)

    Dubois, Jonathan; Lee, Donghwa; Kanai, Yosuke

    2013-03-01

    Charge separation of excitons in materials is one of the most important physical processes to utilize the solar energy in diverse devices including solar cells and photo-catalysts. Heterogeneous interfaces with the so-called type-II character are often employed to infer the interfacial charge transfer in this context. As a simple criterion for designing such an interface, the energy alignment of the quasi-particle states together with the exciton binding energy of electron-donating materials is often discussed in the literature. However, an accurate description of the effect of exciton binding at the interface has not been investigated extensively. Although density functional theory (DFT) is a powerful method to investigate various electronic properties of materials, incomplete description of many-body interactions can lead to an incorrect interpretation of the energy level alignment. While Many-Body Perturbation Theory and Quantum Monte Carlo are promising in this context, much more work is necessary to assess how well these methods perform in practice. In this talk, we will discuss our preliminary results using diffusion Quantum Monte Carlo to calculate the excited states and energy-level alignment at an Oligomer/Quantum-Dot interface - a system that is often discussed in context of solar energy conversion. This work is Prepared by LLNL under Contract DE-AC52-07NA27344.

  6. Quantum Monte Carlo simulations of fidelity at magnetic quantum phase transitions.

    PubMed

    Schwandt, David; Alet, Fabien; Capponi, Sylvain

    2009-10-23

    When a system undergoes a quantum phase transition, the ground-state wave function shows a change of nature, which can be monitored using the fidelity concept. We introduce two quantum Monte Carlo schemes that allow the computation of fidelity and its susceptibility for large interacting many-body systems. These methods are illustrated on a two-dimensional Heisenberg model, where fidelity estimators show marked behavior at two successive quantum phase transitions. We also develop a scaling theory which relates the divergence of the fidelity susceptibility to the critical exponent of the correlation length. A good agreement is found with the numerical results.

  7. Quantum Monte Carlo with Chiral Interactions: New Results and Future Directions

    NASA Astrophysics Data System (ADS)

    Lynn, Joel

    2016-09-01

    Quantum Monte Carlo methods, including the Green's function Monte Carlo (GFMC) method and the auxiliary-field diffusion Monte Carlo (AFDMC) method, are arguably the most accurate many-body methods in nuclear physics. Chiral effective field theory (EFT) presents a systematic way to derive nuclear interactions from an EFT whose organizing principle is the same symmetry as low-energy quantum chromodynamics. The combination of these two is a novel and exciting development. In this talk, I present our recent work on GFMC calculations of light nuclei and AFDMC calculations of neutron matter using local two- and three-nucleon interactions derived from chiral EFT up to next-to-next-to-leading order (N2LO). I discuss the choice of observables we make to fit the two undetermined low-energy constants which enter in the three-nucleon sector at N2LO: the 4He binding energy and n- α elastic scattering P-wave phase shifts. I show that chiral two- and three-nucleon interactions have sufficient freedom to simultaneously fit properties of light nuclei, n- α scattering P-wave phase shifts, and provide a reasonable description of neutron matter. Finally I discuss some exciting applications of this framework which have recently been completed and some future projects. ERC Grant No. 307986 STRONGINT.

  8. Accurate Assignment of Significance to Neuropeptide Identifications Using Monte Carlo K-Permuted Decoy Databases

    PubMed Central

    Andrén, Per E.; Sweedler, Jonathan V.; Rodriguez-Zas, Sandra L.

    2014-01-01

    In support of accurate neuropeptide identification in mass spectrometry experiments, novel Monte Carlo permutation testing was used to compute significance values. Testing was based on k-permuted decoy databases, where k denotes the number of permutations. These databases were integrated with a range of peptide identification indicators from three popular open-source database search software (OMSSA, Crux, and X! Tandem) to assess the statistical significance of neuropeptide spectra matches. Significance p-values were computed as the fraction of the sequences in the database with match indicator value better than or equal to the true target spectra. When applied to a test-bed of all known manually annotated mouse neuropeptides, permutation tests with k-permuted decoy databases identified up to 100% of the neuropeptides at p-value < 10−5. The permutation test p-values using hyperscore (X! Tandem), E-value (OMSSA) and Sp score (Crux) match indicators outperformed all other match indicators. The robust performance to detect peptides of the intuitive indicator “number of matched ions between the experimental and theoretical spectra” highlights the importance of considering this indicator when the p-value was borderline significant. Our findings suggest permutation decoy databases of size 1×105 are adequate to accurately detect neuropeptides and this can be exploited to increase the speed of the search. The straightforward Monte Carlo permutation testing (comparable to a zero order Markov model) can be easily combined with existing peptide identification software to enable accurate and effective neuropeptide detection. The source code is available at http://stagbeetle.animal.uiuc.edu/pepshop/MSMSpermutationtesting. PMID:25329667

  9. Machine Learning of Parameters for Accurate Semiempirical Quantum Chemical Calculations

    PubMed Central

    2015-01-01

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules. PMID:26146493

  10. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    DOE PAGES

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempiricalmore » OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.« less

  11. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    SciTech Connect

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.

  12. Machine Learning of Parameters for Accurate Semiempirical Quantum Chemical Calculations.

    PubMed

    Dral, Pavlo O; von Lilienfeld, O Anatole; Thiel, Walter

    2015-05-12

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.

  13. Quantum Monte Carlo Calculations of Nanostructure Optical Properties

    NASA Astrophysics Data System (ADS)

    Williamson, Andrew

    2003-03-01

    Near linear scaling Quantum Monte Carlo (QMC) calculations[1] are used to calculate the optical gaps, electron affinities, and ionization potentials of silicon and germanium quantum dots ranging in size from 0 to 2 nm[2]. These QMC results are used to examine the accuracy of semi-empirical and density functional (DFT) calculations. We find optical gaps are underestimated by DFT by 1-2 eV depending on choice of functional. Corrections introduced by the time dependent formalisms are found to be minimal in these systems. Our results also show that quantum confinement in germanium is significantly greater than in silicon leading to a crossover of their optical gaps in dots between 2 and 3 nm in size, verifying recent experiment observations. [1] A. J. Williamson, R.Q. Hood and J.C. Grossman, Phys. Rev. Lett. 87, 246406-1 (2001). [2] A.J. Williamson J.C. Grossman, R.Q. Hood, A. Puzder and Giulia Galli, Phys. Rev. Lett, 89, 196803 (2002).

  14. Quantum Monte Carlo simulation of a particular class of non-stoquastic Hamiltonians in quantum annealing.

    PubMed

    Ohzeki, Masayuki

    2017-01-23

    Quantum annealing is a generic solver of the optimization problem that uses fictitious quantum fluctuation. Its simulation in classical computing is often performed using the quantum Monte Carlo simulation via the Suzuki-Trotter decomposition. However, the negative sign problem sometimes emerges in the simulation of quantum annealing with an elaborate driver Hamiltonian, since it belongs to a class of non-stoquastic Hamiltonians. In the present study, we propose an alternative way to avoid the negative sign problem involved in a particular class of the non-stoquastic Hamiltonians. To check the validity of the method, we demonstrate our method by applying it to a simple problem that includes the anti-ferromagnetic XX interaction, which is a typical instance of the non-stoquastic Hamiltonians.

  15. Quantum Monte Carlo simulation of a particular class of non-stoquastic Hamiltonians in quantum annealing

    NASA Astrophysics Data System (ADS)

    Ohzeki, Masayuki

    2017-01-01

    Quantum annealing is a generic solver of the optimization problem that uses fictitious quantum fluctuation. Its simulation in classical computing is often performed using the quantum Monte Carlo simulation via the Suzuki–Trotter decomposition. However, the negative sign problem sometimes emerges in the simulation of quantum annealing with an elaborate driver Hamiltonian, since it belongs to a class of non-stoquastic Hamiltonians. In the present study, we propose an alternative way to avoid the negative sign problem involved in a particular class of the non-stoquastic Hamiltonians. To check the validity of the method, we demonstrate our method by applying it to a simple problem that includes the anti-ferromagnetic XX interaction, which is a typical instance of the non-stoquastic Hamiltonians.

  16. Quantum Monte Carlo simulation of a particular class of non-stoquastic Hamiltonians in quantum annealing

    PubMed Central

    Ohzeki, Masayuki

    2017-01-01

    Quantum annealing is a generic solver of the optimization problem that uses fictitious quantum fluctuation. Its simulation in classical computing is often performed using the quantum Monte Carlo simulation via the Suzuki–Trotter decomposition. However, the negative sign problem sometimes emerges in the simulation of quantum annealing with an elaborate driver Hamiltonian, since it belongs to a class of non-stoquastic Hamiltonians. In the present study, we propose an alternative way to avoid the negative sign problem involved in a particular class of the non-stoquastic Hamiltonians. To check the validity of the method, we demonstrate our method by applying it to a simple problem that includes the anti-ferromagnetic XX interaction, which is a typical instance of the non-stoquastic Hamiltonians. PMID:28112244

  17. 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.

  18. Measuring Renyi entanglement entropy in quantum Monte Carlo simulations.

    PubMed

    Hastings, Matthew B; González, Iván; Kallin, Ann B; Melko, Roger G

    2010-04-16

    We develop a quantum Monte Carlo procedure, in the valence bond basis, to measure the Renyi entanglement entropy of a many-body ground state as the expectation value of a unitary Swap operator acting on two copies of the system. An improved estimator involving the ratio of Swap operators for different subregions enables convergence of the entropy in a simulation time polynomial in the system size. We demonstrate convergence of the Renyi entropy to exact results for a Heisenberg chain. Finally, we calculate the scaling of the Renyi entropy in the two-dimensional Heisenberg model and confirm that the Néel ground state obeys the expected area law for systems up to linear size L=32.

  19. 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.

  20. Quantum Monte Carlo Calculations of Transition Metal Oxides

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas

    2006-03-01

    Quantum Monte Carlo is a powerful computational tool to study correlated systems, allowing us to explicitly treat many-body interactions with favorable scaling in the number of particles. It has been regarded as a benchmark tool for first and second row condensed matter systems, although its accuracy has not been thoroughly investigated in strongly correlated transition metal oxides. QMC has also historically suffered from the mixed estimator error in operators that do not commute with the Hamiltonian and from stochastic uncertainty, which make small energy differences unattainable. Using the Reptation Monte Carlo algorithm of Moroni and Baroni(along with contributions from others), we have developed a QMC framework that makes these previously unavailable quantities computationally feasible for systems of hundreds of electrons in a controlled and consistent way, and apply this framework to transition metal oxides. We compare these results with traditional mean-field results like the LDA and with experiment where available, focusing in particular on the polarization and lattice constants in a few interesting ferroelectric materials. This work was performed in collaboration with Lubos Mitas and Jeffrey Grossman.

  1. 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

  2. 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

  3. High-pressure hydrogen sulfide by diffusion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Azadi, Sam; Kühne, Thomas D.

    2017-02-01

    We revisit the enthalpy-pressure phase diagram of the various products from the different proposed decompositions of H2S at pressures above 150 GPa by means of accurate diffusion Monte Carlo simulations. Our results entail a revision of the ground-state enthalpy-pressure phase diagram. Specifically, we find that the C2/c HS2 structure is persistent up to 440 GPa before undergoing a phase transition into the C2/m phase. Contrary to density functional theory, our calculations suggest that the C2/m phase of HS is more stable than the I41/amd HS structure over the whole pressure range from 150 to 400 GPa. More importantly, we predict that the Im-3m phase is the most likely candidate for H3S, which is consistent with recent experimental x-ray diffraction measurements.

  4. 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.

  5. Accurate and precise determination of critical properties from Gibbs ensemble Monte Carlo simulations

    SciTech Connect

    Dinpajooh, Mohammadhasan; Bai, Peng; Allan, Douglas A.; Siepmann, J. Ilja

    2015-09-21

    Since the seminal paper by Panagiotopoulos [Mol. Phys. 61, 813 (1997)], the Gibbs ensemble Monte Carlo (GEMC) method has been the most popular particle-based simulation approach for the computation of vapor–liquid phase equilibria. However, the validity of GEMC simulations in the near-critical region has been questioned because rigorous finite-size scaling approaches cannot be applied to simulations with fluctuating volume. Valleau [Mol. Simul. 29, 627 (2003)] has argued that GEMC simulations would lead to a spurious overestimation of the critical temperature. More recently, Patel et al. [J. Chem. Phys. 134, 024101 (2011)] opined that the use of analytical tail corrections would be problematic in the near-critical region. To address these issues, we perform extensive GEMC simulations for Lennard-Jones particles in the near-critical region varying the system size, the overall system density, and the cutoff distance. For a system with N = 5500 particles, potential truncation at 8σ and analytical tail corrections, an extrapolation of GEMC simulation data at temperatures in the range from 1.27 to 1.305 yields T{sub c} = 1.3128 ± 0.0016, ρ{sub c} = 0.316 ± 0.004, and p{sub c} = 0.1274 ± 0.0013 in excellent agreement with the thermodynamic limit determined by Potoff and Panagiotopoulos [J. Chem. Phys. 109, 10914 (1998)] using grand canonical Monte Carlo simulations and finite-size scaling. Critical properties estimated using GEMC simulations with different overall system densities (0.296 ≤ ρ{sub t} ≤ 0.336) agree to within the statistical uncertainties. For simulations with tail corrections, data obtained using r{sub cut} = 3.5σ yield T{sub c} and p{sub c} that are higher by 0.2% and 1.4% than simulations with r{sub cut} = 5 and 8σ but still with overlapping 95% confidence intervals. In contrast, GEMC simulations with a truncated and shifted potential show that r{sub cut} = 8σ is insufficient to obtain accurate results. Additional GEMC simulations for hard

  6. Analysis of quantum Monte Carlo dynamics for quantum adiabatic evolution in infinite-range spin systems

    NASA Astrophysics Data System (ADS)

    Inoue, Jun-Ichi

    2011-03-01

    We analytically derive deterministic equations of order parameters such as spontaneous magnetization in infinite-range quantum spin systems obeying quantum Monte Carlo dynamics. By means of the Trotter decomposition, we consider the transition probability of Glauber-type dynamics of microscopic states for the corresponding classical system. Under the static approximation, differential equations with respect to macroscopic order parameters are explicitly obtained from the master equation that describes the microscopic-law. We discuss several possible applications of our approach to disordered spin systems for statistical-mechanical informatics. Especially, we argue the ground state searching for infinite-range random spin systems via quantum adiabatic evolution. We were financially supported by Grant-in-Aid for Scientific Research (C) of Japan Society for the Promotion of Science, No. 22500195.

  7. A hierarchical approach to accurate predictions of macroscopic thermodynamic behavior from quantum mechanics and molecular simulations

    NASA Astrophysics Data System (ADS)

    Garrison, Stephen L.

    2005-07-01

    The combination of molecular simulations and potentials obtained from quantum chemistry is shown to be able to provide reasonably accurate thermodynamic property predictions. Gibbs ensemble Monte Carlo simulations are used to understand the effects of small perturbations to various regions of the model Lennard-Jones 12-6 potential. However, when the phase behavior and second virial coefficient are scaled by the critical properties calculated for each potential, the results obey a corresponding states relation suggesting a non-uniqueness problem for interaction potentials fit to experimental phase behavior. Several variations of a procedure collectively referred to as quantum mechanical Hybrid Methods for Interaction Energies (HM-IE) are developed and used to accurately estimate interaction energies from CCSD(T) calculations with a large basis set in a computationally efficient manner for the neon-neon, acetylene-acetylene, and nitrogen-benzene systems. Using these results and methods, an ab initio, pairwise-additive, site-site potential for acetylene is determined and then improved using results from molecular simulations using this initial potential. The initial simulation results also indicate that a limited range of energies important for accurate phase behavior predictions. Second virial coefficients calculated from the improved potential indicate that one set of experimental data in the literature is likely erroneous. This prescription is then applied to methanethiol. Difficulties in modeling the effects of the lone pair electrons suggest that charges on the lone pair sites negatively impact the ability of the intermolecular potential to describe certain orientations, but that the lone pair sites may be necessary to reasonably duplicate the interaction energies for several orientations. Two possible methods for incorporating the effects of three-body interactions into simulations within the pairwise-additivity formulation are also developed. A low density

  8. A Monte Carlo Method for Making the SDSS u-Band Magnitude More Accurate

    NASA Astrophysics Data System (ADS)

    Gu, Jiayin; Du, Cuihua; Zuo, Wenbo; Jing, Yingjie; Wu, Zhenyu; Ma, Jun; Zhou, Xu

    2016-10-01

    We develop a new Monte Carlo-based method to convert the Sloan Digital Sky Survey (SDSS) u-band magnitude to the south Galactic Cap of the u-band Sky Survey (SCUSS) u-band magnitude. Due to the increased accuracy of SCUSS u-band measurements, the converted u-band magnitude becomes more accurate compared with the original SDSS u-band magnitude, in particular at the faint end. The average u-magnitude error (for both SDSS and SCUSS) of numerous main-sequence stars with 0.2\\lt g-r\\lt 0.8 increases as the g-band magnitude becomes fainter. When g = 19.5, the average magnitude error of the SDSS u is 0.11. When g = 20.5, the average SDSS u error rises to 0.22. However, at this magnitude, the average magnitude error of the SCUSS u is just half as much as that of the SDSS u. The SDSS u-band magnitudes of main-sequence stars with 0.2\\lt g-r\\lt 0.8 and 18.5\\lt g\\lt 20.5 are converted, therefore the maximum average error of the converted u-band magnitudes is 0.11. The potential application of this conversion is to derive a more accurate photometric metallicity calibration from SDSS observations, especially for the more distant stars. Thus, we can explore stellar metallicity distributions either in the Galactic halo or some stream stars.

  9. 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.

  10. How accurate is the Pearson r-from-Z approximation? A Monte Carlo simulation study.

    PubMed

    Hittner, James B; May, Kim

    2012-01-01

    The Pearson r-from-Z approximation estimates the sample correlation (as an effect size measure) from the ratio of two quantities: the standard normal deviate equivalent (Z-score) corresponding to a one-tailed p-value divided by the square root of the total (pooled) sample size. The formula has utility in meta-analytic work when reports of research contain minimal statistical information. Although simple to implement, the accuracy of the Pearson r-from-Z approximation has not been empirically evaluated. To address this omission, we performed a series of Monte Carlo simulations. Results indicated that in some cases the formula did accurately estimate the sample correlation. However, when sample size was very small (N = 10) and effect sizes were small to small-moderate (ds of 0.1 and 0.3), the Pearson r-from-Z approximation was very inaccurate. Detailed figures that provide guidance as to when the Pearson r-from-Z formula will likely yield valid inferences are presented.

  11. Quantum circuit design for accurate simulation of qudit channels

    NASA Astrophysics Data System (ADS)

    Wang, Dong-Sheng; Sanders, Barry C.

    2015-04-01

    We construct a classical algorithm that designs quantum circuits for algorithmic quantum simulation of arbitrary qudit channels on fault-tolerant quantum computers within a pre-specified error tolerance with respect to diamond-norm distance. The classical algorithm is constructed by decomposing a quantum channel into a convex combination of generalized extreme channels by convex optimization of a set of nonlinear coupled algebraïc equations. The resultant circuit is a randomly chosen generalized extreme channel circuit whose run-time is logarithmic with respect to the error tolerance and quadratic with respect to Hilbert space dimension, which requires only a single ancillary qudit plus classical dits.

  12. Evidence for stable square ice from quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Chen, Ji; Zen, Andrea; Brandenburg, Jan Gerit; Alfè, Dario; Michaelides, Angelos

    2016-12-01

    Recent experiments on ice formed by water under nanoconfinement provide evidence for a two-dimensional (2D) "square ice" phase. However, the interpretation of the experiments has been questioned and the stability of square ice has become a matter of debate. Partially this is because the simulation approaches employed so far (force fields and density functional theory) struggle to accurately describe the very small energy differences between the relevant phases. Here we report a study of 2D ice using an accurate wave-function based electronic structure approach, namely diffusion Monte Carlo (DMC). We find that at relatively high pressure, square ice is indeed the lowest enthalpy phase examined, supporting the initial experimental claim. Moreover, at lower pressures, a "pentagonal ice" phase (not yet observed experimentally) has the lowest enthalpy, and at ambient pressure, the "pentagonal ice" phase is degenerate with a "hexagonal ice" phase. Our DMC results also allow us to evaluate the accuracy of various density functional theory exchange-correlation functionals and force field models, and in doing so we extend the understanding of how such methodologies perform to challenging 2D structures presenting dangling hydrogen bonds.

  13. A fast and efficient algorithm for Slater determinant updates in quantum Monte Carlo simulations.

    PubMed

    Nukala, Phani K V V; Kent, P R C

    2009-05-28

    We present an efficient low-rank updating algorithm for updating the trial wave functions used in quantum Monte Carlo (QMC) simulations. The algorithm is based on low-rank updating of the Slater determinants. In particular, the computational complexity of the algorithm is O(kN) during the kth step compared to traditional algorithms that require O(N(2)) computations, where N is the system size. For single determinant trial wave functions the new algorithm is faster than the traditional O(N(2)) Sherman-Morrison algorithm for up to O(N) updates. For multideterminant configuration-interaction-type trial wave functions of M+1 determinants, the new algorithm is significantly more efficient, saving both O(MN(2)) work and O(MN(2)) storage. The algorithm enables more accurate and significantly more efficient QMC calculations using configuration-interaction-type wave functions.

  14. 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.

  15. 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.

  16. Auxiliary-field quantum Monte Carlo method for strongly paired fermions

    SciTech Connect

    Carlson, J.; Gandolfi, Stefano; Schmidt, Kevin E.; Zhang, Shiwei

    2011-12-15

    We solve the zero-temperature unitary Fermi gas problem by incorporating a BCS importance function into the auxiliary-field quantum Monte Carlo method. We demonstrate that this method does not suffer from a sign problem and that it increases the efficiency of standard techniques by many orders of magnitude for strongly paired fermions. We calculate the ground-state energies exactly for unpolarized systems with up to 66 particles on lattices of up to 27{sup 3} sites, obtaining an accurate result for the universal parameter {xi}. We also obtain results for interactions with different effective ranges and find that the energy is consistent with a universal linear dependence on the product of the Fermi momentum and the effective range. This method will have many applications in superfluid cold atom systems and in both electronic and nuclear structures where pairing is important.

  17. Quantum Monte Carlo Simulation of Nanoscale MgH2 Cluster Thermodynamics

    NASA Astrophysics Data System (ADS)

    Wu, Zhigang; Allendorf, Mark; Grossman, Jeffrey

    2010-03-01

    We calculated the desorption energy of MgH2 clusters using the quantum Monte Carlo (QMC) approach, which can provide desorption energies with chemical accuracy (within 1 kcal/mol) and therefore a valuable benchmark for such hydrogen-storage simulations. Compared with these QMC results, the widely used density-functional-theory (DFT) computations cannot reach a consistent and suitable level of accuracy across the thermodynamically tunable range for MgH2 clusters, for a wide range of exchange-correlation functionals. Furthermore, our QMC calculations show that the DFT error depends substantially on cluster size. These results suggest that in simulating metal-hydride systems it is crucial to apply accurate methods that go beyond traditional mean-field approaches as a benchmark of their performance for a given material, and QMC is an appealing method for such a benchmark due to its high level of accuracy and favorable scaling (N^3) with number of electrons.

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

    PubMed

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

    2015-07-28

    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.

  19. 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.

  20. Energy density matrix formalism for interacting quantum systems: a quantum Monte Carlo study

    SciTech Connect

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

    2014-01-01

    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 imple- mented 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 demonstrates a quantita- tive 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 a new avenue for describing energetics with quantum Monte Carlo methods which have traditionally been limited to total energies.

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

    SciTech Connect

    Clay, III, Raymond C.; Morales, Miguel A.

    2015-06-16

    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 study, 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. Finally, 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.

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

    DOE PAGES

    Clay, III, Raymond C.; Morales, Miguel A.

    2015-06-16

    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 applicationmore » of these wavefunctions to large systems and solids. In this study, 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. Finally, 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.« less

  3. Quantum Monte Carlo simulations for disordered Bose systems

    SciTech Connect

    Trivedi, N.

    1992-03-01

    Interacting bosons in a random potential can be used to model {sup 3}He adsorbed in porous media, universal aspects of the superconductor-insulator transition in disordered films, and vortices in disordered type II superconductors. We study a model of bosons on a 2D square lattice with a random potential of strength V and on-site repulsion U. We first describe the path integral Monte Carlo algorithm used to simulate this system. The 2D quantum problem (at T=0) gets mapped onto a classical problem of strings or directed polymers moving in 3D with each string representing the world line of a boson. We discuss efficient ways of sampling the polymer configurations as well as the permutations between the bosons. We calculate the superfluid density and the excitation spectrum. Using these results we distinguish between a superfluid, a localized or Bose glass'' insulator with gapless excitations and a Mott insulator with a finite gap to excitations (found only at commensurate densities). We discover novel effects arising from the interpaly between V and U and present preliminary results for the phase diagram at incommensurate and commensurate densities.

  4. Quantum Monte Carlo simulations for disordered Bose systems

    SciTech Connect

    Trivedi, N.

    1992-03-01

    Interacting bosons in a random potential can be used to model {sup 3}He adsorbed in porous media, universal aspects of the superconductor-insulator transition in disordered films, and vortices in disordered type II superconductors. We study a model of bosons on a 2D square lattice with a random potential of strength V and on-site repulsion U. We first describe the path integral Monte Carlo algorithm used to simulate this system. The 2D quantum problem (at T=0) gets mapped onto a classical problem of strings or directed polymers moving in 3D with each string representing the world line of a boson. We discuss efficient ways of sampling the polymer configurations as well as the permutations between the bosons. We calculate the superfluid density and the excitation spectrum. Using these results we distinguish between a superfluid, a localized or ``Bose glass`` insulator with gapless excitations and a Mott insulator with a finite gap to excitations (found only at commensurate densities). We discover novel effects arising from the interpaly between V and U and present preliminary results for the phase diagram at incommensurate and commensurate densities.

  5. Quantum Monte Carlo applied to Solids under Pressure

    NASA Astrophysics Data System (ADS)

    Shulenburger, Luke; Mattsson, T. R.

    2012-02-01

    Diffusion quantum Monte Carlo (DMC) has been applied to solids under pressure in several different contexts a high degree of success.ootnotetextJ. Kolorenc and L. Mitas. Rep. Prog. Phys. 74 026502 (2011) All of these calculations must address three errors present in DMC calculations of solids: the fixed node approximation, the pseudopotential approximation and the finite size approximation. Due to the varying approximations to address these errors, these calculations suffer from an uncertainty that is almost comparable to that introduced by the choice of functional in density functional theory (DFT). In this presentation, we present lattice constants and bulk moduli of more than fifteen solids under compression performed with a consistent approach to these three approximations. These results help establish the general accuracy that may be expected from DMC calculations of solids under pressure and also provide a reference from which improvements to DMC methods may be judged. [4pt] 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.

  6. Quantum Monte Carlo studies of quantum criticality in low-dimensional spin systems

    NASA Astrophysics Data System (ADS)

    Tang, Ying

    Strongly correlated low-dimensional quantum spin models provide a well-established frame- work to study magnetic properties of insulators, and are of great theoretical interest and experimental relevance in condensed-matter physics. In this thesis, I use quantum Monte Carlo methods to numerically study quantum critical behavior in low-dimensional quantum spin models and wavefunctions. First, I study spinons---emergent spin-1/2 bosonic excitations---at certain one- and two-dimensional quantum phase transitions (QPTs) in spin models, by characterizing their size and confinement length quantitatively. In particular, I focus on the QPT from an antiferromagnetic (AFM) phase into a valence-bond solid (VBS) phase, which is an example of a violation of the standard Landau-Ginzburg-Wilson paradigm for phase transitions. This transition in two dimensions (2D) is instead likely described by a novel theory called "deconfined quantum criticality" (DQC). According to the theory, spinons should be deconfined. The degree of deconfinement is quantified in my calculations. Second, I present a comprehensive study of so-called short-bond resonating-valence-bond (RVB) spin liquids in 2D, which have been suggested as a good starting point for understanding the spin physics of high-temperature cuprates. I find that these RVB states can also be classified as quantum-critical VBS states, which indicates that RVB is less disordered than expected. This work suggests a possible mapping from the quantum RVB states to classical dimer models via a classical continuum field theory---the height model. This map explicitly bridges well-established classical results to future quantum studies. Third, I consider 1D amplitude product (AP) states, which are generalized versions of RVB states, with different wavefunction weightings of bonds according to their lengths. AP states constitute a good ansatz for certain Hamiltonians and are of broad interest in quantum magnetism. I study phase transitions from

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

    SciTech Connect

    Christov, Ivan P.

    2016-08-15

    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.

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

    SciTech Connect

    Rodriquez, Maria Milagos Soto

    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, C2H and C2H2. 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

  9. Quantum Monte Carlo calculations of the dimerization energy of borane.

    PubMed

    Fracchia, Francesco; Bressanini, Dario; Morosi, Gabriele

    2011-09-07

    Accurate thermodynamic data are required to improve the performance of chemical hydrides that are potential hydrogen storage materials. Boron compounds are among the most interesting candidates. However, different experimental measurements of the borane dimerization energy resulted in a rather wide range (-34.3 to -39.1) ± 2 kcal/mol. Diffusion Monte Carlo (DMC) simulations usually recover more than 95% of the correlation energy, so energy differences rely less on error cancellation than other methods. DMC energies of BH(3), B(2)H(6), BH(3)CO, CO, and BH(2)(+) allowed us to predict the borane dimerization energy, both via the direct process and indirect processes such as the dissociation of BH(3)CO. Our D(e) = -43.12(8) kcal/mol, corrected for the zero point energy evaluated by considering the anharmonic contributions, results in a borane dimerization energy of -36.59(8) kcal/mol. The process via the dissociation of BH(3)CO gives -34.5(2) kcal/mol. Overall, our values suggest a slightly less D(e) than the most recent W4 estimate D(e) = -44.47 kcal/mol [A. Karton and J. M. L. Martin, J. Phys. Chem. A 111, 5936 (2007)]. Our results show that reliable thermochemical data for boranes can be predicted by fixed node (FN)-DMC calculations.

  10. Enabling quantum communications through accurate photons polarization control

    NASA Astrophysics Data System (ADS)

    Almeida, Álvaro J.; Muga, Nelson J.; Silva, Nuno A.; Stojanovic, Aleksandar D.; André, Paulo S.; Pinto, Armando N.; Mora, José; Capmany, José

    2013-11-01

    The rapid increase on the information sharing around the world, leads to an utmost requirement for capacity and bandwidth. However, the need for security in the transmission and storage of information is also of major importance. The use of quantum technologies provides a practical solution for secure communications systems. Quantum key distribution (QKD) was the first practical application of quantum mechanics, and nowadays it is the most developed one. In order to share secret keys between two parties can be used several methods of encoding. Due to its simplicity, the encoding into polarization is one of the most used. However, when we use optical fibers as transmission channels, the polarization suffers random rotations that may change the state of polarization (SOP) of the light initially sent to the fiber to a new one at the output. Thus, in order to enable real-time communication using this encoding method it is required the use of a dynamic control system. We describe a scheme of transmission of quantum information, which is based in the polarization encoding, and that allows to share secret keys through optical fibers without interruption. The dynamic polarization control system used in such scheme is described, both theoretically and experimentally. Their advantages and limitations for the use in quantum communications are presented and discussed.

  11. 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.; ...

    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

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

    SciTech Connect

    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 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 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.

  13. 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).

  14. Trail-Needs pseudopotentials in quantum Monte Carlo calculations with plane-wave/blip basis sets

    NASA Astrophysics Data System (ADS)

    Drummond, N. D.; Trail, J. R.; Needs, R. J.

    2016-10-01

    We report a systematic analysis of the performance of a widely used set of Dirac-Fock pseudopotentials for quantum Monte Carlo (QMC) calculations. We study each atom in the periodic table from hydrogen (Z =1 ) to mercury (Z =80 ), with the exception of the 4 f elements (57 ≤Z ≤70 ). We demonstrate that ghost states are a potentially serious problem when plane-wave basis sets are used in density functional theory (DFT) orbital-generation calculations, but that this problem can be almost entirely eliminated by choosing the s channel to be local in the DFT calculation; the d channel can then be chosen to be local in subsequent QMC calculations, which generally leads to more accurate results. We investigate the achievable energy variance per electron with different levels of trial wave function and we determine appropriate plane-wave cutoff energies for DFT calculations for each pseudopotential. We demonstrate that the so-called "T-move" scheme in diffusion Monte Carlo is essential for many elements. We investigate the optimal choice of spherical integration rule for pseudopotential projectors in QMC calculations. The information reported here will prove crucial in the planning and execution of QMC projects involving beyond-first-row elements.

  15. 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.

  16. 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.

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

    DOE PAGES

    Tews, I.; Gandolfi, Stefano; Gezerlis, 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

  18. 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.

  19. 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.

  20. Barrier heights of hydrogen-transfer reactions with diffusion quantum monte carlo method.

    PubMed

    Zhou, Xiaojun; Wang, Fan

    2017-04-30

    Hydrogen-transfer reactions are an important class of reactions in many chemical and biological processes. Barrier heights of H-transfer reactions are underestimated significantly by popular exchange-correlation functional with density functional theory (DFT), while coupled-cluster (CC) method is quite expensive and can be applied only to rather small systems. Quantum Monte-Carlo method can usually provide reliable results for large systems. Performance of fixed-node diffusion quantum Monte-Carlo method (FN-DMC) on barrier heights of the 19 H-transfer reactions in the HTBH38/08 database is investigated in this study with the trial wavefunctions of the single-Slater-Jastrow form and orbitals from DFT using local density approximation. Our results show that barrier heights of these reactions can be calculated rather accurately using FN-DMC and the mean absolute error is 1.0 kcal/mol in all-electron calculations. Introduction of pseudopotentials (PP) in FN-DMC calculations improves efficiency pronouncedly. According to our results, error of the employed PPs is smaller than that of the present CCSD(T) and FN-DMC calculations. FN-DMC using PPs can thus be applied to investigate H-transfer reactions involving larger molecules reliably. In addition, bond dissociation energies of the involved molecules using FN-DMC are in excellent agreement with reference values and they are even better than results of the employed CCSD(T) calculations using the aug-cc-pVQZ basis set. © 2017 Wiley Periodicals, Inc.

  1. Towards accurate quantum simulations of large systems with small computers

    NASA Astrophysics Data System (ADS)

    Yang, Yonggang

    2017-01-01

    Numerical simulations are important for many systems. In particular, various standard computer programs have been developed for solving the quantum Schrödinger equations. However, the accuracy of these calculations is limited by computer capabilities. In this work, an iterative method is introduced to enhance the accuracy of these numerical calculations, which is otherwise prohibitive by conventional methods. The method is easily implementable and general for many systems.

  2. Towards accurate quantum simulations of large systems with small computers.

    PubMed

    Yang, Yonggang

    2017-01-24

    Numerical simulations are important for many systems. In particular, various standard computer programs have been developed for solving the quantum Schrödinger equations. However, the accuracy of these calculations is limited by computer capabilities. In this work, an iterative method is introduced to enhance the accuracy of these numerical calculations, which is otherwise prohibitive by conventional methods. The method is easily implementable and general for many systems.

  3. Towards accurate quantum simulations of large systems with small computers

    PubMed Central

    Yang, Yonggang

    2017-01-01

    Numerical simulations are important for many systems. In particular, various standard computer programs have been developed for solving the quantum Schrödinger equations. However, the accuracy of these calculations is limited by computer capabilities. In this work, an iterative method is introduced to enhance the accuracy of these numerical calculations, which is otherwise prohibitive by conventional methods. The method is easily implementable and general for many systems. PMID:28117366

  4. 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

    2014-12-09

    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.

  5. 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.

  6. Generalized Moment Method for Gap Estimation and Quantum Monte Carlo Level Spectroscopy.

    PubMed

    Suwa, Hidemaro; Todo, Synge

    2015-08-21

    We formulate a convergent sequence for the energy gap estimation in the worldline quantum Monte Carlo method. The ambiguity left in the conventional gap calculation for quantum systems is eliminated. Our estimation will be unbiased in the low-temperature limit, and also the error bar is reliably estimated. The level spectroscopy from quantum Monte Carlo data is developed as an application of the unbiased gap estimation. From the spectral analysis, we precisely determine the Kosterlitz-Thouless quantum phase-transition point of the spin-Peierls model. It is established that the quantum phonon with a finite frequency is essential to the critical theory governed by the antiadiabatic limit, i.e., the k=1 SU(2) Wess-Zumino-Witten model.

  7. Confidence and efficiency scaling in variational quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Delyon, F.; Bernu, B.; Holzmann, Markus

    2017-02-01

    Based on the central limit theorem, we discuss the problem of evaluation of the statistical error of Monte Carlo calculations using a time-discretized diffusion process. We present a robust and practical method to determine the effective variance of general observables and show how to verify the equilibrium hypothesis by the Kolmogorov-Smirnov test. We then derive scaling laws of the efficiency illustrated by variational Monte Carlo calculations on the two-dimensional electron gas.

  8. New approach based on tetrahedral-mesh geometry for accurate 4D Monte Carlo patient-dose calculation

    NASA Astrophysics Data System (ADS)

    Han, Min Cheol; Yeom, Yeon Soo; Kim, Chan Hyeong; Kim, Seonghoon; Sohn, Jason W.

    2015-02-01

    In the present study, to achieve accurate 4D Monte Carlo dose calculation in radiation therapy, we devised a new approach that combines (1) modeling of the patient body using tetrahedral-mesh geometry based on the patient’s 4D CT data, (2) continuous movement/deformation of the tetrahedral patient model by interpolation of deformation vector fields acquired through deformable image registration, and (3) direct transportation of radiation particles during the movement and deformation of the tetrahedral patient model. The results of our feasibility study show that it is certainly possible to construct 4D patient models (= phantoms) with sufficient accuracy using the tetrahedral-mesh geometry and to directly transport radiation particles during continuous movement and deformation of the tetrahedral patient model. This new approach not only produces more accurate dose distribution in the patient but also replaces the current practice of using multiple 3D voxel phantoms and combining multiple dose distributions after Monte Carlo simulations. For routine clinical application of our new approach, the use of fast automatic segmentation algorithms is a must. In order to achieve, simultaneously, both dose accuracy and computation speed, the number of tetrahedrons for the lungs should be optimized. Although the current computation speed of our new 4D Monte Carlo simulation approach is slow (i.e. ~40 times slower than that of the conventional dose accumulation approach), this problem is resolvable by developing, in Geant4, a dedicated navigation class optimized for particle transportation in tetrahedral-mesh geometry.

  9. New approach based on tetrahedral-mesh geometry for accurate 4D Monte Carlo patient-dose calculation.

    PubMed

    Han, Min Cheol; Yeom, Yeon Soo; Kim, Chan Hyeong; Kim, Seonghoon; Sohn, Jason W

    2015-02-21

    In the present study, to achieve accurate 4D Monte Carlo dose calculation in radiation therapy, we devised a new approach that combines (1) modeling of the patient body using tetrahedral-mesh geometry based on the patient's 4D CT data, (2) continuous movement/deformation of the tetrahedral patient model by interpolation of deformation vector fields acquired through deformable image registration, and (3) direct transportation of radiation particles during the movement and deformation of the tetrahedral patient model. The results of our feasibility study show that it is certainly possible to construct 4D patient models (= phantoms) with sufficient accuracy using the tetrahedral-mesh geometry and to directly transport radiation particles during continuous movement and deformation of the tetrahedral patient model. This new approach not only produces more accurate dose distribution in the patient but also replaces the current practice of using multiple 3D voxel phantoms and combining multiple dose distributions after Monte Carlo simulations. For routine clinical application of our new approach, the use of fast automatic segmentation algorithms is a must. In order to achieve, simultaneously, both dose accuracy and computation speed, the number of tetrahedrons for the lungs should be optimized. Although the current computation speed of our new 4D Monte Carlo simulation approach is slow (i.e. ~40 times slower than that of the conventional dose accumulation approach), this problem is resolvable by developing, in Geant4, a dedicated navigation class optimized for particle transportation in tetrahedral-mesh geometry.

  10. 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.

  11. Currents and Green's functions of impurities out of equilibrium: Results from inchworm quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Antipov, Andrey E.; Dong, Qiaoyuan; Kleinhenz, Joseph; Cohen, Guy; Gull, Emanuel

    2017-02-01

    We generalize the recently developed inchworm quantum Monte Carlo method to the full Keldysh contour with forward, backward, and equilibrium branches to describe the dynamics of strongly correlated impurity problems with time-dependent parameters. We introduce a method to compute Green's functions, spectral functions, and currents for inchworm Monte Carlo and show how systematic error assessments in real time can be obtained. We then illustrate the capabilities of the algorithm with a study of the behavior of quantum impurities after an instantaneous voltage quench from a thermal equilibrium state.

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

    PubMed

    Ng, Yee-Hong; Bettens, Ryan P A

    2016-03-03

    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.

  13. Quantum Diffusion Monte Carlo Method for strong field time dependent problems

    NASA Astrophysics Data System (ADS)

    Kalinski, Matt

    2006-05-01

    We formulate the Quantum Diffusion Quantum Monte Carlo (QDMC) method for the solution of the time-dependent Schr"odinger equation for atoms in strong laser fields. Unlike for the normal diffusion Monte Carlo the wave function is represented by walkers with two kinds or colors which solve two coupled and nonlinear diffusion equations. Those diffusion equations are coupled by the potentials similar to those introduced by Shay which must be added to Schr"odingers equation to obtain classical dynamics equivalent to the quantum mechanics [1]. The potentials are calculated semi-analytically similarly to smoothing methods of smooth particle electrodynamics (SPD) with Gaussian smoothing kernels. We apply this method to strong field two electron ionization of Helium. We calculate two electron double ionization rate in full six-dimensional configuration space quantum mechanically. Comparison with classical mechanics and the low dimensional grid models is also provided. 1cm [1] D. Shay, Phys. Rev A 13, 2261 (1976)

  14. Quantum Monte Carlo calculations of three and six-quark states

    NASA Astrophysics Data System (ADS)

    Paris, Mark Wayne

    2001-06-01

    Quantum Monte Carlo techniques are applied to quark descriptions of single baryon and nuclear systems using a non-relativistic constituent quark model Hamiltonian. The assumed interaction includes a three-body term arising due to flux-tube confinement, and two-body interactions arising from one-gluon and one-pion exchange. It is strongly dependent on the spin and isospin of the quarks. We solve for single baryon S and P-wave spectra by solving the Schrödinger equation variationally for the ground state of three interacting light-flavored valence quarks. The variational Monte Carlo method is then used to find the ground state of six quarks confined to a cavity of diameter Rc. The variational wave function is written as a product of three-quark nucleon states with correlations between quarks in different nucleons. We study the role of quark exchange effects by allowing flux-tube configuration mixing. An accurate six-body variational wave function is obtained. It has only ~13% rms fluctuation in the total energy and yields a standard deviation of <=.1% small enough to be useful in discerning nuclear interaction effects from the large rest mass of the two nucleons. Results are presented for three values of the cavity diameter, R c = 2, 4, and 6 fm. They indicate that the flux-tube model Hamiltonian with gluon and pion exchange requires revisions in order to obtain agreement with the energies estimated from realistic two- nucleon interactions. We calculate the two-quark density, spin, isospin, and color distribution functions and show how they may be used to study and adjust the model Hamiltonian.

  15. Exact diagonalization and quantum Monte Carlo study of an ionic Hubbard model in two dimensions

    NASA Astrophysics Data System (ADS)

    Cho, Jongweon; Lee, Ji-Woo

    2017-03-01

    We study quantum phase transitions of an ionic Hubbard model in two dimensions. The ionic Hubbard model explains the quantum states of strongly correlated electrons under the influence of checkerboard-type alternating chemical potentials. For a given amplitude of the alternating potentials Δ, we obtain quantum ground states as we tune the local repulsive energy U between a spin-up electron and a spin-down electron by using an exact diagonalization method of a modified Lanczos algorithm. The system undergoes a quantum phase transition from a band insulator to a Mott insulator as U increases at half-filling. We find the signature of a quantum phase transition by investigating the behavior of ground-state energies and that of double occupancies for the size of L × L = 4 × 4, which was the largest possible lattice in this work. We compare our results with those of quantum Monte Carlo simulations employing the Hirsch-Fye algorithm.

  16. 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.

  17. Quantum Monte-Carlo Study of Mn and Mn-oxide clusters.

    NASA Astrophysics Data System (ADS)

    Kino, Hiori; Wagner, Lucas K.; Mitas, Lubos

    2007-03-01

    Many molecules and clusters of Mn and Mn-oxide have not only interesting physical properties but also can be found in enzymes as important components in biochemical reactions. The electronic structure calculations of these systems are difficult and, for example, choice of exchange-correlation functionals in Density Functional Theory can significantly influence both ground state geometries and spin-state predictions. Therefore, highly accurate calculation is very desirable for these systems. Experimentally, it is established that the Mn dimer is a van der Waals system with weak binding, however, the spin multiplicity has not been settled unambiguously with possibilities covering a range from singlet, triplet, etc, up to 2S+1=11. On the other hand, MnnOn molecules are quite well understood as being a high-spin system, but their geometries depend on the exchange-correlation functionals. We will present our recent results from the fixed-node quantum Monte Carlo calculations of these systems. We will also report on recent progress in modeling the [4Mn-4O-Ca] cluster structural prototypes for the oxygen evolving center in green plants Photosystem II.

  18. 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

  19. 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.

  20. 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.

  1. Efficient orbital storage and evaluation for quantum Monte Carlo simulations of solids

    NASA Astrophysics Data System (ADS)

    Esler, Kenneth

    2008-03-01

    Researchers have applied continuum quantum Monte Carlo methods to solids with great success, but thus far applications have been largely limited to crystals with simple geometry. In these simulations, three-dimensional cubic B-splines have proven to be a fast and accurate means of storing and evaluating electron orbitals. While B-splines require less memory than other spline interpolation schemes, modern cluster nodes often have insufficient memory to store the orbitals for more complex systems. We introduce three techniques, appropriate in different circumstances, to dramatically reduce the memory required for orbital storage, while retaining high accuracy: the generalized tiling of primitive-cell orbitals into a supercell of arbitrary shape, the use of nonuniform grids for localized orbitals, and the periodic replication of localized orbitals. We give examples for cubic boron nitride and wüstite (FeO), and show that these methods can reduce the memory used for orbital storage by more than two orders of magnitude. Finally, we introduce an open-source B-spline library to facilitate the incorporation of these methods into QMC simulation codes.

  2. 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.

  3. 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.

  4. Quantum-trajectory Monte Carlo method for study of electron-crystal interaction in STEM.

    PubMed

    Ruan, Z; Zeng, R G; Ming, Y; Zhang, M; Da, B; Mao, S F; Ding, Z J

    2015-07-21

    In this paper, a novel quantum-trajectory Monte Carlo simulation method is developed to study electron beam interaction with a crystalline solid for application to electron microscopy and spectroscopy. The method combines the Bohmian quantum trajectory method, which treats electron elastic scattering and diffraction in a crystal, with a Monte Carlo sampling of electron inelastic scattering events along quantum trajectory paths. We study in this work the electron scattering and secondary electron generation process in crystals for a focused incident electron beam, leading to understanding of the imaging mechanism behind the atomic resolution secondary electron image that has been recently achieved in experiment with a scanning transmission electron microscope. According to this method, the Bohmian quantum trajectories have been calculated at first through a wave function obtained via a numerical solution of the time-dependent Schrödinger equation with a multislice method. The impact parameter-dependent inner-shell excitation cross section then enables the Monte Carlo sampling of ionization events produced by incident electron trajectories travelling along atom columns for excitation of high energy knock-on secondary electrons. Following cascade production, transportation and emission processes of true secondary electrons of very low energies are traced by a conventional Monte Carlo simulation method to present image signals. Comparison of the simulated image for a Si(110) crystal with the experimental image indicates that the dominant mechanism of atomic resolution of secondary electron image is the inner-shell ionization events generated by a high-energy electron beam.

  5. A Variable Coefficient Method for Accurate Monte Carlo Simulation of Dynamic Asset Price

    NASA Astrophysics Data System (ADS)

    Li, Yiming; Hung, Chih-Young; Yu, Shao-Ming; Chiang, Su-Yun; Chiang, Yi-Hui; Cheng, Hui-Wen

    2007-07-01

    In this work, we propose an adaptive Monte Carlo (MC) simulation technique to compute the sample paths for the dynamical asset price. In contrast to conventional MC simulation with constant drift and volatility (μ,σ), our MC simulation is performed with variable coefficient methods for (μ,σ) in the solution scheme, where the explored dynamic asset pricing model starts from the formulation of geometric Brownian motion. With the method of simultaneously updated (μ,σ), more than 5,000 runs of MC simulation are performed to fulfills basic accuracy of the large-scale computation and suppresses statistical variance. Daily changes of stock market index in Taiwan and Japan are investigated and analyzed.

  6. Quantum Brachistochrone Curves as Geodesics: Obtaining Accurate Minimum-Time Protocols for the Control of Quantum Systems

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoting; Allegra, Michele; Jacobs, Kurt; Lloyd, Seth; Lupo, Cosmo; Mohseni, Masoud

    2015-05-01

    Most methods of optimal control cannot obtain accurate time-optimal protocols. The quantum brachistochrone equation is an exception, and has the potential to provide accurate time-optimal protocols for a wide range of quantum control problems. So far, this potential has not been realized, however, due to the inadequacy of conventional numerical methods to solve it. Here we show that the quantum brachistochrone problem can be recast as that of finding geodesic paths in the space of unitary operators. We expect this brachistochrone-geodesic connection to have broad applications, as it opens up minimal-time control to the tools of geometry. As one such application, we use it to obtain a fast numerical method to solve the brachistochrone problem, and apply this method to two examples demonstrating its power.

  7. 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.

  8. 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

    1 consisting of a dual-core, dualprocessor AMD Opteron 2.2 GHz with a Xilinx Virtex-4 (V4LX160) or Xilinx Virtex-II Pro (XC2VP50) FPGA per node. We use the compute node with the Xilinx Virtex-4 FPGA Operating system: Red Hat Enterprise Linux OS Has the code been vectorised or parallelized?: Yes Classification: 6.1 Nature of problem: Quantum Monte Carlo is a practical method to solve the Schrödinger equation for large many-body systems and obtain the ground-state properties of such systems. This method involves the sampling of a number of configurations of atoms and averaging the properties of the configurations over a number of iterations. We are interested in applying the QMC method to obtain the energy and other properties of highly quantum clusters, such as inert gas clusters. Solution method: The proposed framework provides a combined hardware-software approach, in which the QMC simulation is performed on the host processor, with the computationally intensive functions such as energy and trial wave function computations mapped onto the field-programmable gate array (FPGA) logic device attached as a co-processor to the host processor. We perform the QMC simulation for a number of iterations as in the case of our original software QMC approach, to reduce the statistical uncertainty of the results. However, our proposed HAQMC framework accelerates each iteration of the simulation, by significantly reducing the time taken to calculate the ground-state properties of the configurations of atoms, thereby accelerating the overall QMC simulation. We provide a generic interpolation framework that can be extended to study a variety of pure and doped atomic clusters, irrespective of the chemical identities of the atoms. For the FPGA implementation of the properties, we use a two-region approach for accurately computing the properties over the entire domain, employ deep pipelines and fixed-point for all our calculations guaranteeing the accuracy required for our simulation.

  9. 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.

  10. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    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.

  12. Correlation Effects in Scanning Tunneling Microscopy Images of Molecules Revealed by Quantum Monte Carlo.

    PubMed

    Barborini, Matteo; Sorella, Sandro; Rontani, Massimo; Corni, Stefano

    2016-11-08

    Scanning tunneling microscopy (STM) and spectroscopy probe the local density of states of single molecules electrically insulated from the substrate. The experimental images, although usually interpreted in terms of single-particle molecular orbitals, are associated with quasiparticle wave functions dressed by the whole electron-electron interaction. Here we propose an ab initio approach based on quantum Monte Carlo to calculate the quasiparticle wave functions of molecules. Through the comparison between Monte Carlo wave functions and their uncorrelated Hartree-Fock counterparts we visualize the electronic correlation embedded in the simulated STM images, highlighting the many-body features that might be observed.

  13. Accurate Calculations of Rotationally Inelastic Scattering Cross Sections Using Mixed Quantum/Classical Theory.

    PubMed

    Semenov, Alexander; Babikov, Dmitri

    2014-01-16

    For computational treatment of rotationally inelastic scattering of molecules, we propose to use the mixed quantum/classical theory, MQCT. The old idea of treating translational motion classically, while quantum mechanics is used for rotational degrees of freedom, is developed to the new level and is applied to Na + N2 collisions in a broad range of energies. Comparison with full-quantum calculations shows that MQCT accurately reproduces all, even minor, features of energy dependence of cross sections, except scattering resonances at very low energies. The remarkable success of MQCT opens up wide opportunities for computational predictions of inelastic scattering cross sections at higher temperatures and/or for polyatomic molecules and heavier quenchers, which is computationally close to impossible within the full-quantum framework.

  14. Quantum Monte Carlo calculations of two neutrons in finite volume

    DOE PAGES

    Klos, P.; Lynn, J. E.; Tews, I.; ...

    2016-11-18

    Ab initio calculations provide direct access to the properties of pure neutron systems that are challenging to study experimentally. In addition to their importance for fundamental physics, their properties are required as input for effective field theories of the strong interaction. In this work, we perform auxiliary-field diffusion Monte Carlo calculations of the ground state and first excited state of two neutrons in a finite box, considering a simple contact potential as well as chiral effective field theory interactions. We compare the results against exact diagonalizations and present a detailed analysis of the finite-volume effects, whose understanding is crucial formore » determining observables from the calculated energies. Finally, using the Lüscher formula, we extract the low-energy S-wave scattering parameters from ground- and excited-state energies for different box sizes.« less

  15. Quantum Monte Carlo calculations of two neutrons in finite volume

    SciTech Connect

    Klos, P.; Lynn, J. E.; Tews, I.; Gandolfi, Stefano; Gezerlis, A.; Hammer, H. -W.; Hoferichter, M.; Schwenk, A.

    2016-11-18

    Ab initio calculations provide direct access to the properties of pure neutron systems that are challenging to study experimentally. In addition to their importance for fundamental physics, their properties are required as input for effective field theories of the strong interaction. In this work, we perform auxiliary-field diffusion Monte Carlo calculations of the ground state and first excited state of two neutrons in a finite box, considering a simple contact potential as well as chiral effective field theory interactions. We compare the results against exact diagonalizations and present a detailed analysis of the finite-volume effects, whose understanding is crucial for determining observables from the calculated energies. Finally, using the Lüscher formula, we extract the low-energy S-wave scattering parameters from ground- and excited-state energies for different box sizes.

  16. Random number generators tested on quantum Monte Carlo simulations.

    PubMed

    Hongo, Kenta; Maezono, Ryo; Miura, Kenichi

    2010-08-01

    We have tested and compared several (pseudo) random number generators (RNGs) applied to a practical application, ground state energy calculations of molecules using variational and diffusion Monte Carlo metheds. A new multiple recursive generator with 8th-order recursion (MRG8) and the Mersenne twister generator (MT19937) are tested and compared with the RANLUX generator with five luxury levels (RANLUX-[0-4]). Both MRG8 and MT19937 are proven to give the same total energy as that evaluated with RANLUX-4 (highest luxury level) within the statistical error bars with less computational cost to generate the sequence. We also tested the notorious implementation of linear congruential generator (LCG), RANDU, for comparison.

  17. Charged vanadium-benzene multidecker clusters: DFT and quantum Monte Carlo study

    SciTech Connect

    Tokár, K.; Derian, R.; Mitas, L.; Štich, I.

    2016-02-14

    Using explicitly correlated fixed-node quantum Monte Carlo and density functional theory (DFT) methods, we study electronic properties, ground-state multiplets, ionization potentials, electron affinities, and low-energy fragmentation channels of charged half-sandwich and multidecker vanadium-benzene systems with up to 3 vanadium atoms, including both anions and cations. It is shown that, particularly in anions, electronic correlations play a crucial role; these effects are not systematically captured with any commonly used DFT functionals such as gradient corrected, hybrids, and range-separated hybrids. On the other hand, tightly bound cations can be described qualitatively by DFT. A comparison of DFT and quantum Monte Carlo provides an in-depth understanding of the electronic structure and properties of these correlated systems. The calculations also serve as a benchmark study of 3d molecular anions that require a balanced many-body description of correlations at both short- and long-range distances.

  18. Charged vanadium-benzene multidecker clusters: DFT and quantum Monte Carlo study.

    PubMed

    Tokár, K; Derian, R; Mitas, L; Štich, I

    2016-02-14

    Using explicitly correlated fixed-node quantum Monte Carlo and density functional theory (DFT) methods, we study electronic properties, ground-state multiplets, ionization potentials, electron affinities, and low-energy fragmentation channels of charged half-sandwich and multidecker vanadium-benzene systems with up to 3 vanadium atoms, including both anions and cations. It is shown that, particularly in anions, electronic correlations play a crucial role; these effects are not systematically captured with any commonly used DFT functionals such as gradient corrected, hybrids, and range-separated hybrids. On the other hand, tightly bound cations can be described qualitatively by DFT. A comparison of DFT and quantum Monte Carlo provides an in-depth understanding of the electronic structure and properties of these correlated systems. The calculations also serve as a benchmark study of 3d molecular anions that require a balanced many-body description of correlations at both short- and long-range distances.

  19. 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.

  20. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1999-07-01

    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 we use the variational Monte Carlo method to study two kinds of relativistic effects in 3H and 4He, using relativistic Hamiltonians. 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 ~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 3H (4He) and account for ~37% of the phenomenological part of the three-nucleon interaction needed in the nonrelativistic Hamiltonians. The wave functions of nuclei are not significantly changed by these effects.

  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. Cold Atomic Fermi Gases: Effective Interactions and Quantum Monte Carlo Studies

    NASA Astrophysics Data System (ADS)

    Gilbreth, Christopher Newman

    Cold atomic Fermi gases are clean, highly experimentally tunable systems with connections to many different fields of physics. However, in the strongly-interacting regime they are nonperturbative and difficult to study theoretically. One challenge is to calculate the energy spectra of few-body cold atom systems along the crossover from a gas of molecular dimers [the Bose-Einstein condensate (BEC) regime] to a gas described by Bardeen-Cooper-Schrieffer (BCS) theory. The configuration-interaction (CI) method is widely used for such problems, but the finite model spaces employed require carefully chosen interactions with good convergence characteristics. Here we study a recently introduced effective interaction for the unitary Fermi gas in the CI approach, extending it to the BEC-BCS crossover and examining its properties analytically and numerically. We find it exhibits fast convergence, which allows us to accurately calculate the low-lying energy spectrum of three- and four-particle systems along the crossover. For larger systems of cold atoms, the superfluid phase transition is a subject of principal interest, but is still incompletely understood. Realistic ab initio calculations of the heat capacity across the superfluid phase transition have not to date been achieved, and the nature of the pseudogap effect in the unitary regime is still a subject of debate. Here we apply the auxiliary-field quantum Monte Carlo (AFMC) method to shed light on the superfluid phase transition by studying a finite-size unitary trapped gas in the canonical ensemble. The AFMC method permits fully nonperturbative calculations without introducing uncontrolled approximations, but can be computationally intensive. Our calculations are made feasible by introducing a new stabilization technique to improve the scaling of the method with the size of the single-particle model space. Applying this method, we present new results concerning the signatures of the superfluid phase transition and

  4. 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.

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

    DOE PAGES

    Santana Palacio, Juan A.; Krogel, Jaron T.; Kim, Jeongnim; ...

    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

  6. 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.

  7. Simulation of Quantum Many-Body Systems with Strings of Operators and Monte Carlo Tensor Contractions

    SciTech Connect

    Schuch, Norbert; Wolf, Michael M.; Cirac, J. Ignacio; Verstraete, Frank

    2008-02-01

    We introduce string-bond states, a class of states obtained by placing strings of operators on a lattice, which encompasses the relevant states in quantum information. For string-bond states, expectation values of local observables can be computed efficiently using Monte Carlo sampling, making them suitable for a variational algorithm which extends the density matrix renormalization group to higher dimensional and irregular systems. Numerical results demonstrate the applicability of these states to the simulation of many-body systems.0.

  8. Monte-Carlo simulations of photoinduced fluorescence enhancement in semiconductor quantum dot arrays

    NASA Astrophysics Data System (ADS)

    Maenosono, Shinya

    2005-03-01

    Photoinduced fluorescence enhancement (PFE) in semiconductor quantum dot (QD) arrays is simulated by a Monte-Carlo method based on the distributed tunneling model. PFE, a property of a QD ensemble, is directly related to the blinking behavior of single QDs. The origin of PFE is attributed not to an increase in the emission intensity during the 'on' period, but to the prolongation of average 'on' time.

  9. Correlated adatom trimer on a metal surface: a continuous-time quantum Monte Carlo study.

    PubMed

    Savkin, V V; Rubtsov, A N; Katsnelson, M I; Lichtenstein, A I

    2005-01-21

    The problem of three interacting Kondo impurities is solved within a numerically exact continuous-time quantum Monte Carlo scheme. A suppression of the Kondo resonance by interatomic exchange interactions for different cluster geometries is investigated. It is shown that a drastic difference between the Heisenberg and Ising cases appears for antiferromagnetically coupled adatoms. The effects of magnetic frustrations in the adatom trimer are investigated, and possible connections with available experimental data are discussed.

  10. 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.

  11. Accurate Monte Carlo modeling of cyclotrons for optimization of shielding and activation calculations in the biomedical field

    NASA Astrophysics Data System (ADS)

    Infantino, Angelo; Marengo, Mario; Baschetti, Serafina; Cicoria, Gianfranco; Longo Vaschetto, Vittorio; Lucconi, Giulia; Massucci, Piera; Vichi, Sara; Zagni, Federico; Mostacci, Domiziano

    2015-11-01

    Biomedical cyclotrons for production of Positron Emission Tomography (PET) radionuclides and radiotherapy with hadrons or ions are widely diffused and established in hospitals as well as in industrial facilities and research sites. Guidelines for site planning and installation, as well as for radiation protection assessment, are given in a number of international documents; however, these well-established guides typically offer analytic methods of calculation of both shielding and materials activation, in approximate or idealized geometry set up. The availability of Monte Carlo codes with accurate and up-to-date libraries for transport and interactions of neutrons and charged particles at energies below 250 MeV, together with the continuously increasing power of nowadays computers, makes systematic use of simulations with realistic geometries possible, yielding equipment and site specific evaluation of the source terms, shielding requirements and all quantities relevant to radiation protection. In this work, the well-known Monte Carlo code FLUKA was used to simulate two representative models of cyclotron for PET radionuclides production, including their targetry; and one type of proton therapy cyclotron including the energy selection system. Simulations yield estimates of various quantities of radiological interest, including the effective dose distribution around the equipment, the effective number of neutron produced per incident proton and the activation of target materials, the structure of the cyclotron, the energy degrader, the vault walls and the soil. The model was validated against experimental measurements and comparison with well-established reference data. Neutron ambient dose equivalent H*(10) was measured around a GE PETtrace cyclotron: an average ratio between experimental measurement and simulations of 0.99±0.07 was found. Saturation yield of 18F, produced by the well-known 18O(p,n)18F reaction, was calculated and compared with the IAEA recommended

  12. Overcoming Critical Slowing Down in Quantum Monte Carlo Simulations

    NASA Astrophysics Data System (ADS)

    Evertz, Hans Gerd; Marcu, Mihai

    The classical d+1-dimensional spin systems used for the simulation of quantum spin systems in d dimensions are, quite generally, vertex models. Standard simulation methods for such models strongly suffer from critical slowing down. Recently, we developed the loop algorithm, a new type of cluster algorithm that to a large extent overcomes critical slowing down for vertex models. We present the basic ideas on the example of the F model, a special case of the 6-vertex model. Numerical results clearly demonstrate the effectiveness of the loop algorithm. Then, using the framework for cluster algorithms developed by Kandel and Domany, we explain how to adapt our algorithm to the cases of the 6-vertex model and the 8-vertex model, which are relevant for spin 1/2 systems. The techniqes presented here can be applied without modification to 2-dimensional spin 1/2 systems, provided that in the Suzuki-Trotter formula the Hamiltonian is broken up into 4 sums of link terms. Generalizations to more complicated situations (higher spins, different uses of the Suzuki-Trotter formula) are, at least in principle, straightforward.

  13. 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.

  14. Fermionic Quantum Monte Carlo simulations without fixed nodes

    NASA Astrophysics Data System (ADS)

    Dornheim, Tobias; Schoof, Tim; Groth, Simon; Bonitz, Michael

    Recent restricted PIMC (RPIMC) simulations [PRL 110, 146405 (2013)] of the uniform electron gas (UEG) at finite temperature have turned out to be surprisingly inaccurate [PRL 115, 130402 (2015)]. Therefore, there exists a high need for alternative approaches which circumvent the fermion sign problem (FSP). In this work, we present two independent approaches which exhibit a complementary behavior. The configuration PIMC (CPIMC) method [Contrib. Plasma Phys. 51, 687-697 (2011)], which operates in Fock space, excels at high density and allows for cutting edge results at strong degeneracy. In contrast, the permutation blocking PIMC (PB-PIMC) approach [New J. Phys. 17, 073017 (2015)] is formulated in coordinate space and combines antisymmetric imaginary time propagators (determinants) with a higher order factorization of the density matrix. This leads to a significant reduction of the sign problem and extends the range of applicability of standard PIMC towards higher density and lower temperature [arXiv:1508.03221 (2015)]. Joining these two complementary methods allows us to present accurate thermodynamic results for the uniform electron gas over a broad parameter range and, therefore, to partly avoid the FSP.

  15. 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; ...

    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

  16. 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.

  17. Monte Carlo simulations of the disordered three-color quantum Ashkin-Teller chain

    NASA Astrophysics Data System (ADS)

    Ibrahim, Ahmed K.; Vojta, Thomas

    2017-02-01

    We investigate the zero-temperature quantum phase transitions of the disordered three-color quantum Ashkin-Teller spin chain by means of large-scale Monte Carlo simulations. We find that the first-order phase transitions of the clean system are rounded by the quenched disorder. For weak intercolor coupling, the resulting emergent quantum critical point between the paramagnetic phase and the magnetically ordered Baxter phase is of infinite-randomness type and belongs to the universality class of the random transverse-field Ising model, as predicted by recent strong-disorder renormalization group calculations. We also find evidence for unconventional critical behavior in the case of strong intercolor coupling, even though an unequivocal determination of the universality class is beyond our numerical capabilities. We compare our results to earlier simulations, and we discuss implications for the classification of phase transitions in the presence of disorder.

  18. Direct simulation Monte Carlo study of quantum effects on the spherical expansion of 4He

    NASA Astrophysics Data System (ADS)

    Koura, Katsuhisa

    1999-10-01

    Quantum effects on the translational nonequilibrium at low temperatures in a spherical expansion of 4He from room temperature are studied using the direct simulation Monte Carlo method to make a comparison with the experimental measurements along the axis of a helium free jet expansion. The quantum-mechanical scattering cross sections are obtained by a quantum phase-shift calculation for the Lennard-Jones and more elaborate Hartree-Fock dispersion potentials. It is shown that the parallel and perpendicular kinetic temperatures are higher and lower, respectively, for the quantum-mechanical scattering than for the classical-mechanical scattering. A comparison with the parallel temperature determined by fitting the ellipsoidal velocity distribution function to the measured spectral profiles indicates that the parallel kinetic temperature for the quantum-mechanical scattering is higher than the measured temperature, with which the parallel kinetic temperature for the classical-mechanical scattering is fortuitously in better agreement. Because both the parallel and perpendicular velocity distribution functions appreciably deviate from Maxwellians and the Maxwellian (half-width) fit temperatures are lower than the kinetic temperatures, the discrepancy between the quantum-mechanical and measured parallel temperatures may partly be resolved by the difference between the kinetic and fitting temperatures.

  19. An efficient monte carlo method for calculating the equilibrium properties for a quantum system coupled strongly to a classical one

    NASA Astrophysics Data System (ADS)

    Carmeli, Benny; Metiu, Horia

    1987-02-01

    We calculate the equilibrium properties of a system consisting of two strongly interacting quantum and classical subsystems, by using a fast Fourier transform method to evaluate the quantum contribution and a Monte Carlo method to evaluate the contribution of the classical part. The method is applied to a model relevant to tunneling problems.

  20. Quantum Monte Carlo Studies of Dense Hydrogen and Two-Dimensional Bose Liquids.

    NASA Astrophysics Data System (ADS)

    Magro, William R.

    Quantum Monte Carlo techniques; in their various incarnations, calculate ground state or finite temperature properties of many-body quantum systems. We apply the path-integral Monte Carlo method to hydrogen at densities and temperatures in the regime of cooperative thermal and pressure dissociation, relevant to structural models of the giant planets' interiors. We treat the protons and electrons as quantum particles, thereby avoiding the Born -Oppenheimer approximation. Fermi-Dirac exchange statistics are treated within the fixed-node approximation, with the nodes specified by the free Fermi gas. In the region of molecular dissociation, we observe properties consistent with and suggestive of a first order phase transition with positive density discontinuity (n_{ rm H2}Monte Carlo techniques to study the ground state properties of two distinct, but related, two-dimensional systems: the Bose Yukawa liquid and the Bose Coulomb liquid. The Yukawa system is a model for flux line interactions in high temperature superconductors. We determine the phase diagram as a function of mass and density and find a high density scaling relation describing the crossover to Coulomb behavior. We apply our results to a sample superconducting compound, rm Bi_2Sr_2CaCu_2O _8. Next the results of the Coulomb system are presented. We show that the predominance of long wavelength plasmons destroys Bose condensation in this system. The ground state of this system is closely related to the bosonic representation of Laughlin's wave function for the fractional quantum Hall system.

  1. Monte Carlo modeling of the dual-mode regime in quantum-well and quantum-dot semiconductor lasers.

    PubMed

    Chusseau, Laurent; Philippe, Fabrice; Disanto, Filippo

    2014-03-10

    Monte Carlo markovian models of a dual-mode semiconductor laser with quantum well (QW) or quantum dot (QD) active regions are proposed. Accounting for carriers and photons as particles that may exchange energy in the course of time allows an ab initio description of laser dynamics such as the mode competition and intrinsic laser noise. We used these models to evaluate the stability of the dual-mode regime when laser characteristics are varied: mode gains and losses, non-radiative recombination rates, intraband relaxation time, capture time in QD, transfer of excitation between QD via the wetting layer... As a major result, a possible steady-state dual-mode regime is predicted for specially designed QD semiconductor lasers thereby acting as a CW microwave or terahertz-beating source whereas it does not occur for QW lasers.

  2. Path Integral Monte Carlo finite-temperature electronic structure of quantum dots

    NASA Astrophysics Data System (ADS)

    Leino, Markku; Rantala, Tapio T.

    2003-03-01

    Quantum Monte Carlo methods allow a straightforward procedure for evaluation of electronic structures with a proper treatment of electronic correlations. This can be done even at finite temperatures [1]. We apply the Path Integral Monte Carlo (PIMC) simulation method [2] for one and two electrons in a single and double quantum dots. With this approach we evaluate the electronic distributions and correlations, and finite temperature effects on those. Temperature increase broadens the one-electron distribution as expected. This effect is smaller for correlated electrons than for single ones. The simulated one and two electron distributions of a single and two coupled quantum dots are also compared to those from experiments and other theoretical (0 K) methods [3]. Computational capacity is found to become the limiting factor in simulations with increasing accuracy. This and other essential aspects of PIMC and its capability in this type of calculations are also discussed. [1] R.P. Feynman: Statistical Mechanics, Addison Wesley, 1972. [2] D.M. Ceperley, Rev.Mod.Phys. 67, 279 (1995). [3] M. Pi, A. Emperador and M. Barranco, Phys.Rev.B 63, 115316 (2001).

  3. 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

  4. 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.

  5. Auxiliary-Field Quantum Monte Carlo Simulations of Strongly-Correlated Molecules and Solids

    SciTech Connect

    Chang, C.; Morales, M. A.

    2016-11-10

    We propose a method of implementing projected wave functions for second-quantized auxiliary- field quantum Monte Carlo (AFQMC) techniques. The method is based on expressing the two-body projector as one-body terms coupled to binary Ising fields. To benchmark the method, we choose to study the two-dimensional (2D) one-band Hubbard model with repulsive interactions using the constrained-path MC (CPMC). The CPMC uses a trial wave function to guide the random walks so that the so-called fermion sign problem can be eliminated. The trial wave function also serves as the importance function in Monte Carlo sampling. AS such, the quality of the trial wave function has a direct impact to the efficiency and accuracy of the simulations.

  6. 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.

  7. Reptation Quantum Monte Carlo Calculation of Charge Transfer in The Na-Cl Dimer

    NASA Astrophysics Data System (ADS)

    Yao, Yi; Kanai, Yosuke

    2015-03-01

    Reptation Quantum Monte Carlo (QMC) calculations are performed to describe the charge transfer behavior in a NaCl dimer. Influence of fixed node approximation on the charge transfer was examined by obtaining electron density via reputation QMC. We employ Slater-Jastrow wavefunction as the trial wavefunction, and the fermion nodes are obtained from single particle orbitals of Hartree-Fock and Density Functional Theory (DFT) with several exchange-correlation approximations. We will discuss our QMC results together with DFT calculations to give insights into observed dependence of the charge transfer behavior on the fixed-node approximation.

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

    NASA Astrophysics Data System (ADS)

    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. The method is applied to address the longstanding discrepancy between 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 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, in contrast to DAC data.

  9. Slave-boson mean field versus quantum Monte Carlo results for the Hubbard model

    NASA Astrophysics Data System (ADS)

    Lilly, L.; Muramatsu, A.; Hanke, W.

    1990-09-01

    The one-band Hubbard model is considered in the slave-boson formulation first introduced by Kotliar and Ruckenstein. It is shown that a mean-field approximation, where broken-symmetry states appropriate for a bipartite lattice are allowed, leads to a quantitative agreement with quantum Monte Carlo results for local observables over a wide range of interactions (0<=1). Thus, our saddle-point solutions constitute an excellent starting point for a systematic treatment of fluctuations.

  10. 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.

  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. Auxiliary-Field Quantum Monte Carlo Method for Strongly Paired Fermions

    DTIC Science & Technology

    2011-12-07

    effective range: E/EFG = ξ + SkF re + · · · . A method is introduced to allow the use of a BCS trial wave function in the auxiliary-field quantum Monte...down by 0.02 to enable comparison of the slopes. universal in continuum Hamiltonians: ξ (re) = ξ + SkF re. Of course, a finite-range purely attractive...find results consistent with a universal dependence of the ground-state energy upon the effective range:E/EFG = ξ + SkF re + · · · with S = 0.12(0.03

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

    DOE PAGES

    Buraczynski, M.; Gandolfi, S.; Gezerlis, A.; ...

    2016-03-14

    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.

  14. 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.

  15. 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.

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

    PubMed

    Fracchia, Francesco; Filippi, Claudia; Amovilli, Claudio

    2014-01-05

    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.

  17. Quantum Monte Carlo computations of phase stability, equations of state, and elasticity of high-pressure silica.

    PubMed

    Driver, K P; Cohen, R E; Wu, Zhigang; Militzer, B; Ríos, P López; Towler, M D; Needs, R J; Wilkins, J W

    2010-05-25

    Silica (SiO(2)) is an abundant component of the Earth whose crystalline polymorphs play key roles in its structure and dynamics. First principle density functional theory (DFT) methods have often been used to accurately predict properties of silicates, but fundamental failures occur. Such failures occur even in silica, the simplest silicate, and understanding pure silica is a prerequisite to understanding the rocky part of the Earth. Here, we study silica with quantum Monte Carlo (QMC), which until now was not computationally possible for such complex materials, and find that QMC overcomes the failures of DFT. QMC is a benchmark method that does not rely on density functionals but rather explicitly treats the electrons and their interactions via a stochastic solution of Schrödinger's equation. Using ground-state QMC plus phonons within the quasiharmonic approximation of density functional perturbation theory, we obtain the thermal pressure and equations of state of silica phases up to Earth's core-mantle boundary. Our results provide the best constrained equations of state and phase boundaries available for silica. QMC indicates a transition to the dense alpha-PbO(2) structure above the core-insulating D" layer, but the absence of a seismic signature suggests the transition does not contribute significantly to global seismic discontinuities in the lower mantle. However, the transition could still provide seismic signals from deeply subducted oceanic crust. We also find an accurate shear elastic constant for stishovite and its geophysically important softening with pressure.

  18. 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.

  19. Quantum Monte Carlo study of entanglement entropy for dipolar hardcore bosons in optical lattices

    NASA Astrophysics Data System (ADS)

    Wang, Wei; Safavi-Naini, Arghavan; Capogrosso-Sansone, Barbara

    2016-05-01

    Entanglement entropy and its scaling with system size provide an alternative way to characterize quantum phases and phase transitions, and can be used to probe topological order. Motivated by the recent theoretical investigation of entanglement properties of the ground-states of hard-core lattice bosons, we use Quantum Monte Carlo simulations, well suited to studying equilibrium properties, to calculate the Renyi entropy and topological entanglement entropy of the ground state of dipolar lattice bosons. In contrast to the traditional observables, these probes allow us to study the emergence of long-range entanglement in the ground state, as well as its dependence on the dipolar coupling. Additionally, in light of recent experimental success in creating low entropy dipolar lattice gases we discuss the possibility of observing these phases experimentally.

  20. Monte Carlo study of GaN versus GaAs terahertz quantum cascade structures

    NASA Astrophysics Data System (ADS)

    Bellotti, Enrico; Driscoll, Kristina; Moustakas, Theodore D.; Paiella, Roberto

    2008-03-01

    Due to their large optical phonon energies, nitride semiconductors are promising for the development of terahertz quantum cascade lasers with dramatically improved high-temperature performance relative to existing GaAs devices. Here, we present a rigorous Monte Carlo study of carrier dynamics in two structures based on the same design scheme for emission at 2THz, consisting of GaN /AlGaN or GaAs /AlGaAs quantum wells. The population inversion and hence the gain coefficient of the nitride device are found to exhibit a much weaker (by a factor of over 3) temperature dependence and to remain large enough for laser action even without cryogenic cooling.

  1. 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.

  2. 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.

  3. Quantum annealing of an Ising spin-glass by Green's function Monte Carlo.

    PubMed

    Stella, Lorenzo; Santoro, Giuseppe E

    2007-03-01

    We present an implementation of quantum annealing (QA) via lattice Green's function Monte Carlo (GFMC), focusing on its application to the Ising spin glass in transverse field. In particular, we study whether or not such a method is more effective than the path-integral Monte Carlo- (PIMC) based QA, as well as classical simulated annealing (CA), previously tested on the same optimization problem. We identify the issue of importance sampling, i.e., the necessity of possessing reasonably good (variational) trial wave functions, as the key point of the algorithm. We performed GFMC-QA runs using such a Boltzmann-type trial wave function, finding results for the residual energies that are qualitatively similar to those of CA (but at a much larger computational cost), and definitely worse than PIMC-QA. We conclude that, at present, without a serious effort in constructing reliable importance sampling variational wave functions for a quantum glass, GFMC-QA is not a true competitor of PIMC-QA.

  4. 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

  5. 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

    2013-10-08

    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.

  6. Methods for Efficiently and Accurately Computing Quantum Mechanical Free Energies for Enzyme Catalysis.

    PubMed

    Kearns, F L; Hudson, P S; Boresch, S; Woodcock, H L

    2016-01-01

    Enzyme activity is inherently linked to free energies of transition states, ligand binding, protonation/deprotonation, etc.; these free energies, and thus enzyme function, can be affected by residue mutations, allosterically induced conformational changes, and much more. Therefore, being able to predict free energies associated with enzymatic processes is critical to understanding and predicting their function. Free energy simulation (FES) has historically been a computational challenge as it requires both the accurate description of inter- and intramolecular interactions and adequate sampling of all relevant conformational degrees of freedom. The hybrid quantum mechanical molecular mechanical (QM/MM) framework is the current tool of choice when accurate computations of macromolecular systems are essential. Unfortunately, robust and efficient approaches that employ the high levels of computational theory needed to accurately describe many reactive processes (ie, ab initio, DFT), while also including explicit solvation effects and accounting for extensive conformational sampling are essentially nonexistent. In this chapter, we will give a brief overview of two recently developed methods that mitigate several major challenges associated with QM/MM FES: the QM non-Boltzmann Bennett's acceptance ratio method and the QM nonequilibrium work method. We will also describe usage of these methods to calculate free energies associated with (1) relative properties and (2) along reaction paths, using simple test cases with relevance to enzymes examples.

  7. Materials Design of Core-Shell Nanostructure Catalysts and New Quantum Monte Carlo Methods, with Application to Combustion

    DTIC Science & Technology

    2010-02-12

    reconstruction containing undercoor- dinated (and not fully oxidized) Ti ions . Will examine reactivity of these Ti ions for water splitting, perhaps...calculations of energies and atomic forces for diatomic and polyatomic molecules", Advances in Quantum Monte Carlo, J. B. Anderson and S. M. Rothstein...perovskite", Chem. Mater. 19, 1418-26 (2007). 4. M. W. Lee, S. V. Levchenko, and A. M. Rappe, "Force calculation of polyatomic molecules in quantum

  8. Scaling analysis and instantons for thermally assisted tunneling and quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

    We develop an instantonic calculus to derive an analytical expression for the thermally assisted tunneling decay rate of a metastable state in a fully connected quantum spin model. The tunneling decay problem can be mapped onto the Kramers escape problem of a classical random dynamical field. This dynamical field is simulated efficiently by path-integral quantum Monte Carlo (QMC). We show analytically that the exponential scaling with the number of spins of the thermally assisted quantum tunneling rate and the escape rate of the QMC process are identical. We relate this effect to the existence of a dominant instantonic tunneling path. The instanton trajectory is described by nonlinear dynamical mean-field theory equations for a single-site magnetization vector, which we solve exactly. Finally, we derive scaling relations for the "spiky" barrier shape when the spin tunneling and QMC rates scale polynomially with the number of spins N while a purely classical over-the-barrier activation rate scales exponentially with N .

  9. Recent developments in quantum Monte Carlo methods for electronic structure of atomic clusters

    NASA Astrophysics Data System (ADS)

    Mitas, Lubos

    2004-03-01

    Recent developments of quantum Monte Carlo (QMC) for electronic structure calculations of clusters, other nanomaterials and quantum systems will be reviewed. QMC methodology is based on a combination of analytical insights about properties of exact wavefunctions, explicit treatment of electron-electron correlation and robustness of computational stochastic techniques. In the course of QMC development for calculations of real materials, small and medium size clusters proved to be invaluable systems both for testing and for revealing unique insights into electron correlation effects in nanostructured materials. The method shows remarkable accuracy which will be demonstrated on calculations of magnetic states of transition metal atoms encapsulated in silicon cluster cages, optical excitations in quantum nanodots and molecules and on studies of reactions in biomolecular metallic centers. Indeed, in some cases QMC turned out to be the only feasible method to provide the necessary accuracy. I will also discuss current QMC developments in using correlated sampling techniques for efficient evaluation of energy differences, efforts to reach beyond the fixed-node approximation and on incorporating QMC methods into multi-scale simulation approaches. In collaboration with P. Sen, L.K. Wagner, Z.M. Helms, M. Bajdich, G. Drobny, and J.C. Grossman. Supported by NSF, ONR and DARPA.

  10. Toward an Accurate Estimate of the Exfoliation Energy of Black Phosphorus: A Periodic Quantum Chemical Approach.

    PubMed

    Sansone, Giuseppe; Maschio, Lorenzo; Usvyat, Denis; Schütz, Martin; Karttunen, Antti

    2016-01-07

    The black phosphorus (black-P) crystal is formed of covalently bound layers of phosphorene stacked together by weak van der Waals interactions. An experimental measurement of the exfoliation energy of black-P is not available presently, making theoretical studies the most important source of information for the optimization of phosphorene production. Here, we provide an accurate estimate of the exfoliation energy of black-P on the basis of multilevel quantum chemical calculations, which include the periodic local Møller-Plesset perturbation theory of second order, augmented by higher-order corrections, which are evaluated with finite clusters mimicking the crystal. Very similar results are also obtained by density functional theory with the D3-version of Grimme's empirical dispersion correction. Our estimate of the exfoliation energy for black-P of -151 meV/atom is substantially larger than that of graphite, suggesting the need for different strategies to generate isolated layers for these two systems.

  11. Cluster size convergence of the density matrix embedding theory and its dynamical cluster formulation: A study with an auxiliary-field quantum Monte Carlo solver

    NASA Astrophysics Data System (ADS)

    Zheng, Bo-Xiao; Kretchmer, Joshua S.; Shi, Hao; Zhang, Shiwei; Chan, Garnet Kin-Lic

    2017-01-01

    We investigate the cluster size convergence of the energy and observables using two forms of density matrix embedding theory (DMET): the original cluster form (CDMET) and a new formulation motivated by the dynamical cluster approximation (DCA-DMET). Both methods are applied to the half-filled one- and two-dimensional Hubbard models using a sign-problem free auxiliary-field quantum Monte Carlo impurity solver, which allows for the treatment of large impurity clusters of up to 100 sites. While CDMET is more accurate at smaller impurity cluster sizes, DCA-DMET exhibits faster asymptotic convergence towards the thermodynamic limit. We use our two formulations to produce new accurate estimates for the energy and local moment of the two-dimensional Hubbard model for U /t =2 ,4 ,6 . These results compare favorably with the best data available in the literature, and help resolve earlier uncertainties in the moment for U /t =2 .

  12. 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.; ...

    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

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

    SciTech Connect

    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 the 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.

  14. 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.

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

    DOE PAGES

    Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T.; ...

    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

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

    DOE PAGES

    Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T.; ...

    2016-06-07

    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. In this paper, 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. Ourmore » 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. Finally, 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    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, semi-local, and hybrid 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, semi-local, and hybrid DFT approximations, the deviation is 3.06, 0.94, and 1.23 eV, respectively. For lattice constants, the mean absolute deviations in DMC, local, semi-local, and hybrid DFT approximations are 0.017(1), 0.07, 0.05, and 0.04 Å, respectively. DMC is a highly accurate method, outperforming the DFT approximations in describing the cohesive energies and structural parameters of these binary oxides.

  18. The ground state tunneling splitting and the zero point energy of malonaldehyde: a quantum Monte Carlo determination.

    PubMed

    Viel, Alexandra; Coutinho-Neto, Maurício D; Manthe, Uwe

    2007-01-14

    Quantum dynamics calculations of the ground state tunneling splitting and of the zero point energy of malonaldehyde on the full dimensional potential energy surface proposed by Yagi et al. [J. Chem. Phys. 1154, 10647 (2001)] are reported. The exact diffusion Monte Carlo and the projection operator imaginary time spectral evolution methods are used to compute accurate benchmark results for this 21-dimensional ab initio potential energy surface. A tunneling splitting of 25.7+/-0.3 cm-1 is obtained, and the vibrational ground state energy is found to be 15 122+/-4 cm-1. Isotopic substitution of the tunneling hydrogen modifies the tunneling splitting down to 3.21+/-0.09 cm-1 and the vibrational ground state energy to 14 385+/-2 cm-1. The computed tunneling splittings are slightly higher than the experimental values as expected from the potential energy surface which slightly underestimates the barrier height, and they are slightly lower than the results from the instanton theory obtained using the same potential energy surface.

  19. 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.

  20. Quantum Monte Carlo study of the itinerant-localized model of strongly correlated electrons: Spin-spin correlation functions

    NASA Astrophysics Data System (ADS)

    Ivantsov, Ilya; Ferraz, Alvaro; Kochetov, Evgenii

    2016-12-01

    We perform quantum Monte Carlo simulations of the itinerant-localized periodic Kondo-Heisenberg model for the underdoped cuprates to calculate the associated spin correlation functions. The strong electron correlations are shown to play a key role in the abrupt destruction of the quasi-long-range antiferromagnetic order in the lightly doped regime.

  1. Worm-improved estimators in continuous-time quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Gunacker, P.; Wallerberger, M.; Ribic, T.; Hausoel, A.; Sangiovanni, G.; Held, K.

    2016-09-01

    We derive the improved estimators for general interactions and employ these for the continuous-time quantum Monte Carlo method. Using a worm algorithm we show how measuring higher-ordered correlators leads to an improved high-frequency behavior in irreducible quantities such as the one-particle self-energy or the irreducible two-particle vertex for non-density-density interactions. A good knowledge of the asymptotics of the two-particle vertex is essential for calculating nonlocal electronic correlations using diagrammatic extensions to the dynamical mean field theory as well as for calculating susceptibilities. We test our algorithm against analytic results for the multiorbital atomic limit and the Falicov-Kimball model.

  2. 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.

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

    PubMed

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

    2016-07-14

    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.

  4. 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

  5. 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.

  6. 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.

  7. Quantum Monte Carlo study of the electric properties of a ferroelectric superlattice

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    By using quantum Monte Carlo (MC) simulation, the electric properties of an Ising spin superlattice formed by two ferroelectric slabs A and B with an antiferroelectric interfacial coupling was studied within the framework of the Transverse Ising Model (TIM). We have examined the effects of the temperature T and the transverse field Ω on the polarization properties. We have also examined the effects of the interfacial coupling JAB, T, and Ω on the hysteresis behavior. Our results are in good agreement with the previous theoretical results; we have found that the critical temperature Tc and the critical transverse field Ωc decrease with the increase of Ω and T respectively. In addition one or triple hysteresis loops can appear in the present system.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. A quantum Monte Carlo study of mono(benzene) TM and bis(benzene) TM systems

    NASA Astrophysics Data System (ADS)

    Bennett, M. Chandler; Kulahlioglu, A. H.; Mitas, L.

    2017-01-01

    We present a study of mono(benzene) TM and bis(benzene) TM systems, where TM = {Mo, W}. We calculate the binding energies by quantum Monte Carlo (QMC) approaches and compare the results with other methods and available experiments. The orbitals for the determinantal part of each trial wave function were generated from several types of DFT functionals in order to optimize for fixed-node errors. We estimate and compare the size of the fixed-node errors for both the Mo and W systems with regard to the electron density and degree of localization in these systems. For the W systems we provide benchmarking results of the binding energies, given that experimental data is not available.

  13. Quantum Monte Carlo of atomic and molecular systems with heavy elements

    NASA Astrophysics Data System (ADS)

    Mitas, Lubos; Kulahlioglu, Adem; Melton, Cody; Bennett, Chandler

    2015-03-01

    We carry out quantum Monte Carlo calculations of atomic and molecular systems with several heavy atoms such as Mo, W and Bi. In particular, we compare the correlation energies vs their lighter counterparts in the same column of the periodic table in order to reveal trends with regard to the atomic number Z. One of the observations is that the correlation energy for the isoelectronic valence space/states is mildly decreasing with increasing Z. Similar observation applies also to the fixed-node errors, supporting thus our recent observation that the fixed-node error increases with electronic density for the same (or similar) complexity of the wave function and bonding. In addition, for Bi systems we study the impact of the spin-orbit on the electronic structure, in particular, on binding, correlation and excitation energies.

  14. Solving fermion sign problem in quantum Monte Carlo by Majorana representation

    NASA Astrophysics Data System (ADS)

    Yao, Hong; Li, Zi-Xiang; Jiang, Yi-Fan

    2015-03-01

    We discover a new quantum Monte Carlo (QMC) method to solve the fermion sign problem in interacting fermion models by employing Majorana representation of complex fermions. We call it Majorana QMC (MQMC). Especially, MQMC is fermion sign free in simulating a class of spinless fermion models on bipartite lattices at half filling and with arbitrary range of (unfrustrated) interactions. To the best of our knowledge, MQMC is the first auxiliary field QMC method to solve fermion sign problem in spinless (more generally, odd number of species) fermion models. MQMC simulations can be performed efficiently both at finite and zero temperatures. We believe that MQMC could pave a new avenue to solve fermion sign problem in more generic fermionic models. (Zi-Xiang Li, Yi-Fan Jiang, and Hong Yao, arXiv:1408.2269).

  15. Itinerant ferromagnetism of a repulsive atomic Fermi gas: a quantum monte carlo study.

    PubMed

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

    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.

  16. Static and Dynamical Correlation in Diradical Molecules by Quantum Monte Carlo Using the Jastrow Antisymmetrized Geminal Power Ansatz.

    PubMed

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

    2014-03-11

    Diradical molecules are essential species involved in many organic and inorganic chemical reactions. The computational study of their electronic structure is often challenging, because a reliable description of the correlation, and in particular of the static one, requires multireference techniques. The Jastrow correlated antisymmetrized geminal power (JAGP) is a compact and efficient wave function ansatz, based on the valence-bond representation, which can be used within quantum Monte Carlo (QMC) approaches. The AGP part can be rewritten in terms of molecular orbitals, obtaining a multideterminant expansion with zero-seniority number. In the present work we demonstrate the capability of the JAGP ansatz to correctly describe the electronic structure of two diradical prototypes: the orthogonally twisted ethylene, C2H4, and the methylene, CH2, representing respectively a homosymmetric and heterosymmetric system. In the orthogonally twisted ethylene, we find a degeneracy of π and π* molecular orbitals, as correctly predicted by multireference procedures, and our best estimates of the twisting barrier, using respectively the variational Monte Carlo (VMC) and the lattice regularized diffusion Monte Carlo (LRDMC) methods, are 71.9(1) and 70.2(2) kcal/mol, in very good agreement with the high-level MR-CISD+Q value, 69.2 kcal/mol. In the methylene we estimate an adiabatic triplet-singlet (X̃(3)B1-ã(1)A1) energy gap of 8.32(7) and 8.64(6) kcal/mol, using respectively VMC and LRDMC, consistently with the experimental-derived finding for Te, 9.363 kcal/mol. On the other hand, we show that the simple ansatz of a Jastrow correlated single determinant (JSD) wave function is unable to provide an accurate description of the electronic structure in these diradical molecules, both at variational level (VMC torsional barrier of C2H4 of 99.3(2) kcal/mol, triplet-singlet energy gap of CH2 of 13.45(10) kcal/mol) and, more remarkably, in the fixed-nodes projection schemes (LRDMC

  17. Theory and software for large Quantum Monte Carlo super-computer simulations over exponential type orbitals.

    NASA Astrophysics Data System (ADS)

    Hoggan, Philip E.

    2009-03-01

    Slater-type orbitals (STO) are rarely used as atomic basis sets for molecular structure and property calculations, since integrals are expensive to evaluate, reliable basis sets are scarce and exact properties such as Kato's cusp condition and the correct exponential decay of the electron density are not significantly better described numerically than with commonly used Gaussian basis sets. We adopt the systematic parallelized development of integration routines for multi-centre integrals, and high-quality basis sets over STOs, useful for modern electron correlation calculations via compact low-variance trial wave-functions for QMC (Quantum Monte Carlo). Molecular QMC applications are also rare, because the method is comparatively complicated to use, however it is extremely precise and can be made to include nearly all the correlation energy. It also scales well for large numbers of processors (1000 s at nearly 100 percent efficiency). Applications need to be carried out on a large scale, to determine electronic structure and properties of large (about 100 atoms) molecules of chemical interest, including intermolecular interactions, best described using Slater trial wave-functions for QMC. Such functions combined as hydrogen-like atomic orbitals possess the correct nodal structure for the high precision FN-MC (Fixed Node Monte Carlo) methods, which include more than 95 percent of the electron correlation energy.

  18. Quantum Monte Carlo simulations of a single iron impurity in MgO

    NASA Astrophysics Data System (ADS)

    Driver, Kevin; Zhang, Shuai; Militzer, Burkhard; Cohen, R. E.

    2014-03-01

    Ferropericlase [(Mg,Fe)O] is the second most abundant mineral in Earth's lower mantle. A high-spin to low-spin transition in Fe2+ that occurs in the middle of the lower mantle has been observed in diamond anvil experiments and confirmed within density functional theory (DFT). The spin transition has significant influence on the physical properties and behavior of the lower mantle. However, details on the mechanism of spin transition are still being understood in both experiment and DFT. Here, we aim to benchmark the high-spin to low-spin transition of a single iron atom impurity in MgO using quantum Monte Carlo (QMC). High-spin and low-spin equations of state are initially computed using density functional theory within the LDA+U approximation, which provide trial Slater-Jastrow wave functions for QMC. Equations of state are then computed with variational and diffusion Monte Carlo in 8- and 64-atom cells using the QMCPACK code.. QMC results are in general agreement with experiment and DFT studies. Grants: Funding provided by the NSF (DMS-1025370, DMS-1025392). Computational resources provided by the NCAR and LBL.

  19. 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).

  20. Quantum Monte Carlo simulations of the BCS-BEC crossover at finite temperature

    NASA Astrophysics Data System (ADS)

    Bulgac, Aurel; Drut, Joaquín E.; Magierski, Piotr

    2008-08-01

    The quantum Monte Carlo method for spin- (1)/(2) fermions at finite temperature is formulated for dilute systems with an s -wave interaction. The motivation and the formalism are discussed along with descriptions of the algorithm and various numerical issues. We report on results for the energy, entropy, and chemical potential as a function of temperature. We give upper bounds on the critical temperature Tc for the onset of superfluidity, obtained by studying the finite-size scaling of the condensate fraction. All of these quantities were computed for couplings around the unitary regime in the range -0.5⩽(kFa)-1⩽0.2 , where a is the s -wave scattering length and kF is the Fermi momentum of a noninteracting gas at the same density. In all cases our data are consistent with normal Fermi gas behavior above a characteristic temperature T0>Tc , which depends on the coupling and is obtained by studying the deviation of the caloric curve from that of a free Fermi gas. For TcMonte Carlo results by other groups.

  1. Study of dispersion forces with quantum Monte Carlo: toward a continuum model for solvation.

    PubMed

    Amovilli, Claudio; Floris, Franca Maria

    2015-05-28

    We present a general method to compute dispersion interaction energy that, starting from London's interpretation, is based on the measure of the electronic electric field fluctuations, evaluated on electronic sampled configurations generated by quantum Monte Carlo. A damped electric field was considered in order to avoid divergence in the variance. Dispersion atom-atom C6 van der Waals coefficients were computed by coupling electric field fluctuations with static dipole polarizabilities. The dipole polarizability was evaluated at the diffusion Monte Carlo level by studying the response of the system to a constant external electric field. We extended the method to the calculation of the dispersion contribution to the free energy of solvation in the framework of the polarizable continuum model. We performed test calculations on pairs of some atomic systems. We considered He in ground and low lying excited states and Ne in the ground state and obtained a good agreement with literature data. We also made calculations on He, Ne, and F(-) in water as the solvent. Resulting dispersion contribution to the free energy of solvation shows the reliability of the method illustrated here.

  2. Quantum Monte Carlo study of the Retinal Minimal Model C5H6NH2+.

    PubMed

    Coccia, Emanuele; Guidoni, Leonardo

    2012-11-05

    In this work, we study the electronic and geometrical properties of the ground state of the Retinal Minimal Model C(5)H(6)NH(2)(+) using the variational Monte Carlo (VMC) method by means of the Jastrow antisymmetrized geminal power (JAGP) wavefunction. A full optimization of all wavefunction parameters, including coefficients, and exponents of the atomic basis, has been achieved, giving converged geometries with a compact and correlated wavefunction. The relaxed geometries of the cis and trans isomers present a pronounced bond length alternation pattern characterized by a C=C central double bond slightly shorter than that reported by the CASPT2 structures. The comparison between different basis sets indicates converged values of geometrical parameters, energy differences, and dipole moments even when the smallest wavefunction is used. The compactness of the wavefunction as well as the scalability of VMC optimization algorithms on massively parallel computers opens the way to perform full structural optimizations of conjugated biomolecules of hundreds of electrons by correlated methods like Quantum Monte Carlo.

  3. Investigation of the full configuration interaction quantum Monte Carlo method using homogeneous electron gas models.

    PubMed

    Shepherd, James J; Booth, George H; Alavi, Ali

    2012-06-28

    Using the homogeneous electron gas (HEG) as a model, we investigate the sources of error in the "initiator" adaptation to full configuration interaction quantum Monte Carlo (i-FCIQMC), with a view to accelerating convergence. In particular, we find that the fixed-shift phase, where the walker number is allowed to grow slowly, can be used to effectively assess stochastic and initiator error. Using this approach we provide simple explanations for the internal parameters of an i-FCIQMC simulation. We exploit the consistent basis sets and adjustable correlation strength of the HEG to analyze properties of the algorithm, and present finite basis benchmark energies for N = 14 over a range of densities 0.5 ≤ r(s) ≤ 5.0 a.u. A single-point extrapolation scheme is introduced to produce complete basis energies for 14, 38, and 54 electrons. It is empirically found that, in the weakly correlated regime, the computational cost scales linearly with the plane wave basis set size, which is justifiable on physical grounds. We expect the fixed-shift strategy to reduce the computational cost of many i-FCIQMC calculations of weakly correlated systems. In addition, we provide benchmarks for the electron gas, to be used by other quantum chemical methods in exploring periodic solid state systems.

  4. Ab initio quantum Monte Carlo simulations of the uniform electron gas without fixed nodes

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    The uniform electron gas (UEG) at finite temperature is of key relevance for many applications in the warm dense matter regime, e.g., dense plasmas and laser excited solids. Also, the quality of density functional theory calculations crucially relies on the availability of accurate data for the exchange-correlation energy. Recently, results for N =33 spin-polarized electrons at high density, rs=r ¯/aB≲4 , and low temperature have been obtained with the configuration path integral Monte Carlo (CPIMC) method [T. Schoof et al., Phys. Rev. Lett. 115, 130402 (2015), 10.1103/PhysRevLett.115.130402]. To achieve these results, the original CPIMC algorithm [T. Schoof et al., Contrib. Plasma Phys. 51, 687 (2011), 10.1002/ctpp.201100012] had to be further optimized to cope with the fermion sign problem (FSP). It is the purpose of this paper to give detailed information on the manifestation of the FSP in CPIMC simulations of the UEG and to demonstrate how it can be turned into a controllable convergence problem. In addition, we present new thermodynamic results for higher temperatures. Finally, to overcome the limitations of CPIMC towards strong coupling, we invoke an independent method—the recently developed permutation blocking path integral Monte Carlo approach [T. Dornheim et al., J. Chem. Phys. 143, 204101 (2015), 10.1063/1.4936145]. The combination of both approaches is able to yield ab initio data for the UEG over the entire density range, above a temperature of about one half of the Fermi temperature. Comparison with restricted path integral Monte Carlo data [E. W. Brown et al., Phys. Rev. Lett. 110, 146405 (2013), 10.1103/PhysRevLett.110.146405] allows us to quantify the systematic error arising from the free particle nodes.

  5. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

    All-electron Fixed-node Diffusion Monte 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 × 106 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 number n 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 interaction nodes 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 diffusion Monte Carlo.

  7. Automated generation of quantum-accurate classical interatomic potentials for metals and semiconductors

    NASA Astrophysics Data System (ADS)

    Thompson, Aidan; Foiles, Stephen; Schultz, Peter; Swiler, Laura; Trott, Christian; Tucker, Garritt

    2013-03-01

    Molecular dynamics (MD) is a powerful condensed matter simulation tool for bridging between macroscopic continuum models and quantum models (QM) treating a few hundred atoms, but is limited by the accuracy of available interatomic potentials. Sound physical and chemical understanding of these interactions have resulted in a variety of concise potentials for certain systems, but it is difficult to extend them to new materials and properties. The growing availability of large QM data sets has made it possible to use more automated machine-learning approaches. Bartók et al. demonstrated that the bispectrum of the local neighbor density provides good regression surrogates for QM models. We adopt a similar bispectrum representation within a linear regression scheme. We have produced potentials for silicon and tantalum, and we are currently extending the method to III-V compounds. Results will be presented demonstrating the accuracy of these potentials relative to the training data, as well as their ability to accurately predict material properties not explicitly included in the training data. 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. Dept. of Energy Nat. Nuclear Security Admin. under Contract DE-AC04-94AL85000.

  8. Spectral neighbor analysis method for automated generation of quantum-accurate interatomic potentials

    SciTech Connect

    Thompson, A.P.; Swiler, L.P.; Trott, C.R.; Foiles, S.M.; Tucker, G.J.

    2015-03-15

    We present a new interatomic potential for solids and liquids called Spectral Neighbor Analysis Potential (SNAP). The SNAP potential has a very general form and uses machine-learning techniques to reproduce the energies, forces, and stress tensors of a large set of small configurations of atoms, which are obtained using high-accuracy quantum electronic structure (QM) calculations. The local environment of each atom is characterized by a set of bispectrum components of the local neighbor density projected onto a basis of hyperspherical harmonics in four dimensions. The bispectrum components are the same bond-orientational order parameters employed by the GAP potential [1]. The SNAP potential, unlike GAP, assumes a linear relationship between atom energy and bispectrum components. The linear SNAP coefficients are determined using weighted least-squares linear regression against the full QM training set. This allows the SNAP potential to be fit in a robust, automated manner to large QM data sets using many bispectrum components. The calculation of the bispectrum components and the SNAP potential are implemented in the LAMMPS parallel molecular dynamics code. We demonstrate that a previously unnoticed symmetry property can be exploited to reduce the computational cost of the force calculations by more than one order of magnitude. We present results for a SNAP potential for tantalum, showing that it accurately reproduces a range of commonly calculated properties of both the crystalline solid and the liquid phases. In addition, unlike simpler existing potentials, SNAP correctly predicts the energy barrier for screw dislocation migration in BCC tantalum.

  9. Spectral neighbor analysis method for automated generation of quantum-accurate interatomic potentials

    NASA Astrophysics Data System (ADS)

    Thompson, A. P.; Swiler, L. P.; Trott, C. R.; Foiles, S. M.; Tucker, G. J.

    2015-03-01

    We present a new interatomic potential for solids and liquids called Spectral Neighbor Analysis Potential (SNAP). The SNAP potential has a very general form and uses machine-learning techniques to reproduce the energies, forces, and stress tensors of a large set of small configurations of atoms, which are obtained using high-accuracy quantum electronic structure (QM) calculations. The local environment of each atom is characterized by a set of bispectrum components of the local neighbor density projected onto a basis of hyperspherical harmonics in four dimensions. The bispectrum components are the same bond-orientational order parameters employed by the GAP potential [1]. The SNAP potential, unlike GAP, assumes a linear relationship between atom energy and bispectrum components. The linear SNAP coefficients are determined using weighted least-squares linear regression against the full QM training set. This allows the SNAP potential to be fit in a robust, automated manner to large QM data sets using many bispectrum components. The calculation of the bispectrum components and the SNAP potential are implemented in the LAMMPS parallel molecular dynamics code. We demonstrate that a previously unnoticed symmetry property can be exploited to reduce the computational cost of the force calculations by more than one order of magnitude. We present results for a SNAP potential for tantalum, showing that it accurately reproduces a range of commonly calculated properties of both the crystalline solid and the liquid phases. In addition, unlike simpler existing potentials, SNAP correctly predicts the energy barrier for screw dislocation migration in BCC tantalum.

  10. Approximate but accurate quantum dynamics from the Mori formalism. II. Equilibrium time correlation functions.

    PubMed

    Montoya-Castillo, Andrés; Reichman, David R

    2017-02-28

    The ability to efficiently and accurately calculate equilibrium time correlation functions of many-body condensed phase quantum systems is one of the outstanding problems in theoretical chemistry. The Nakajima-Zwanzig-Mori formalism coupled to the self-consistent solution of the memory kernel has recently proven to be highly successful for the computation of nonequilibrium dynamical averages. Here, we extend this formalism to treat symmetrized equilibrium time correlation functions for the spin-boson model. Following the first paper in this series [A. Montoya-Castillo and D. R. Reichman, J. Chem. Phys. 144, 184104 (2016)], we use a Dyson-type expansion of the projected propagator to obtain a self-consistent solution for the memory kernel that requires only the calculation of normally evolved auxiliary kernels. We employ the approximate mean-field Ehrenfest method to demonstrate the feasibility of this approach. Via comparison with numerically exact results for the correlation function Czz(t)=Re⟨σz(0)σz(t)⟩, we show that the current scheme affords remarkable boosts in accuracy and efficiency over bare Ehrenfest dynamics. We further explore the sensitivity of the resulting dynamics to the choice of kernel closures and the accuracy of the initial canonical density operator.

  11. A Monte Carlo Resampling Approach for the Calculation of Hybrid Classical and Quantum Free Energies.

    PubMed

    Cave-Ayland, Christopher; Skylaris, Chris-Kriton; Essex, Jonathan W

    2017-02-14

    Hybrid free energy methods allow estimation of free energy differences at the quantum mechanics (QM) level with high efficiency by performing sampling at the classical mechanics (MM) level. Various approaches to allow the calculation of QM corrections to classical free energies have been proposed. The single step free energy perturbation approach starts with a classically generated ensemble, a subset of structures of which are postprocessed to obtain QM energies for use with the Zwanzig equation. This gives an estimate of the free energy difference associated with the change from an MM to a QM Hamiltonian. Owing to the poor numerical properties of the Zwanzig equation, however, recent developments have produced alternative methods which aim to provide access to the properties of the true QM ensemble. Here we propose an approach based on the resampling of MM structural ensembles and application of a Monte Carlo acceptance test which in principle, can generate the exact QM ensemble or intermediate ensembles between the MM and QM states. We carry out a detailed comparison against the Zwanzig equation and recently proposed non-Boltzmann methods. As a test system we use a set of small molecule hydration free energies for which hybrid free energy calculations are performed at the semiempirical Density Functional Tight Binding level. Equivalent ensembles at this level of theory have also been generated allowing the reverse QM to MM perturbations to be performed along with a detailed analysis of the results. Additionally, a previously published nucleotide base pair data set simulated at the QM level using ab initio molecular dynamics is also considered. We provide a strong rationale for the use of the Monte Carlo Resampling and non-Boltzmann approaches by showing that configuration space overlaps can be estimated which provide useful diagnostic information regarding the accuracy of these hybrid approaches.

  12. Highly accurate nuclear and electronic stopping cross sections derived using Monte Carlo simulations to reproduce measured range data

    NASA Astrophysics Data System (ADS)

    Wittmaack, Klaus; Mutzke, Andreas

    2017-03-01

    We have examined and confirmed the previously unexplored concept of using Monte Carlo calculations in combination with measured projected ranges of ions implanted in solids to derive a quantitative description of nuclear interaction and electronic stopping. The study involved 98 ranges of 11B in Si between 1 keV and 8 MeV, contained in 12 sets of 10 different groups. Systematic errors by up to ±8% were removed to establish a refined data base with 93 ranges featuring only statistical uncertainties (±1.8%). The Monte Carlo calculations could be set up to reproduce the refined ranges with a mean ratio 1.002 ± 1.7%. The input parameters required for this very high level of agreement are as follows. Nuclear interaction is best described by the Kr-C potential, but in obligatory combination with the Lindhard-Scharff (LS) screening length. Up to 300 keV, the electronic stopping cross section is proportional to the projectile velocity, Se = kSe,LS, with k = 1.46 ± 0.01. At higher energies, Se falls progressively short of kSe,LS. Around the Bragg peak, i.e., between 0.8 and 10 MeV, Se is modeled by an adjustable function serving to tailor the peak shape properly. Calculated and measured isotope effects for ranges of 10B and 11B in Si agree within the experimental uncertainty (±0.25%). The range-based Se,R(E) reported here predicts the scarce experimental data derived from the energy loss in projectile transmission through thin Si foils to within 2% or better. By contrast, Se(E) data of available stopping power tables exhibit deviations from Se,R(E) between -40% and +14%.

  13. 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.

  14. Direct orientation sampling of diatomic molecules for path integral Monte Carlo calculation of fully quantum virial coefficients

    NASA Astrophysics Data System (ADS)

    Subramanian, Ramachandran; Schultz, Andrew J.; Kofke, David A.

    2017-03-01

    We develop an orientation sampling algorithm for rigid diatomic molecules, which allows direct generation of rings of images used for path-integral calculation of nuclear quantum effects. The algorithm treats the diatomic molecule as two independent atoms as opposed to one (quantum) rigid rotor. Configurations are generated according to a solvable approximate distribution that is corrected via the acceptance decision of the Monte Carlo trial. Unlike alternative methods that treat the systems as a quantum rotor, this atom-based approach is better suited for generalization to multi-atomic (more than two atoms) and flexible molecules. We have applied this algorithm in combination with some of the latest ab initio potentials of rigid H2 to compute fully quantum second virial coefficients, for which we observe excellent agreement with both experimental and simulation data from the literature.

  15. Interaction effects on topological phase transitions via numerically exact quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Hung, Hsiang-Hsuan; Chua, Victor; Wang, Lei; Fiete, Gregory A.

    2014-06-01

    We theoretically study topological phase transitions in four generalized versions of the Kane-Mele-Hubbard model with up to 2×182 sites. All models are free of the fermion-sign problem allowing numerically exact quantum Monte Carlo (QMC) calculations to be performed to extremely low temperatures. We numerically compute the Z2 invariant and spin Chern number Cσ directly from the zero-frequency single-particle Green's functions, and study the topological phase transitions driven by the tight-binding parameters at different on-site interaction strengths. The Z2 invariant and spin Chern number, which are complementary to each another, characterize the topological phases and identify the critical points of topological phase transitions. Although the numerically determined phase boundaries are nearly identical for different system sizes, we find strong system-size dependence of the spin Chern number, where quantized values are only expected upon approaching the thermodynamic limit. For the Hubbard models we considered, the QMC results show that correlation effects lead to shifts in the phase boundaries relative to those in the noninteracting limit, without any spontaneously symmetry breaking. The interaction-induced shift is nonperturbative in the interactions and cannot be captured within a "simple" self-consistent calculation either, such as Hartree-Fock. Furthermore, our QMC calculations suggest that quantum fluctuations from interactions stabilize topological phases in systems where the one-body terms preserve the D3 symmetry of the lattice, and destabilize topological phases when the one-body terms break the D3 symmetry.

  16. FIFTH SEMINAR IN MEMORY OF D.N. KLYSHKO: Simulation of quantum systems by the tomography Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Bogdanov, Yu I.

    2007-12-01

    A new method of statistical simulation of quantum systems is presented which is based on the generation of data by the Monte Carlo method and their purposeful tomography with the energy minimisation. The numerical solution of the problem is based on the optimisation of the target functional providing a compromise between the maximisation of the statistical likelihood function and the energy minimisation. The method does not involve complicated and ill-posed multidimensional computational procedures and can be used to calculate the wave functions and energies of the ground and excited stationary sates of complex quantum systems. The applications of the method are illustrated.

  17. 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.

  18. Auxiliary-field-based trial wave functions in quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Chang, Chia-Chen; Rubenstein, Brenda M.; Morales, Miguel A.

    2016-12-01

    Quantum Monte Carlo (QMC) algorithms have long relied on Jastrow factors to incorporate dynamic correlation into trial wave functions. While Jastrow-type wave functions have been widely employed in real-space algorithms, they have seen limited use in second-quantized QMC methods, particularly in projection methods that involve a stochastic evolution of the wave function in imaginary time. Here we propose a scheme for generating Jastrow-type correlated trial wave functions for auxiliary-field QMC methods. The method is based on decoupling the two-body Jastrow into one-body projectors coupled to auxiliary fields, which then operate on a single determinant to produce a multideterminant trial wave function. We demonstrate that intelligent sampling of the most significant determinants in this expansion can produce compact trial wave functions that reduce errors in the calculated energies. Our technique may be readily generalized to accommodate a wide range of two-body Jastrow factors and applied to a variety of model and chemical systems.

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

    SciTech Connect

    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 understanding 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.

  20. Determinant quantum Monte Carlo study of d -wave pairing in the plaquette Hubbard hamiltonian

    DOE PAGES

    Ying, T.; Mondaini, R.; Sun, X. D.; ...

    2014-08-13

    We used the determinant Quantum Monte Carlo (DQMC) to determine the pairing and magnetic response for a Hubbard model built up from four-site clusters - a two-dimensional square lattice consisting of elemental 2x2 plaquettes with hopping t and on-site repulsion U coupled by an interplaquette hopping t' ≤ t. Superconductivity in this geometry has previously been studied by a variety of analytic and numeric methods, with differing conclusions concerning whether the pairing correlations and transition temperature are raised near half-filling by the inhomogeneous hopping or not. For U/t = 4, DQMC indicates an optimal t'/t ≈ 0.4 at which themore » pairing vertex is most attractive. We also found that optimal t'/t increases with U/t. We then contrast our results for this plaquette model with a Hamiltonian which instead involves a regular pattern of site energies whose large site energy limit is the three band CuO2 model; we show that there the inhomogeneity rapidly, and monotonically, suppresses pairing.« less

  1. Quantum Monte Carlo investigation of Knight shift anomaly in Periodic Anderson model

    NASA Astrophysics Data System (ADS)

    Jiang, Mi; Curro, Nicholas; Scalettar, Richard; UC Davis Team; UC Davis Team

    2014-03-01

    We report a Determinant Quantum Monte Carlo investigation of the Knight shift anomaly observed in nuclear magnetic resonance (NMR) of heavy fermion materials. As opposed to normal Fermi liquids, the Knight shift in heavy fermion materials deviates from the total susceptibility χ below a crossover temperature T*. This deviation is believed to originate in the different temperature dependence of the conduction electron and local moment components of the total susceptibility χ. Here we quantify the behavior of χcc(T) ,χcf(T) , and χff(T) in the framework of periodic Anderson model (PAM), focussing on the evolution with different degree of conduction electron-local moment hybridization. These results confirm several predictions of the two-fluid theory of the Knight shift anomaly, including the demonstration of a universal logarithmic divergence of the contribution of the heavy electrons to the Knight shift. This universal behavior, which occurs with decreasing temperature below T* in the paramagnetic state, agrees well with experimental findings, and indicates that different heavy fermion materials exhibit a common scaling, differing only in the coherence temperature scale, T*.

  2. 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.

  3. 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.

  4. 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)

  5. 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.

  6. Auxiliary field quantum Monte Carlo with a localized basis--applications to atoms and molecules

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

    We extended the recently introduced phaseless auxiliary field quantum Monte Carlo approach [1] to any single-particle basis, and applied it to study atoms and molecules using localized Gaussian basis. This method maps the interacting many-body problem into a linear combination of non-interacting problems using a complex Hubbard-Stratonovich transformation, and controls the phase/sign problem using a trial wave function. It employs a random walk approach in Slater determinant space to project the many-body ground state of the system. The computational cost scales as a low power of system size. In all of the presented results the trial wave function was from a Hartree-Fock calculation. The obtained total energies of the atoms and molecules agree to within a few milli Hartrees with the exact value from full configuration interaction or density matrix renormalization group. The results are comparable in accuracy to those of CCSD(T) for equilibrium geometries but are superior for bond breaking. [1] S. Zhang and H. Krakauer, Phys. Rev. Lett. 90, 136401 (2003).

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

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

    DOE PAGES

    Kung, Y. F.; Chen, C. -C.; Wang, Yao; ...

    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

  9. Optimized Non-Orthogonal Localized Orbitals for Linear Scaling Quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Williamson, Andrew; Reboredo, Fernando; Galli, Giulia

    2004-03-01

    It has been shown [1] that Quantum Monte Carlo calculations of total energies of interacting systems can be made to scale nearly linearly with the number of electrons (N), by using localized single particle orbitals to construct Slater determinants. Here we propose a new way of defining the localized orbitals required for O(N)-QMC calculation, by minimizing an appropriate cost function yielding a set of N non-orthogonal (NO) localized orbitals considerably smoother in real space than Maximally localized Wannier functions (MLWF). These NO orbitals have better localization properties than MLWFs. We show that for semiconducting systems NO orbitals can be localized in a much smaller region of space than orthogonal orbitals (typically, one eighth of the volume) and give total energies with the same accuracy, thus yielding a linear scaling QMC algorithm which is 5 times faster than the one originally proposed [1]. We also discuss the extension of O(N)-QMC with NO orbitals to the calculations of total energies of metallic systems. This work was performed under the auspices of the U.S. Department of Energy by the University of California, Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48. [1] A. J. Williamson, R.Q. Hood and J.C. Grossman, Phys. Rev. Lett. 87, 246406 (2001)

  10. Effects of strong interactions in a half-metallic magnet: A determinant quantum Monte Carlo study

    SciTech Connect

    Jiang, M.; Pickett, W. E.; Scalettar, R. T.

    2013-04-03

    Understanding the effects of electron-electron interactions in half-metallic magnets (HMs), which have band structures with one gapped spin channel and one metallic channel, poses fundamental theoretical issues as well as having importance for their potential applications. Here we use determinant quantum Monte Carlo to study the impacts of an on-site Hubbard interaction U, finite temperature, and an external (Zeeman) magnetic field on a bilayer tight-binding model which is a half-metal in the absence of interactions, by calculating the spectral density, conductivity, spin polarization of carriers, and local magnetic properties. We quantify the effect of U on the degree of thermal depolarization, and follow relative band shifts and monitor when significant gap states appear, each of which can degrade the HM character. For this model, Zeeman coupling induces, at fixed particle number, two successive transitions: compensated half-metal with spin-down band gap → metallic ferromagnet → saturated ferromagnetic insulator. However, over much of the more relevant parameter regime, the half-metallic properties are rather robust to U.

  11. Effects of strong interactions in a half-metallic magnet: A determinant quantum Monte Carlo study

    DOE PAGES

    Jiang, M.; Pickett, W. E.; Scalettar, R. T.

    2013-04-03

    Understanding the effects of electron-electron interactions in half-metallic magnets (HMs), which have band structures with one gapped spin channel and one metallic channel, poses fundamental theoretical issues as well as having importance for their potential applications. Here we use determinant quantum Monte Carlo to study the impacts of an on-site Hubbard interaction U, finite temperature, and an external (Zeeman) magnetic field on a bilayer tight-binding model which is a half-metal in the absence of interactions, by calculating the spectral density, conductivity, spin polarization of carriers, and local magnetic properties. We quantify the effect of U on the degree of thermalmore » depolarization, and follow relative band shifts and monitor when significant gap states appear, each of which can degrade the HM character. For this model, Zeeman coupling induces, at fixed particle number, two successive transitions: compensated half-metal with spin-down band gap → metallic ferromagnet → saturated ferromagnetic insulator. However, over much of the more relevant parameter regime, the half-metallic properties are rather robust to U.« less

  12. A study of electron affinities using the initiator approach to full configuration interaction quantum Monte Carlo.

    PubMed

    Cleland, D M; Booth, George H; Alavi, Ali

    2011-01-14

    For the atoms with Z ≤ 11, energies obtained using the "initiator" extension to full configuration interaction quantum Monte Carlo (i-FCIQMC) come to within statistical errors of the FCIQMC results. As these FCIQMC values have been shown to converge onto FCI results, the i-FCIQMC method allows similar accuracy to be achieved while significantly reducing the scaling with the size of the Slater determinant space. The i-FCIQMC electron affinities of the Z ≤ 11 atoms in the aug-cc-pVXZ basis sets are presented here. In every case, values are obtained to well within chemical accuracy [the mean absolute deviation (MAD) from the relativistically corrected experimental values is 0.41 mE(h)], and significantly improve on coupled cluster with singles, doubles and perturbative triples [CCSD(T)] results. Since the only remaining source of error is basis set incompleteness, we have investigated using CCSD(T)-F12 contributions to correct the i-FCIQMC results. By doing so, much faster convergence with respect to basis set size may be achieved for both the electron affinities and the FCIQMC ionization potentials presented in a previous paper. With this F12 correction, the MAD can be further reduced to 0.13 mE(h) for the electron affinities and 0.31 mE(h) for the ionization potentials.

  13. Auxiliary-field-based trial wave functions in quantum Monte Carlo calculations

    DOE PAGES

    Chang, Chia -Chen; Rubenstein, Brenda M.; Morales, Miguel A.

    2016-12-19

    Quantum Monte Carlo (QMC) algorithms have long relied on Jastrow factors to incorporate dynamic correlation into trial wave functions. While Jastrow-type wave functions have been widely employed in real-space algorithms, they have seen limited use in second-quantized QMC methods, particularly in projection methods that involve a stochastic evolution of the wave function in imaginary time. Here we propose a scheme for generating Jastrow-type correlated trial wave functions for auxiliary-field QMC methods. The method is based on decoupling the two-body Jastrow into one-body projectors coupled to auxiliary fields, which then operate on a single determinant to produce a multideterminant trial wavemore » function. We demonstrate that intelligent sampling of the most significant determinants in this expansion can produce compact trial wave functions that reduce errors in the calculated energies. Lastly, our technique may be readily generalized to accommodate a wide range of two-body Jastrow factors and applied to a variety of model and chemical systems.« less

  14. Auxiliary-field-based trial wave functions in quantum Monte Carlo calculations

    SciTech Connect

    Chang, Chia -Chen; Rubenstein, Brenda M.; Morales, Miguel A.

    2016-12-19

    Quantum Monte Carlo (QMC) algorithms have long relied on Jastrow factors to incorporate dynamic correlation into trial wave functions. While Jastrow-type wave functions have been widely employed in real-space algorithms, they have seen limited use in second-quantized QMC methods, particularly in projection methods that involve a stochastic evolution of the wave function in imaginary time. Here we propose a scheme for generating Jastrow-type correlated trial wave functions for auxiliary-field QMC methods. The method is based on decoupling the two-body Jastrow into one-body projectors coupled to auxiliary fields, which then operate on a single determinant to produce a multideterminant trial wave function. We demonstrate that intelligent sampling of the most significant determinants in this expansion can produce compact trial wave functions that reduce errors in the calculated energies. Lastly, our technique may be readily generalized to accommodate a wide range of two-body Jastrow factors and applied to a variety of model and chemical systems.

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

    SciTech Connect

    Zhuang Guilin; Chen Wulin; Zheng Jun; Yu Huiyou; Wang Jianguo

    2012-08-15

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 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 Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Sign 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.

  16. Markov chain Monte Carlo estimation of a multiparameter decision model: consistency of evidence and the accurate assessment of uncertainty.

    PubMed

    Ades, A E; Cliffe, S

    2002-01-01

    Decision models are usually populated 1 parameter at a time, with 1 item of information informing each parameter. Often, however, data may not be available on the parameters themselves but on several functions of parameters, and there may be more items of information than there are parameters to be estimated. The authors show how in these circumstances all the model parameters can be estimated simultaneously using Bayesian Markov chain Monte Carlo methods. Consistency of the information and/or the adequacy of the model can also be assessed within this framework. Statistical evidence synthesis using all available data should result in more precise estimates of parameters and functions of parameters, and is compatible with the emphasis currently placed on systematic use of evidence. To illustrate this, WinBUGS software is used to estimate a simple 9-parameter model of the epidemiology of HIV in women attending prenatal clinics, using information on 12 functions of parameters, and to thereby compute the expected net benefit of 2 alternative prenatal testing strategies, universal testing and targeted testing of high-risk groups. The authors demonstrate improved precision of estimates, and lower estimates of the expected value of perfect information, resulting from the use of all available data.

  17. Accurate nonadiabatic quantum dynamics on the cheap: Making the most of mean field theory with master equations

    NASA Astrophysics Data System (ADS)

    Kelly, Aaron; Brackbill, Nora; Markland, Thomas E.

    2015-03-01

    In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.

  18. Accurate nonadiabatic quantum dynamics on the cheap: making the most of mean field theory with master equations.

    PubMed

    Kelly, Aaron; Brackbill, Nora; Markland, Thomas E

    2015-03-07

    In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.

  19. Accurate nonadiabatic quantum dynamics on the cheap: Making the most of mean field theory with master equations

    SciTech Connect

    Kelly, Aaron; Markland, Thomas E.; Brackbill, Nora

    2015-03-07

    In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.

  20. An Efficient and Accurate Quantum Lattice-Gas Model for the Many-Body Schroedinger Wave Equation

    DTIC Science & Technology

    2002-01-01

    CONTRACT NUMBER AN EFFICIENT AND ACCURATE QUANTUM LATTICE-GAS MODEL FOR THE MANY-BODY SCHROEDINGER WAVE EQUATION 5b. GRANT NUMBER SC. PROGRAM ELEMENT...for simulating the time-dependent evolution of a many-body jiiantum mechanical system of particles governed by the non-relativistic Schroedinger " wave...the numerical dispersion of the simulated wave packets is compared with the analytical solutions. 15. SUBJECT TERM: Schroedinger wave equation

  1. Accurate Monte Carlo simulations on FCC and HCP Lennard-Jones solids at very low temperatures and high reduced densities up to 1.30.

    PubMed

    Adidharma, Hertanto; Tan, Sugata P

    2016-07-07

    Canonical Monte Carlo simulations on face-centered cubic (FCC) and hexagonal closed packed (HCP) Lennard-Jones (LJ) solids are conducted at very low temperatures (0.10 ≤ T(∗) ≤ 1.20) and high densities (0.96 ≤ ρ(∗) ≤ 1.30). A simple and robust method is introduced to determine whether or not the cutoff distance used in the simulation is large enough to provide accurate thermodynamic properties, which enables us to distinguish the properties of FCC from that of HCP LJ solids with confidence, despite their close similarities. Free-energy expressions derived from the simulation results are also proposed, not only to describe the properties of those individual structures but also the FCC-liquid, FCC-vapor, and FCC-HCP solid phase equilibria.

  2. Accurate Monte Carlo simulations on FCC and HCP Lennard-Jones solids at very low temperatures and high reduced densities up to 1.30

    NASA Astrophysics Data System (ADS)

    Adidharma, Hertanto; Tan, Sugata P.

    2016-07-01

    Canonical Monte Carlo simulations on face-centered cubic (FCC) and hexagonal closed packed (HCP) Lennard-Jones (LJ) solids are conducted at very low temperatures (0.10 ≤ T∗ ≤ 1.20) and high densities (0.96 ≤ ρ∗ ≤ 1.30). A simple and robust method is introduced to determine whether or not the cutoff distance used in the simulation is large enough to provide accurate thermodynamic properties, which enables us to distinguish the properties of FCC from that of HCP LJ solids with confidence, despite their close similarities. Free-energy expressions derived from the simulation results are also proposed, not only to describe the properties of those individual structures but also the FCC-liquid, FCC-vapor, and FCC-HCP solid phase equilibria.

  3. 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.

  4. Monte Carlo study of PbSe quantum dots as the fluorescent material in luminescent solar concentrators.

    PubMed

    Wilton, S R; Fetterman, M R; Low, J J; You, Guanjun; Jiang, Zhenyu; Xu, Jian

    2014-01-13

    In this paper, Monte Carlo simulations were performed to determine the potential efficiencies of luminescent solar concentrator (LSC) systems using PbSe quantum dots (QDs) as the active fluorescent material. The simulation results suggest that PbSe QD LSCs display good absorption characteristics, but yield limited LSC power conversion efficiency due to self-absorption and down-conversion loss. It is proposed that the self-absorption loss can be reduced by utilizing Förster resonance energy transfer between two different sizes of PbSe QDs, yielding pronounced improvement in the optical efficiency of LSCs.

  5. 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., http://doi.org/10.1038/nature16485, Nature (London) 530, 194 (2016); I. Ferrier-Barbut et al., http://arxiv.org/abs/1601.03318, arXiv:1601.03318] and theoretical prediction (F. Wächtler and L. Santos, http://arxiv.org/abs/1601.04501, 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.

  6. Electrically controllable magnetic order in the bilayer Hubbard model on honeycomb lattice: A determinant quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Sun, Jinhua; Xu, Dong-Hui; Zhou, Yi; Zhang, Fu-Chun

    2014-09-01

    In this paper, we use the determinant quantum Monte Carlo method to study the effect of the electric field on the magnetic order in a bilayer Hubbard model on a honeycomb lattice, in which only the direct interlayer hopping energy is included. Our results qualitatively support the layered antiferromagnetic, spin-density wave ground state found in the mean-field theory at the charge neutrality point. The obtained magnetic moments, however, are much smaller than what are estimated in the mean-field theory. As the electric field increases, the magnetic order parameter rapidly decreases.

  7. Accurate polyatomic quantum dynamics studies of combustion reactions. Final progress report, July 1, 1994--June 30, 1998

    SciTech Connect

    Zhang, J.Z.H.

    1998-12-31

    This program is designed to develop accurate yet practical computational methods, primarily based on time-dependent quantum mechanics, for studying the dynamics of polyatomic reactions beyond the atom-diatom systems. Efficient computational methodologies are developed and the applications of these methods to practical chemical reactions relevant to combustion processes are carried out. The program emphasizes the practical aspects of accurate quantum dynamics calculations in order to understand, explain and predict the dynamical properties of important combustion reactions. The aim of this research is to help provide not only qualitative dynamics information but also quantitative prediction of reaction dynamics of combustion reactions at the microscopic level. Through accurate theoretical calculations, the authors wish to be able to quantitatively predict reaction cross sections and rate constants of relatively small gas-phase reactions from first principles that are of direct interest to combustion. The long-term goal of this research is to develop practical computational methods that are capable of quantitatively predicting dynamics of more complex polyatomic gas-phase reactions that are of interest to combustion.

  8. 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

  9. Values of dimensional quantities from Monte Carlo calculations in quantum chromodynamics

    SciTech Connect

    Makeenko, Y.M.; Polikarpov, M.I.

    1983-10-25

    An expression is derived for ..lambda../sub L/(..beta..) to describe the behavior of the Monte Carlo data on the string tension coefficient in the transition region in the SU(3) lattice gauge theory. This expression leads to a 25% increase in ..lambda../sub mom/, while there are no changes in the other dimensional quantities (the deconfinement temperature, for example) found by the Monte Carlo method.

  10. Accurate analysis of electron transfer from quantum dots to metal oxides in quantum dot sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Javad Fahimi, Mohammad; Fathi, Davood; Ansari-Rad, Mehdi

    2015-09-01

    Electron transfer rate from quantum dot (QD) to metal oxide (MO) in quantum dot sensitized solar cells (QDSSCs) has an important role in the efficiency. In this work, we analyse the electron transfer rate from CdSe, CdS and CdTe QDs to TiO2, ZnO and SnO2 MOs by extending the related equations with considering various effects, based on the Marcus theory. In this regard, the effects of QD diameter, QD-MO spacing, the crystalline defects, temperature, and the reorganizational energy, on the electron transfer rate are investigated. The results show that, the maximum electron transfer rate is achieved for CdTe QD with the mentioned three MOs. Moreover, in order to direct the designer to reach the appropriate QDs-MOs combinations for obtaining the maximum electron transfer rate, the average electron transfer rate for various combinations is calculated. For the verification of simulation method, a part of work has been compared with the previous experimental and theoretical results, which indicates the correctness of our simulation algorithm.

  11. Fast and accurate Monte Carlo modeling of a kilovoltage X-ray therapy unit using a photon-source approximation for treatment planning in complex media

    PubMed Central

    Zeinali-Rafsanjani, B.; Mosleh-Shirazi, M. A.; Faghihi, R.; Karbasi, S.; Mosalaei, A.

    2015-01-01

    To accurately recompute dose distributions in chest-wall radiotherapy with 120 kVp kilovoltage X-rays, an MCNP4C Monte Carlo model is presented using a fast method that obviates the need to fully model the tube components. To validate the model, half-value layer (HVL), percentage depth doses (PDDs) and beam profiles were measured. Dose measurements were performed for a more complex situation using thermoluminescence dosimeters (TLDs) placed within a Rando phantom. The measured and computed first and second HVLs were 3.8, 10.3 mm Al and 3.8, 10.6 mm Al, respectively. The differences between measured and calculated PDDs and beam profiles in water were within 2 mm/2% for all data points. In the Rando phantom, differences for majority of data points were within 2%. The proposed model offered an approximately 9500-fold reduced run time compared to the conventional full simulation. The acceptable agreement, based on international criteria, between the simulations and the measurements validates the accuracy of the model for its use in treatment planning and radiobiological modeling studies of superficial therapies including chest-wall irradiation using kilovoltage beam. PMID:26170553

  12. When do perturbative approaches accurately capture the dynamics of complex quantum systems?

    PubMed Central

    Fruchtman, Amir; Lambert, Neill; Gauger, Erik M.

    2016-01-01

    Understanding the dynamics of higher-dimensional quantum systems embedded in a complex environment remains a significant theoretical challenge. While several approaches yielding numerically converged solutions exist, these are computationally expensive and often provide only limited physical insight. Here we address the question: when do more intuitive and simpler-to-compute second-order perturbative approaches provide adequate accuracy? We develop a simple analytical criterion and verify its validity for the case of the much-studied FMO dynamics as well as the canonical spin-boson model. PMID:27335176

  13. Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry.

    PubMed

    Tao, Jianmin; Mo, Yuxiang

    2016-08-12

    Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals.

  14. Accurate Semilocal Density Functional for Condensed-Matter Physics and Quantum Chemistry

    NASA Astrophysics Data System (ADS)

    Tao, Jianmin; Mo, Yuxiang

    2016-08-01

    Most density functionals have been developed by imposing the known exact constraints on the exchange-correlation energy, or by a fit to a set of properties of selected systems, or by both. However, accurate modeling of the conventional exchange hole presents a great challenge, due to the delocalization of the hole. Making use of the property that the hole can be made localized under a general coordinate transformation, here we derive an exchange hole from the density matrix expansion, while the correlation part is obtained by imposing the low-density limit constraint. From the hole, a semilocal exchange-correlation functional is calculated. Our comprehensive test shows that this functional can achieve remarkable accuracy for diverse properties of molecules, solids, and solid surfaces, substantially improving upon the nonempirical functionals proposed in recent years. Accurate semilocal functionals based on their associated holes are physically appealing and practically useful for developing nonlocal functionals.

  15. 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

  16. TU-EF-204-01: Accurate Prediction of CT Tube Current Modulation: Estimating Tube Current Modulation Schemes for Voxelized Patient Models Used in Monte Carlo Simulations

    SciTech Connect

    McMillan, K; Bostani, M; McNitt-Gray, M; McCollough, C

    2015-06-15

    Purpose: Most patient models used in Monte Carlo-based estimates of CT dose, including computational phantoms, do not have tube current modulation (TCM) data associated with them. While not a problem for fixed tube current simulations, this is a limitation when modeling the effects of TCM. Therefore, the purpose of this work was to develop and validate methods to estimate TCM schemes for any voxelized patient model. Methods: For 10 patients who received clinically-indicated chest (n=5) and abdomen/pelvis (n=5) scans on a Siemens CT scanner, both CT localizer radiograph (“topogram”) and image data were collected. Methods were devised to estimate the complete x-y-z TCM scheme using patient attenuation data: (a) available in the Siemens CT localizer radiograph/topogram itself (“actual-topo”) and (b) from a simulated topogram (“sim-topo”) derived from a projection of the image data. For comparison, the actual TCM scheme was extracted from the projection data of each patient. For validation, Monte Carlo simulations were performed using each TCM scheme to estimate dose to the lungs (chest scans) and liver (abdomen/pelvis scans). Organ doses from simulations using the actual TCM were compared to those using each of the estimated TCM methods (“actual-topo” and “sim-topo”). Results: For chest scans, the average differences between doses estimated using actual TCM schemes and estimated TCM schemes (“actual-topo” and “sim-topo”) were 3.70% and 4.98%, respectively. For abdomen/pelvis scans, the average differences were 5.55% and 6.97%, respectively. Conclusion: Strong agreement between doses estimated using actual and estimated TCM schemes validates the methods for simulating Siemens topograms and converting attenuation data into TCM schemes. This indicates that the methods developed in this work can be used to accurately estimate TCM schemes for any patient model or computational phantom, whether a CT localizer radiograph is available or not

  17. Quantum Dynamics of Vinylidene Photodetachment on an Accurate Global Acetylene-Vinylidene Potential Energy Surface.

    PubMed

    Guo, Lifen; Han, Huixian; Ma, Jianyi; Guo, Hua

    2015-08-06

    Vinylidene is a high-energy isomer of acetylene, and the rearrangement of bonds in the two species serves as a prototype for isomerization reactions. Here, a full-dimensional quantum mechanical study of the vinylidene vibration is carried out on a recently developed global acetylene-vinylidene potential energy surface by simulating the photodetachment dynamics of the vinylidene anion. Several low-lying vibrational levels of the anion were first determined on a new ab initio based potential energy surface, and their photoelectron spectra were obtained within the Condon approximation. The vibrational features of the vinylidene isomer are found to agree well with the experiment in both positions and intensities, validating the global acetylene-vinylidene potential energy surface.

  18. Towards a scalable and accurate quantum approach for describing vibrations of molecule–metal interfaces

    PubMed Central

    Madebene, Bruno; Ulusoy, Inga; Mancera, Luis; Scribano, Yohann; Chulkov, Sergey

    2011-01-01

    Summary We present a theoretical framework for the computation of anharmonic vibrational frequencies for large systems, with a particular focus on determining adsorbate frequencies from first principles. We give a detailed account of our local implementation of the vibrational self-consistent field approach and its correlation corrections. We show that our approach is both robust, accurate and can be easily deployed on computational grids in order to provide an efficient computational tool. We also present results on the vibrational spectrum of hydrogen fluoride on pyrene, on the thiophene molecule in the gas phase, and on small neutral gold clusters. PMID:22003450

  19. Exploring the foundations of quantum mechanics using Monte Carlo simulations of the Freedman-Clauser experimental test of Bell's Inequality

    NASA Astrophysics Data System (ADS)

    Foulkes, Stephen

    2013-04-01

    Monte Carlo simulations of the Freedman-Clauser experiment are used to test the Copenhagen interpretation and a local realistic interpretation of Quantum Mechanics. The simulated results are compared to the actual results of the experiment which confirmed the quantum mechanical calculation for nine different relative angles between the two polarization analyzers. For each simulation 5x10^7 total simulated photon pairs were generated at each relative angle. The Copenhagen interpretation model closely followed the general shape of the theoretical calculation but differed from the calculated values by 2.5% to 3.3% for angles less than or equal to π/8 and differed by 15.0% to 52.5% for angles greater than or equal to 3π/8. The local realistic interpretation model did not replicate the experimental results but was generally within 1% of a classical calculation for all analyzer angles. An alternative, ``fuzzy polarization'' interpretation wherein the photon polarization is not assumed to have a fixed value, yielded values within 1% of the quantum mechanical calculation.

  20. Utilizing fast multipole expansions for efficient and accurate quantum-classical molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Schwörer, Magnus; Lorenzen, Konstantin; Mathias, Gerald; Tavan, Paul

    2015-03-01

    Recently, a novel approach to hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations has been suggested [Schwörer et al., J. Chem. Phys. 138, 244103 (2013)]. Here, the forces acting on the atoms are calculated by grid-based density functional theory (DFT) for a solute molecule and by a polarizable molecular mechanics (PMM) force field for a large solvent environment composed of several 103-105 molecules as negative gradients of a DFT/PMM hybrid Hamiltonian. The electrostatic interactions are efficiently described by a hierarchical fast multipole method (FMM). Adopting recent progress of this FMM technique [Lorenzen et al., J. Chem. Theory Comput. 10, 3244 (2014)], which particularly entails a strictly linear scaling of the computational effort with the system size, and adapting this revised FMM approach to the computation of the interactions between the DFT and PMM fragments of a simulation system, here, we show how one can further enhance the efficiency and accuracy of such DFT/PMM-MD simulations. The resulting gain of total performance, as measured for alanine dipeptide (DFT) embedded in water (PMM) by the product of the gains in efficiency and accuracy, amounts to about one order of magnitude. We also demonstrate that the jointly parallelized implementation of the DFT and PMM-MD parts of the computation enables the efficient use of high-performance computing systems. The associated software is available online.

  1. Accurate Intermolecular Potential for the C60 Dimer: The Performance of Different Levels of Quantum Theory.

    PubMed

    Sharapa, Dmitry I; Margraf, Johannes T; Hesselmann, Andreas; Clark, Timothy

    2017-01-10

    The self-assembly of molecular building blocks is a promising route to low-cost nanoelectronic devices. It would be very appealing to use computer-aided design to identify suitable molecules. However, molecular self-assembly is guided by weak interactions, such as dispersion, which have long been notoriously difficult to describe with quantum chemical methods. In recent years, several viable techniques have emerged, ranging from empirical dispersion corrections for DFT to fast perturbation and coupled-cluster theories. In this work, we test these methods for the dimer of the prototypical building block for nanoelectronics, C60-fullerene. Benchmark quality data is obtained from DFT-based symmetry-adapted perturbation theory (SAPT), the adiabatic-connection fluctuation dissipation (ACFD) theorem using an adiabatic LDA kernel, and domain-based local pair natural orbital (DLPNO) coupled-pair and coupled-cluster methods. These benchmarks are used to evaluate economical dispersion-corrected DFT methods, double-hybrid DFT functionals, and second-order Møller-Plesset theory. Furthermore, we provide analytical fits to the benchmark interaction curves, which can be used for a coarse-grain description of fullerene self-assembly. These analytical expressions differ significantly from those reported previously based on bulk data.

  2. Utilizing fast multipole expansions for efficient and accurate quantum-classical molecular dynamics simulations

    SciTech Connect

    Schwörer, Magnus; Lorenzen, Konstantin; Mathias, Gerald; Tavan, Paul

    2015-03-14

    Recently, a novel approach to hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations has been suggested [Schwörer et al., J. Chem. Phys. 138, 244103 (2013)]. Here, the forces acting on the atoms are calculated by grid-based density functional theory (DFT) for a solute molecule and by a polarizable molecular mechanics (PMM) force field for a large solvent environment composed of several 10{sup 3}-10{sup 5} molecules as negative gradients of a DFT/PMM hybrid Hamiltonian. The electrostatic interactions are efficiently described by a hierarchical fast multipole method (FMM). Adopting recent progress of this FMM technique [Lorenzen et al., J. Chem. Theory Comput. 10, 3244 (2014)], which particularly entails a strictly linear scaling of the computational effort with the system size, and adapting this revised FMM approach to the computation of the interactions between the DFT and PMM fragments of a simulation system, here, we show how one can further enhance the efficiency and accuracy of such DFT/PMM-MD simulations. The resulting gain of total performance, as measured for alanine dipeptide (DFT) embedded in water (PMM) by the product of the gains in efficiency and accuracy, amounts to about one order of magnitude. We also demonstrate that the jointly parallelized implementation of the DFT and PMM-MD parts of the computation enables the efficient use of high-performance computing systems. The associated software is available online.

  3. Efficient and accurate evaluation of potential energy matrix elements for quantum dynamics using Gaussian process regression

    NASA Astrophysics Data System (ADS)

    Alborzpour, Jonathan P.; Tew, David P.; Habershon, Scott

    2016-11-01

    Solution of the time-dependent Schrödinger equation using a linear combination of basis functions, such as Gaussian wavepackets (GWPs), requires costly evaluation of integrals over the entire potential energy surface (PES) of the system. The standard approach, motivated by computational tractability for direct dynamics, is to approximate the PES with a second order Taylor expansion, for example centred at each GWP. In this article, we propose an alternative method for approximating PES matrix elements based on PES interpolation using Gaussian process regression (GPR). Our GPR scheme requires only single-point evaluations of the PES at a limited number of configurations in each time-step; the necessity of performing often-expensive evaluations of the Hessian matrix is completely avoided. In applications to 2-, 5-, and 10-dimensional benchmark models describing a tunnelling coordinate coupled non-linearly to a set of harmonic oscillators, we find that our GPR method results in PES matrix elements for which the average error is, in the best case, two orders-of-magnitude smaller and, in the worst case, directly comparable to that determined by any other Taylor expansion method, without requiring additional PES evaluations or Hessian matrices. Given the computational simplicity of GPR, as well as the opportunities for further refinement of the procedure highlighted herein, we argue that our GPR methodology should replace methods for evaluating PES matrix elements using Taylor expansions in quantum dynamics simulations.

  4. Accurate quantum calculation of the bound and resonant rovibrational states of Li-(H2)

    NASA Astrophysics Data System (ADS)

    Xiao, Yingsheng; Poirier, Bill

    2005-03-01

    In a recent paper [B. Poirier, Chem. Phys. 308, 305 (2005)] a full-dimensional quantum method for computing the rovibrational dynamics of triatomic systems was presented, incorporating three key features: (1) exact analytical treatment of Coriolis coupling, (2) three-body "effective potential," and (3) a single bend angle basis for all rotational states. In this paper, these ideas are applied to the Li-(H2) electrostatic complex, to compute all of the rovibrational bound state energies, and a number of resonance energies and widths, to very high accuracy (thousandths of a wave number). This application is very challenging, owing to the long-range nature of the interaction and to narrow level spacings near dissociation. Nevertheless, by combining the present method with a G4 symmetry-adapted phase-space-optimized representation, only modest basis sizes are required for which the matrices are amenable to direct diagonalization. Several new bound levels are reported, as compared with a previous calculation [D. T. Chang, G. Surratt, G. Ristroff, and G. I. Gellene, J. Chem. Phys. 116, 9188 (2002)]. The resonances exhibit a clear-cut separation into shape and Feshbach varieties, with the latter characterized by extremely long lifetimes (microseconds or longer).

  5. 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.

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

    SciTech Connect

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

    2016-06-07

    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. In this paper, 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. Finally, 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.

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

    SciTech Connect

    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 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. 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.

  8. A sufficient condition for the absence of the sign problem in the fermionic quantum Monte-Carlo algorithm

    SciTech Connect

    Wu, Congjun; Zhang, Shou-Cheng; /Stanford U., Phys. Dept.

    2010-01-15

    Quantum Monte-Carlo (QMC) simulations involving fermions have the notorious sign problem. Some well-known exceptions of the auxiliary field QMC algorithm rely on the factorizibility of the fermion determinant. Recently, a fermionic QMC algorithm has been found in which the fermion determinant may not necessarily factorizable, but can instead be expressed as a product of complex conjugate pairs of eigenvalues, thus eliminating the sign problem for a much wider class of models. In this paper, we present general conditions for the applicability of this algorithm and point out that it is deeply related to the time reversal symmetry of the fermion matrix. We apply this method to various models of strongly correlated systems at all doping levels and lattice geometries, and show that many novel phases can be simulated without the sign problem.

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

    DOE PAGES

    Dornheim, Tobias; Groth, Simon; Sjostrom, Travis; ...

    2016-10-07

    Here 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 F xc of the macroscopic electron gas withmore » an unprecedented accuracy of | Δ V | / | V | , | Δ Fxc | / | F | xc ~ 10 $-$3. Finally, a comparison of our new data to the recent parametrization of F xc by Karasiev et al. [Phys. Rev. Lett. 112, 076403 (2014)] reveals significant deviations to the latter.« less

  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. The roles of antiferromagnetic and nematic fluctuations in cuprate superconductors: a sign-free quantum Monte-Carlo study

    NASA Astrophysics Data System (ADS)

    Li, Zixiang; Yao, Hong; Wang, Fa; Lee, Dung-Hai

    Superconductivity is an emergent phenomena in the sense that the energy scale at which Cooper pairs form is generically much lower than the bare energy scale, namely the electron kinetic energy bandwidth. Addressing the mechanism of Cooper pairing amounts to finding out the effective interaction (or the renormalized interaction) that operates at the low energies. Finding such interaction from the bare microscopic Hamiltonian has not been possible for strong correlated superconductors such as the copper-oxide high temperature superconductor. In fact even one is given the effective interaction, determining its implied electronic instabilities without making any approximation has been a formidable task. Here, we perform sign-free quantum Monte-Carlo simulations to study the antiferromagnetic, superconducting, and the charge density wave instabilities which are ubiquitous in both electron and hole doped cuprates. Our result suggests only after including both the nematic and antiferromagnetic fluctuation, are the observed properties associated with these instabilities reproduced by the theory.

  12. Quantum Disordered State without Frustration in the Double Layer Heisenberg Antiferromagnet —Dimer Expansion and Projector Monte Carlo Study—

    NASA Astrophysics Data System (ADS)

    Hida, Kazuo

    1992-03-01

    The quantum disordered state (QDOS) of the spin 1/2 double layer square lattice Heisenberg antiferromagnet is studied. Using the dimer expansion from the limit of the large interlayer coupling J', the staggered susceptibility χ, the antiferromagnetic structure factor Sπ and the antiferromagnetic correlation length ξ are calculated up to the 6-th order in the intralayer coupling J. The ratio analysis shows that the QDOS becomes unstable against the Néel ordering at J'/J≃2.56. The critical exponents are not inconsistent with the universality class of the 3-dimensional classical Heisenberg model, suggesting that our QDOS corresponds to that expected in the 2-dimensional square lattice Heisenberg antiferromagnet with unphysically small spin (<0.276). The results of the projector Monte Carlo simulation also confirms the dimer expansion results.

  13. Determinant quantum Monte Carlo study of the two-dimensional single-band Hubbard-Holstein model

    SciTech Connect

    Johnston, S.; Nowadnick, E. A.; Kung, Y. F.; Moritz, B.; Scalettar, R. T.; Devereaux, T. P.

    2013-06-24

    Here, we performed numerical studies of the Hubbard-Holstein model in two dimensions using determinant quantum Monte Carlo (DQMC). We also present details of the method, emphasizing the treatment of the lattice degrees of freedom, and then study the filling and behavior of the fermion sign as a function of model parameters. We find a region of parameter space with large Holstein coupling where the fermion sign recovers despite large values of the Hubbard interaction. This indicates that studies of correlated polarons at finite carrier concentrations are likely accessible to DQMC simulations. We then restrict ourselves to the half-filled model and examine the evolution of the antiferromagnetic structure factor, other metrics for antiferromagnetic and charge-density-wave order, and energetics of the electronic and lattice degrees of freedom as a function of electron-phonon coupling. From this we find further evidence for a competition between charge-density-wave and antiferromagnetic order at half- filling.

  14. Majorana-Time-Reversal Symmetries: A Fundamental Principle for Sign-Problem-Free Quantum Monte Carlo Simulations

    NASA Astrophysics Data System (ADS)

    Li, Zi-Xiang; Jiang, Yi-Fan; Yao, Hong

    2016-12-01

    A fundamental open issue in physics is whether and how the fermion sign problem in quantum Monte Carlo (QMC) simulations can be solved generically. Here, we show that Majorana-time-reversal (MTR) symmetries can provide a unifying principle to solve the fermion sign problem in interacting fermionic models. By systematically classifying Majorana-bilinear operators according to the anticommuting MTR symmetries they respect, we rigorously prove that there are two and only two fundamental symmetry classes which are sign-problem-free and which we call the "Majorana class" and "Kramers class," respectively. Novel sign-problem-free models in the Majorana class include interacting topological superconductors and interacting models of charge-4 e superconductors. We believe that our MTR unifying principle could shed new light on sign-problem-free QMC simulation on strongly correlated systems and interacting topological matters.

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

    SciTech Connect

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

    2016-10-07

    Here 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 F xc of the macroscopic electron gas with an unprecedented accuracy of | Δ V | / | V | , | Δ Fxc | / | F | xc ~ 10 $-$3. Finally, a comparison of our new data to the recent parametrization of F xc by Karasiev et al. [Phys. Rev. Lett. 112, 076403 (2014)] reveals significant deviations to the latter.

  16. Spin gap and string order parameter in the ferromagnetic spiral staircase heisenberg ladder: a quantum Monte Carlo study.

    PubMed

    Brünger, C; Assaad, F F; Capponi, S; Alet, F; Aristov, D N; Kiselev, M N

    2008-01-11

    We consider a spin-1/2 ladder with a ferromagnetic rung coupling J perpendicular and inequivalent chains. This model is obtained by a twist (theta) deformation of the ladder and interpolates between the isotropic ladder (theta=0) and the SU(2) ferromagnetic Kondo necklace model (theta = pi). We show that the ground state in the (theta, J perpendicular) plane has a finite string order parameter characterizing the Haldane phase. Twisting the chain introduces a new energy scale, which we interpret in terms of a Suhl-Nakamura interaction. As a consequence we observe a crossover in the scaling of the spin gap at weak coupling from delta/J parallel proportional, variant J perpendicular/J parallel for theta < theta c approximately 8 pi/9 to delta/J parallel proportional, variant (J perpendicular/J parallel)2 for theta > theta c. Those results are obtained on the basis of large scale quantum Monte Carlo calculations.

  17. 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.

  18. The Quantum Monte Carlo Database: towards high-accuracy and high-throughput calculation of material properties

    NASA Astrophysics Data System (ADS)

    Schiller, Joshua; Plante, Raymond; Wagner, Lucas; Ertekin, Elif

    Quantum Monte Carlo (QMC) techniques comprise a class of promising methods that offer a path towards higher accuracy for materials property prediction. However, their application in bulk materials has historically been limited to one-at-a-time evaluation of a given material. While these results often provide benchmark-level accuracy for quantities of interest, they do not allow for high-throughput analysis of the data since each calculation is done slightly differently. We present a combined data format and automatic generation platform based on the QWalk code for QMC data: QMCDB. This platform collects QMC results and provenance information automatically and stores the information in a database. We will report on the construction of this database and what lessons can be learned about using QMC for high-throughput applications.

  19. 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

  20. Binding energies of trions and biexcitons in two-dimensional semiconductors from diffusion quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Szyniszewski, M.; Mostaani, E.; Drummond, N. D.; Fal'ko, V. I.

    2017-02-01

    Excitonic effects play a particularly important role in the optoelectronic behavior of two-dimensional (2D) semiconductors. To facilitate the interpretation of experimental photoabsorption and photoluminescence spectra we provide statistically exact diffusion quantum Monte Carlo binding-energy data for Mott-Wannier models of excitons, trions, and biexcitons in 2D semiconductors. We also provide contact pair densities to allow a description of contact (exchange) interactions between charge carriers using first-order perturbation theory. Our data indicate that the binding energy of a trion is generally larger than that of a biexciton in 2D semiconductors. We provide interpolation formulas giving the binding energy and contact density of 2D semiconductors as functions of the electron and hole effective masses and the in-plane polarizability.

  1. On the systematic improvement of fixed-node diffusion quantum Monte Carlo energies using pair natural orbital CI guide functions

    NASA Astrophysics Data System (ADS)

    Lüchow, Arne; Fink, Reinhold F.

    2000-11-01

    While the diffusion quantum Monte Carlo method (DQMC) is capable, in principle, of calculating exact ground state energies, in practice the fixed-node (FN) approximation leads to node location errors which make FN-DQMC energies upper bounds. It is shown that the node location error can be reduced systematically and without prohibitive increase of computer time requirements by using nodes derived from pair natural orbital CI wave functions (PNO-CI). The reduction is demonstrated for the N atom and the molecules N2 and H2O. With the DQMC/PNOCI method, we obtain a variational energy of -109.520(3) H for the N2 molecule and -76.429(1) H for the ground state of the water molecule which is only 22 and 9 mH above the estimated nonrelativistic ground state energy, respectively.

  2. Ab initio quantum Monte Carlo study of the binding of a positron to alkali-metal hydrides.

    PubMed

    Kita, Yukiumi; Maezono, Ryo; Tachikawa, Masanori; Towler, Mike D; Needs, Richard J

    2011-08-07

    Quantum Monte Carlo methods are used to investigate the binding of a positron to the alkali-metal hydrides, XH (X = Na and K). We obtain positron affinities for the NaH and KH molecules of 1.422(10) eV and 2.051(39) eV, respectively. These are considerably larger than the previous results of 1.035 eV and 1.273 eV obtained from multireference single- and double-excitation configuration interaction calculations. Together with our previous results for [LiH;e(+)] [Y. Kita et al., J. Chem. Phys. 131, 134310 (2009)], our study confirms the strong correlation between the positron affinity and dipole moment of alkali-metal hydrides.

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

    PubMed

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

    2016-10-07

    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 F_{xc} of the macroscopic electron gas with an unprecedented accuracy of |ΔV|/|V|,|ΔF_{xc}|/|F|_{xc}∼10^{-3}. A comparison of our new data to the recent parametrization of F_{xc} by Karasiev et al. [Phys. Rev. Lett. 112, 076403 (2014)] reveals significant deviations to the latter.

  4. 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.

  5. Benchmark studies of the Bending Corrected Rotating Linear Model (BCRLM) reactive scattering code: Implications for accurate quantum calculations

    SciTech Connect

    Hayes, E.F.; Darakjian, Z. . Dept. of Chemistry); Walker, R.B. )

    1990-01-01

    The Bending Corrected Rotating Linear Model (BCRLM), developed by Hayes and Walker, is a simple approximation to the true multidimensional scattering problem for reaction of the type: A + BC {yields} AB + C. While the BCRLM method is simpler than methods designed to obtain accurate three dimensional quantum scattering results, this turns out to be a major advantage in terms of our benchmarking studies. The computer code used to obtain BCRLM scattering results is written for the most part in standard FORTRAN and has been reported to several scalar, vector, and parallel architecture computers including the IBM 3090-600J, the Cray XMP and YMP, the Ardent Titan, IBM RISC System/6000, Convex C-1 and the MIPS 2000. Benchmark results will be reported for each of these machines with an emphasis on comparing the scalar, vector, and parallel performance for the standard code with minimum modifications. Detailed analysis of the mapping of the BCRLM approach onto both shared and distributed memory parallel architecture machines indicates the importance of introducing several key changes in the basic strategy and algorithums used to calculate scattering results. This analysis of the BCRLM approach provides some insights into optimal strategies for mapping three dimensional quantum scattering methods, such as the Parker-Pack method, onto shared or distributed memory parallel computers.

  6. 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.

  7. 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.

  8. 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.

  9. Quantum Monte Carlo study of the Bose-polaron problem in a one-dimensional gas with contact interactions

    NASA Astrophysics Data System (ADS)

    Parisi, L.; Giorgini, S.

    2017-02-01

    We present a theoretical study based upon quantum Monte Carlo methods of the Bose polaron in one-dimensional systems with contact interactions. In this instance of the problem of a single impurity immersed in a quantum bath, the medium is a Lieb-Liniger gas of bosons ranging from the weakly interacting to the Tonks-Girardeau regime, whereas the impurity is coupled to the bath via a different contact potential, producing both repulsive and attractive interactions. Both the case of a mobile impurity, having the same mass as the particles in the medium, and the case of a static impurity with infinite mass are considered. We make use of numerical techniques that allow us to calculate the ground-state energy of the impurity, its effective mass, and the contact parameter between the impurity and the bath. These quantities are investigated as a function of the strength of interactions between the impurity and the bath and within the bath. In particular, we find that the effective mass rapidly increases to very large values when the impurity gets strongly coupled to an otherwise weakly repulsive bath. This heavy impurity hardly moves within the medium, thereby realizing the "self-localization" regime of the Landau-Pekar polaron. Furthermore, we compare our results with predictions of perturbation theory valid for weak interactions and with exact solutions available when the bosons in the medium behave as impenetrable particles.

  10. Monte Carlo studies of the self-correcting properties of the Majorana quantum error correction code under braiding

    NASA Astrophysics Data System (ADS)

    Pedrocchi, Fabio L.; Bonesteel, N. E.; DiVincenzo, David P.

    2015-09-01

    The Majorana code is an example of a stabilizer code where the quantum information is stored in a system supporting well-separated Majorana bound states (MBSs). We focus on one-dimensional realizations of the Majorana code, as well as networks of such structures, and investigate their lifetime when coupled to a parity-preserving thermal environment. We apply the Davies prescription, a standard method that describes the basic aspects of a thermal environment, and derive a master equation in the Born-Markov limit. We first focus on a single wire with immobile MBSs and perform error correction to annihilate thermal excitations. In the high-temperature limit, we show both analytically and numerically that the lifetime of the Majorana qubit grows logarithmically with the size of the wire. We then study a trijunction with four MBSs when braiding is executed. We study the occurrence of dangerous error processes that prevent the lifetime of the Majorana code from growing with the size of the trijunction. The origin of the dangerous processes is the braiding itself, which separates pairs of excitations and renders the noise nonlocal; these processes arise from the basic constraints of moving MBSs in one-dimensional (1D) structures. We confirm our predictions with Monte Carlo simulations in the low-temperature regime, i.e., the regime of practical relevance. Our results put a restriction on the degree of self-correction of this particular 1D topological quantum computing architecture.

  11. Numerical stabilization of entanglement computation in auxiliary-field quantum Monte Carlo simulations of interacting many-fermion systems

    NASA Astrophysics Data System (ADS)

    Broecker, Peter; Trebst, Simon

    2016-12-01

    In the absence of a fermion sign problem, auxiliary-field (or determinantal) quantum Monte Carlo (DQMC) approaches have long been the numerical method of choice for unbiased, large-scale simulations of interacting many-fermion systems. More recently, the conceptual scope of this approach has been expanded by introducing ingenious schemes to compute entanglement entropies within its framework. On a practical level, these approaches, however, suffer from a variety of numerical instabilities that have largely impeded their applicability. Here we report on a number of algorithmic advances to overcome many of these numerical instabilities and significantly improve the calculation of entanglement measures in the zero-temperature projective DQMC approach, ultimately allowing us to reach similar system sizes as for the computation of conventional observables. We demonstrate the applicability of this improved DQMC approach by providing an entanglement perspective on the quantum phase transition from a magnetically ordered Mott insulator to a band insulator in the bilayer square lattice Hubbard model at half filling.

  12. Numerical stabilization of entanglement computation in auxiliary-field quantum Monte Carlo simulations of interacting many-fermion systems.

    PubMed

    Broecker, Peter; Trebst, Simon

    2016-12-01

    In the absence of a fermion sign problem, auxiliary-field (or determinantal) quantum Monte Carlo (DQMC) approaches have long been the numerical method of choice for unbiased, large-scale simulations of interacting many-fermion systems. More recently, the conceptual scope of this approach has been expanded by introducing ingenious schemes to compute entanglement entropies within its framework. On a practical level, these approaches, however, suffer from a variety of numerical instabilities that have largely impeded their applicability. Here we report on a number of algorithmic advances to overcome many of these numerical instabilities and significantly improve the calculation of entanglement measures in the zero-temperature projective DQMC approach, ultimately allowing us to reach similar system sizes as for the computation of conventional observables. We demonstrate the applicability of this improved DQMC approach by providing an entanglement perspective on the quantum phase transition from a magnetically ordered Mott insulator to a band insulator in the bilayer square lattice Hubbard model at half filling.

  13. 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.

  14. 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.

  15. Two- and Three-Nucleon Chiral Interactions in Quantum Monte Carlo Calculations for Nuclear Physics

    NASA Astrophysics Data System (ADS)

    Lynn, Joel; Carlson, Joseph; Gandolfi, Stefano; Gezerlis, Alexandros; Schmidt, Kevin; Schwenk, Achim; Tews, Ingo

    2015-10-01

    I present our recent work on Green's function Monte Carlo (GFMC) calculations of light nuclei using local two- and three-nucleon interactions derived from chiral effective field theory (EFT) up to next-to-next-to-leading order (N2LO). GFMC provides important benchmarking capabilities for other methods which rely on techniques to soften the nuclear interaction and also allows for nonperturbative studies of the convergence of the chiral EFT expansion. I discuss the choice of observables we make to fit the two low-energy constants which enter in the three-nucleon sector at N2LO: the 4He binding energy and n- α elastic scattering P-wave phase shifts. I then show some results for light nuclei. I also show our results for the energy per neutron in pure neutron matter using the auxiliary-field diffusion Monte Carlo method and discuss regulator choices. Finally I discuss some exciting future projects which are now possible. The NUCLEI SciDAC program and the National Energy Research Scientific Computing Center (NERSC), which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

  16. Unbiased expectation values from diffusion quantum Monte Carlo simulations with a fixed number of walkers

    NASA Astrophysics Data System (ADS)

    Bosá, Ivana; Rothstein, Stuart M.

    2004-09-01

    We append forward walking to a diffusion Monte Carlo algorithm which maintains a fixed number of walkers. This removes the importance sampling bias of expectation values of operators which do not commute with the Hamiltonian. We demonstrate the effectiveness of this approach by employing three importance sampling functions for the hydrogen atom ground state, two very crude. We estimate moments of the electron-nuclear distance, static polarizabilities, and high-order hyperpolarizabilites up to the fourth power in the electric field, where no use is made of the finite field approximation. The results agree with the analytical values, with a statistical error which increases substantially with decreasing overlap of the guiding function with the exact wave function.

  17. Nuclear Quantum Effects in Liquid Water: A Highly Accurate ab initio Path-Integral Molecular Dynamics Study

    NASA Astrophysics Data System (ADS)

    Distasio, Robert A., Jr.; Santra, Biswajit; Ko, Hsin-Yu; Car, Roberto

    2014-03-01

    In this work, we report highly accurate ab initio path-integral molecular dynamics (AI-PIMD) simulations on liquid water at ambient conditions utilizing the recently developed PBE0+vdW(SC) exchange-correlation functional, which accounts for exact exchange and a self-consistent pairwise treatment of van der Waals (vdW) or dispersion interactions, combined with nuclear quantum effects (via the colored-noise generalized Langevin equation). The importance of each of these effects in the theoretical prediction of the structure of liquid water will be demonstrated by a detailed comparative analysis of the predicted and experimental oxygen-oxygen (O-O), oxygen-hydrogen (O-H), and hydrogen-hydrogen (H-H) radial distribution functions as well as other structural properties. In addition, we will discuss the theoretically obtained proton momentum distribution, computed using the recently developed Feynman path formulation, in light of the experimental deep inelastic neutron scattering (DINS) measurements. DOE: DE-SC0008626, DOE: DE-SC0005180.

  18. Solvent effects on global reactivity properties for neutral and charged systems using the sequential Monte Carlo quantum mechanics model.

    PubMed

    Jaramillo, Paula; Pérez, Patricia; Fuentealba, Patricio; Canuto, Sylvio; Coutinho, Kaline

    2009-04-02

    The energy of the frontier molecular orbitals and reactivity indices such as chemical potential, hardness, and electrophilicity of neutral and charged molecules have been investigated in aqueous solution using explicit model for the solvent with the sequential Monte Carlo/quantum mechanics methodology. The supermolecular structures of the solute-solvent system were generated by Monte Carlo simulation. Statistically uncorrelated structures have been extracted for quantum mechanical calculations of the solute surrounded by the first solvation shell, using explicit water molecules, and the second and third shells as atomic point charges. The supermolecular calculations treating both the solute and the solvent explicitly were performed within density functional theory. The solvent dependence of the frontier molecular orbital energies was analyzed and used to calculate the reactivity indices in solution. The dependence of the results with respect to the number of explicit solvent molecules is also analyzed. It is seen that for the systems considered here, the energies of the highest occupied molecular orbital and the lowest unoccupied molecular orbital show a strong dependence with the number of solvent molecules. However, the properties derived from these are relatively stable. In particular, the results reported here for the reactivity indices obtained using the first solvation shell are similar to those obtained for the limit bulk value. For comparison, the reactivity indices were also calculated in the gas phase and using the polarizable continuum model (PCM). As frequently reported in the literature, neutral molecules do not show significant changes in the reactivity indices between gas phase and the PCM model. However, with the explicit solvent model some important changes were observed: a larger negative chemical potential, a smaller hardness, and a larger electrophilicity. The stabilization of an anion corresponding to a negative chemical potential is obtained

  19. Quantum Monte Carlo studies of relativistic effects in 3H and 4He

    NASA Astrophysics Data System (ADS)

    Arriaga, A.

    2000-03-01

    Relativistic effects in 3H and 4He have been studied in the context of Relativistic Hamiltonian Dynamics, using Variational Monte Carlo Methods. Relativistic invariance is achieved through Poincaré group algebra, which introduces a boost interaction term defining the first relativistic effect considered. The second consists in the nonlocalities associated with the relativistic kinetic energy operator and with the relativistic one-pion exchange potential (OPEP). These nonlocalities tend to cancel, being the total effect on the binding energy attractive and very small, of the order of 1%. The dominant relativistic effect is due to the boost interaction, whose contribution is repulsive and of the order of 5%. The repulsive term of the nonrelativistic 3-body interaction has to be reduced by 37% so that the optimal triton binding energy is recovered, meaning that around 1/3 of this phenomenological term accounts for relativisitic effects. The changes induced on the wave functions of nuclei by these relativistic effetcs are very small and short ranged. Although the nonlocalities of OPEP, resulting in a reduction of 15%, are cancelled by other relativistic contributions, they may have significant effects on pion exchange currents in nuclei.

  20. Ensemble Monte Carlo simulation of electron transport in GaAs/AlAs quantum wire structure under the effect of terahertz electric field

    NASA Astrophysics Data System (ADS)

    Borzdov, Andrei V.; Borzdov, Vladimir M.; V'yurkov, Vladimir V.

    2016-12-01

    Ensemble Monte Carlo simulation of electron transport in GaAs/AlAs quantum wire transistor structure is performed. The response of electron drift velocity on the action of harmonic longitudinal electric field is calculated for several values of electric field strength amplitude and gate bias at 77 and 300 K. The periodical electric field has a 1 THz frequency. The nonlinear behaviour of electron drift velocity due to scattering processes is observed.

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

    PubMed

    Barborini, Matteo; Guidoni, Leonardo

    2012-12-14

    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.

  2. Theoretical study of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction by a diffusion quantum Monte Carlo approach.

    PubMed

    Lu, Shih-I

    2005-05-15

    Ab initio calculations of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction has been carried out by the fixed-node diffusion quantum Monte Carlo method in this study. The Monte Carlo sampling is based on the Ornstein-Uhlenbeck random walks guided by a trial wave function constructed from the floating spherical Gaussian orbitals and spherical Gaussian geminals. The Monte Carlo calculated barrier height of 1.09(16) kcal/mol is consistent with the experimental values, 0.86(10)/1.18(10) kcal/mol, and the calculated value from the multireference-type coupled-cluster (MRCC) calculation with the aug-cc-pVQZ(F)/cc-pVQZ(H) basis set, 1.11 kcal/mol. The Monte Carlo-based calculation also gives a similar value of the reaction enthalpy, -32.00(4) kcal/mol, compared with the experimental value, -32.06(17) kcal/mol, and the calculated value from a MRCC/aug-cc-pVQZ(F)/cc-pVQZ(H) calculation, -31.94 kcal/mol. This study clearly indicates a further application of the random-walk-based approach in the field of quantum chemical calculation.

  3. Accurate Characterization of the Peptide Linkage in the Gas Phase: a Joint Quantum-Chemical and Rotational Spectroscopy Study of the Glycine Dipeptide Analogue

    NASA Astrophysics Data System (ADS)

    Puzzarini, Cristina; Biczysko, Malgorzata; Barone, Vincenzo; Largo, Laura; Peña, Isabel; Cabezas, Carlos; Alonso, José L.

    2014-06-01

    Accurate structures of aminoacids in the gas phase have been obtained by joint microwave and quantum-chemical investigations. However, the structure and conformational behavior of α-aminoacids once incorporated into peptide chains are completely different and have not yet been characterized with the same accuracy. To fill this gap, we present here an accurate characterization of the simplest dipeptide analogue (N-acetylglycinamide) involving peptidic bonds. State-of-the-art quantum-chemical computations are complemented by a comprehensive study of the rotational spectrum using a combination of Fourier transform microwave spectroscopy with laser ablation. The coexistence of the C_7 and C_5 conformers has been proved and energetically as well as spectroscopically characterized. This joint theoretical-experimental investigation demonstrated the feasibility of obtaining accurate structures for flexible small biomolecules, thus paving the route to the elucidation of the inherent behavior of peptides.

  4. 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.

  5. 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.

  6. 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)

  7. Breaking the carbon dimer: the challenges of multiple bond dissociation with full configuration interaction quantum Monte Carlo methods.

    PubMed

    Booth, George H; Cleland, Deidre; Thom, Alex J W; Alavi, Ali

    2011-08-28

    The full configuration interaction quantum Monte Carlo (FCIQMC) method, as well as its "initiator" extension (i-FCIQMC), is used to tackle the complex electronic structure of the carbon dimer across the entire dissociation reaction coordinate, as a prototypical example of a strongly correlated molecular system. Various basis sets of increasing size up to the large cc-pVQZ are used, spanning a fully accessible N-electron basis of over 10(12) Slater determinants, and the accuracy of the method is demonstrated in each basis set. Convergence to the FCI limit is achieved in the largest basis with only O[10(7)] walkers within random errorbars of a few tenths of a millihartree across the binding curve, and extensive comparisons to FCI, CCSD(T), MRCI, and CEEIS results are made where possible. A detailed exposition of the convergence properties of the FCIQMC methods is provided, considering convergence with elapsed imaginary time, number of walkers and size of the basis. Various symmetries which can be incorporated into the stochastic dynamic, beyond the standard abelian point group symmetry and spin polarisation are also described. These can have significant benefit to the computational effort of the calculations, as well as the ability to converge to various excited states. The results presented demonstrate a new benchmark accuracy in basis-set energies for systems of this size, significantly improving on previous state of the art estimates.

  8. A density functional and quantum Monte Carlo study of glutamic acid in vacuo and in a dielectric continuum medium.

    PubMed

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

    2012-08-21

    We present density functional theory (DFT) and quantum Monte Carlo (QMC) calculations of the glutamic acid and glutamate ion in vacuo and in various dielectric continuum media within the polarizable continuum model (PCM). In DFT, we employ the integral equation formalism variant of PCM while, in QMC, we use a PCM scheme we have developed to include both surface and volume polarization. We investigate the gas-phase protonation thermochemistry of the glutamic acid using a large set of structural conformations, and find that QMC is in excellent agreement with the best available theoretical and experimental results. For the solvated glutamic acid and glutamate ion, we perform DFT calculations for dielectric constants, ε, between 4 and 78. We find that the glutamate ion in the zwitterionic form is more stable than the non-zwitterionic form over the whole range of dielectric constants, while the glutamic acid is more stable in its non-zwitterionic form at ε = 4. The dielectric constant at which the two glutamic acid species have the same energy depends on the cavity size and lies between 5 and 12.5. We validate these results with QMC for the two limiting values of the dielectric constant, and find qualitative agreement with DFT even though the solvent polarization is less pronounced at the QMC level.

  9. Kernel polynomial representation for imaginary-time Green’s functions in continuous-time quantum Monte Carlo impurity solver

    NASA Astrophysics Data System (ADS)

    Huang, Li

    2016-11-01

    Inspired by the recently proposed Legendre orthogonal polynomial representation for imaginary-time Green’s functions G(τ), we develop an alternate and superior representation for G(τ) and implement it in the hybridization expansion continuous-time quantum Monte Carlo impurity solver. This representation is based on the kernel polynomial method, which introduces some integral kernel functions to filter the numerical fluctuations caused by the explicit truncations of polynomial expansion series and can improve the computational precision significantly. As an illustration of the new representation, we re-examine the imaginary-time Green’s functions of the single-band Hubbard model in the framework of dynamical mean-field theory. The calculated results suggest that with carefully chosen integral kernel functions, whether the system is metallic or insulating, the Gibbs oscillations found in the previous Legendre orthogonal polynomial representation have been vastly suppressed and remarkable corrections to the measured Green’s functions have been obtained. Project supported by the National Natural Science Foundation of China (Grant No. 11504340).

  10. Superconductivity and nematic fluctuations in a model of doped FeSe monolayers: Determinant quantum Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Dumitrescu, Philipp T.; Serbyn, Maksym; Scalettar, Richard T.; Vishwanath, Ashvin

    2016-10-01

    In contrast to bulk FeSe, which exhibits nematic order and low temperature superconductivity, highly doped FeSe reverses the situation, having high temperature superconductivity appearing alongside a suppression of nematic order. To investigate this phenomenon, we study a minimal electronic model of FeSe, with interactions that enhance nematic fluctuations. This model is sign problem free, and is simulated using determinant quantum Monte Carlo (DQMC). We developed a DQMC algorithm with parallel tempering, which proves to be an efficient source of global updates and allows us to access the region of strong interactions. Over a wide range of intermediate couplings, we observe superconductivity with an extended s -wave order parameter, along with enhanced, but short-ranged, q =(0 ,0 ) ferro-orbital (nematic) order. These results are consistent with approximate weak-coupling treatments that predict that nematic fluctuations lead to superconducting pairing. Surprisingly, in the parameter range under study, we do not observe nematic long-range order. Instead, at stronger coupling an unusual insulating phase with q =(π ,π ) antiferro-orbital order appears, which is missed by weak-coupling approximations.

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    We compute two- and three-body cluster functions that describe contributions of composite entities, like hydrogen atoms, ions H-, H_2^+, 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.

  12. 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.

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

    NASA Astrophysics Data System (ADS)

    Lin, J. Y. Y.; Aczel, A. A.; Abernathy, D. L.; Nagler, S. E.; Buyers, W. J. L.; Granroth, G. E.

    2014-04-01

    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., Nat. Commun. 3, 1124 (2012), 10.1038/ncomms2117]. These modes are well described by three-dimensional 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 nitrogen QHO scattering, contributions that arise from the acoustic portion of the partial phonon density of states, 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.

  14. 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.; ...

    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

  15. 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.

  16. Predicting absorption and dispersion in acoustics by direct simulation Monte Carlo: Quantum and classical models for molecular relaxation.

    PubMed

    Hanford, Amanda D; O'Connor, Patrick D; Anderson, James B; Long, Lyle N

    2008-06-01

    In the current study, real gas effects in the propagation of sound waves are simulated using the direct simulation Monte Carlo method for a wide range of frequencies. This particle method allows for treatment of acoustic phenomena at high Knudsen numbers, corresponding to low densities and a high ratio of the molecular mean free path to wavelength. Different methods to model the internal degrees of freedom of diatomic molecules and the exchange of translational, rotational and vibrational energies in collisions are employed in the current simulations of a diatomic gas. One of these methods is the fully classical rigid-rotor/harmonic-oscillator model for rotation and vibration. A second method takes into account the discrete quantum energy levels for vibration with the closely spaced rotational levels classically treated. This method gives a more realistic representation of the internal structure of diatomic and polyatomic molecules. Applications of these methods are investigated in diatomic nitrogen gas in order to study the propagation of sound and its attenuation and dispersion along with their dependence on temperature. With the direct simulation method, significant deviations from continuum predictions are also observed for high Knudsen number flows.

  17. Determinant quantum Monte Carlo study of the two-dimensional single-band Hubbard-Holstein model

    DOE PAGES

    Johnston, S.; Nowadnick, E. A.; Kung, Y. F.; ...

    2013-06-24

    Here, we performed numerical studies of the Hubbard-Holstein model in two dimensions using determinant quantum Monte Carlo (DQMC). We also present details of the method, emphasizing the treatment of the lattice degrees of freedom, and then study the filling and behavior of the fermion sign as a function of model parameters. We find a region of parameter space with large Holstein coupling where the fermion sign recovers despite large values of the Hubbard interaction. This indicates that studies of correlated polarons at finite carrier concentrations are likely accessible to DQMC simulations. We then restrict ourselves to the half-filled model andmore » examine the evolution of the antiferromagnetic structure factor, other metrics for antiferromagnetic and charge-density-wave order, and energetics of the electronic and lattice degrees of freedom as a function of electron-phonon coupling. From this we find further evidence for a competition between charge-density-wave and antiferromagnetic order at half- filling.« less

  18. 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.

  19. 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.

  20. Accurate and efficient quantum chemistry calculations for noncovalent interactions in many-body systems: the XSAPT family of methods.

    PubMed

    Lao, Ka Un; Herbert, John M

    2015-01-15

    We present an overview of "XSAPT", a family of quantum chemistry methods for noncovalent interactions. These methods combine an efficient, iterative, monomer-based approach to computing many-body polarization interactions with a two-body version of symmetry-adapted perturbation theory (SAPT). The result is an efficient method for computing accurate intermolecular interaction energies in large noncovalent assemblies such as molecular and ionic clusters, molecular crystals, clathrates, or protein-ligand complexes. As in traditional SAPT, the XSAPT energy is decomposable into physically meaningful components. Dispersion interactions are problematic in traditional low-order SAPT, and two new approaches are introduced here in an attempt to improve this situation: (1) third-generation empirical atom-atom dispersion potentials, and (2) an empirically scaled version of second-order SAPT dispersion. Comparison to high-level ab initio benchmarks for dimers, water clusters, halide-water clusters, a methane clathrate hydrate, and a DNA intercalation complex illustrate both the accuracy of XSAPT-based methods as well as their limitations. The computational cost of XSAPT scales as O(N(3))-O(N(5)) with respect to monomer size, N, depending upon the particular version that is employed, but the accuracy is typically superior to alternative ab initio methods with similar scaling. Moreover, the monomer-based nature of XSAPT calculations makes them trivially parallelizable, such that wall times scale linearly with respect to the number of monomer units. XSAPT-based methods thus open the door to both qualitative and quantitative studies of noncovalent interactions in clusters, biomolecules, and condensed-phase systems.

  1. Self-consistent phonons: An accurate and practical method to account for anharmonic effects in equilibrium properties of general classical or quantum many-body systems

    NASA Astrophysics Data System (ADS)

    Brown, Sandra E.; Mandelshtam, Vladimir A.

    2016-12-01

    The self-consistent phonons (SCP) method is a practical approach for computing structural and dynamical properties of a general quantum or classical many-body system while incorporating anharmonic effects. However, a convincing demonstration of the accuracy of SCP and its advantages over the standard harmonic approximation is still lacking. Here we apply SCP to classical Lennard-Jones (LJ) clusters and compare with numerically exact results. The close agreement between the two reveals that SCP accurately describes structural properties of the classical LJ clusters from zero-temperature (where the method is exact) up to the temperatures at which the chosen cluster conformation becomes unstable. Given the similarities between thermal and quantum fluctuations, both physically and within the SCP ansatz, the accuracy of classical SCP over a range of temperatures suggests that quantum SCP is also accurate over a range of quantum de Boer parameter Λ = ℏ / (σ√{ mε }) , which describes the degree of quantum character of the system.

  2. Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

    NASA Technical Reports Server (NTRS)

    Haugen, H. K.; Weitz, E.; Leone, S. R.

    1985-01-01

    Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

  3. Accurate and efficient radiation transport in optically thick media -- by means of the Symbolic Implicit Monte Carlo method in the difference formulation

    SciTech Connect

    Szoke, A; Brooks, E D; McKinley, M; Daffin, F

    2005-03-30

    The equations of radiation transport for thermal photons are notoriously difficult to solve in thick media without resorting to asymptotic approximations such as the diffusion limit. One source of this difficulty is that in thick, absorbing media thermal emission is almost completely balanced by strong absorption. In a previous publication [SB03], the photon transport equation was written in terms of the deviation of the specific intensity from the local equilibrium field. We called the new form of the equations the difference formulation. The difference formulation is rigorously equivalent to the original transport equation. It is particularly advantageous in thick media, where the radiation field approaches local equilibrium and the deviations from the Planck distribution are small. The difference formulation for photon transport also clarifies the diffusion limit. In this paper, the transport equation is solved by the Symbolic Implicit Monte Carlo (SIMC) method and a comparison is made between the standard formulation and the difference formulation. The SIMC method is easily adapted to the derivative source terms of the difference formulation, and a remarkable reduction in noise is obtained when the difference formulation is applied to problems involving thick media.

  4. 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.

  5. 1H NMR z-spectra of acetate methyl in stretched hydrogels: Quantum-mechanical description and Markov chain Monte Carlo relaxation-parameter estimation

    NASA Astrophysics Data System (ADS)

    Shishmarev, Dmitry; Chapman, Bogdan E.; Naumann, Christoph; Mamone, Salvatore; Kuchel, Philip W.

    2015-01-01

    The 1H NMR signal of the methyl group of sodium acetate is shown to be a triplet in the anisotropic environment of stretched gelatin gel. The multiplet structure of the signal is due to the intra-methyl residual dipolar couplings. The relaxation properties of the spin system were probed by recording steady-state irradiation envelopes ('z-spectra'). A quantum-mechanical model based on irreducible spherical tensors formed by the three magnetically equivalent spins of the methyl group was used to simulate and fit experimental z-spectra. The multiple parameter values of the relaxation model were estimated by using a Bayesian-based Markov chain Monte Carlo algorithm.

  6. MO-A-BRD-10: A Fast and Accurate GPU-Based Proton Transport Monte Carlo Simulation for Validating Proton Therapy Treatment Plans

    SciTech Connect

    Wan Chan Tseung, H; Ma, J; Beltran, C

    2014-06-15

    Purpose: To build a GPU-based Monte Carlo (MC) simulation of proton transport with detailed modeling of elastic and non-elastic (NE) protonnucleus interactions, for use in a very fast and cost-effective proton therapy treatment plan verification system. Methods: Using the CUDA framework, we implemented kernels for the following tasks: (1) Simulation of beam spots from our possible scanning nozzle configurations, (2) Proton propagation through CT geometry, taking into account nuclear elastic and multiple scattering, as well as energy straggling, (3) Bertini-style modeling of the intranuclear cascade stage of NE interactions, and (4) Simulation of nuclear evaporation. To validate our MC, we performed: (1) Secondary particle yield calculations in NE collisions with therapeutically-relevant nuclei, (2) Pencil-beam dose calculations in homogeneous phantoms, (3) A large number of treatment plan dose recalculations, and compared with Geant4.9.6p2/TOPAS. A workflow was devised for calculating plans from a commercially available treatment planning system, with scripts for reading DICOM files and generating inputs for our MC. Results: Yields, energy and angular distributions of secondaries from NE collisions on various nuclei are in good agreement with the Geant4.9.6p2 Bertini and Binary cascade models. The 3D-gamma pass rate at 2%–2mm for 70–230 MeV pencil-beam dose distributions in water, soft tissue, bone and Ti phantoms is 100%. The pass rate at 2%–2mm for treatment plan calculations is typically above 98%. The net computational time on a NVIDIA GTX680 card, including all CPU-GPU data transfers, is around 20s for 1×10{sup 7} proton histories. Conclusion: Our GPU-based proton transport MC is the first of its kind to include a detailed nuclear model to handle NE interactions on any nucleus. Dosimetric calculations demonstrate very good agreement with Geant4.9.6p2/TOPAS. Our MC is being integrated into a framework to perform fast routine clinical QA of pencil

  7. Accurate molecular dynamics and nuclear quantum effects at low cost by multiple steps in real and imaginary time: Using density functional theory to accelerate wavefunction methods

    NASA Astrophysics Data System (ADS)

    Kapil, V.; VandeVondele, J.; Ceriotti, M.

    2016-02-01

    The development and implementation of increasingly accurate methods for electronic structure calculations mean that, for many atomistic simulation problems, treating light nuclei as classical particles is now one of the most serious approximations. Even though recent developments have significantly reduced the overhead for modeling the quantum nature of the nuclei, the cost is still prohibitive when combined with advanced electronic structure methods. Here we present how multiple time step integrators can be combined with ring-polymer contraction techniques (effectively, multiple time stepping in imaginary time) to reduce virtually to zero the overhead of modelling nuclear quantum effects, while describing inter-atomic forces at high levels of electronic structure theory. This is demonstrated for a combination of MP2 and semi-local DFT applied to the Zundel cation. The approach can be seamlessly combined with other methods to reduce the computational cost of path integral calculations, such as high-order factorizations of the Boltzmann operator or generalized Langevin equation thermostats.

  8. Accurate molecular dynamics and nuclear quantum effects at low cost by multiple steps in real and imaginary time: Using density functional theory to accelerate wavefunction methods

    SciTech Connect

    Kapil, V.; Ceriotti, M.; VandeVondele, J.

    2016-02-07

    The development and implementation of increasingly accurate methods for electronic structure calculations mean that, for many atomistic simulation problems, treating light nuclei as classical particles is now one of the most serious approximations. Even though recent developments have significantly reduced the overhead for modeling the quantum nature of the nuclei, the cost is still prohibitive when combined with advanced electronic structure methods. Here we present how multiple time step integrators can be combined with ring-polymer contraction techniques (effectively, multiple time stepping in imaginary time) to reduce virtually to zero the overhead of modelling nuclear quantum effects, while describing inter-atomic forces at high levels of electronic structure theory. This is demonstrated for a combination of MP2 and semi-local DFT applied to the Zundel cation. The approach can be seamlessly combined with other methods to reduce the computational cost of path integral calculations, such as high-order factorizations of the Boltzmann operator or generalized Langevin equation thermostats.

  9. Methods for modeling non-equilibrium degenerate statistics and quantum-confined scattering in 3D ensemble Monte Carlo transport simulations

    NASA Astrophysics Data System (ADS)

    Crum, Dax M.; Valsaraj, Amithraj; David, John K.; Register, Leonard F.; Banerjee, Sanjay K.

    2016-12-01

    Particle-based ensemble semi-classical Monte Carlo (MC) methods employ quantum corrections (QCs) to address quantum confinement and degenerate carrier populations to model tomorrow's ultra-scaled metal-oxide-semiconductor-field-effect-transistors. Here, we present the most complete treatment of quantum confinement and carrier degeneracy effects in a three-dimensional (3D) MC device simulator to date, and illustrate their significance through simulation of n-channel Si and III-V FinFETs. Original contributions include our treatment of far-from-equilibrium degenerate statistics and QC-based modeling of surface-roughness scattering, as well as considering quantum-confined phonon and ionized-impurity scattering in 3D. Typical MC simulations approximate degenerate carrier populations as Fermi distributions to model the Pauli-blocking (PB) of scattering to occupied final states. To allow for increasingly far-from-equilibrium non-Fermi carrier distributions in ultra-scaled and III-V devices, we instead generate the final-state occupation probabilities used for PB by sampling the local carrier populations as function of energy and energy valley. This process is aided by the use of fractional carriers or sub-carriers, which minimizes classical carrier-carrier scattering intrinsically incompatible with degenerate statistics. Quantum-confinement effects are addressed through quantum-correction potentials (QCPs) generated from coupled Schrödinger-Poisson solvers, as commonly done. However, we use these valley- and orientation-dependent QCPs not just to redistribute carriers in real space, or even among energy valleys, but also to calculate confinement-dependent phonon, ionized-impurity, and surface-roughness scattering rates. FinFET simulations are used to illustrate the contributions of each of these QCs. Collectively, these quantum effects can substantially reduce and even eliminate otherwise expected benefits of considered In0.53Ga0.47 As FinFETs over otherwise identical

  10. 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

  11. Extending the molecular size in accurate quantum-chemical calculations: the equilibrium structure and spectroscopic properties of uracil.

    PubMed

    Puzzarini, Cristina; Barone, Vincenzo

    2011-04-21

    The equilibrium structure of uracil has been investigated using both theoretical and experimental data. With respect to the former, quantum-chemical calculations at the coupled-cluster level in conjunction with a triple-zeta basis set have been carried out. Extrapolation to the basis set limit, performed employing the second-order Møller-Plesset perturbation theory, and inclusion of core-correlation and diffuse-function corrections have also been considered. Based on the available rotational constants for various isotopic species together with corresponding computed vibrational corrections, the semi-experimental equilibrium structure of uracil has been determined for the first time. Theoretical and semi-experimental structures have been found in remarkably good agreement, thus pointing out the limitations of previous experimental determinations. Molecular and spectroscopic properties of uracil have then been studied by means of the composite computational approach introduced for the molecular structure evaluation. Among the results achieved, we mention the revision of the dipole moment. On the whole, it has been proved that the computational procedure presented is able to provide parameters with the proper accuracy to support experimental investigations of large molecules of biological interest.

  12. 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

    2015-12-08

    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.

  13. 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.

  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; ...

    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. 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.

  17. Accurate Ab Initio Quantum Mechanics Simulations of Bi2Se3 and Bi2Te3 Topological Insulator Surfaces.

    PubMed

    Crowley, Jason M; Tahir-Kheli, Jamil; Goddard, William A

    2015-10-01

    It has been established experimentally that Bi2Te3 and Bi2Se3 are topological insulators, with zero band gap surface states exhibiting linear dispersion at the Fermi energy. Standard density functional theory (DFT) methods such as PBE lead to large errors in the band gaps for such strongly correlated systems, while more accurate GW methods are too expensive computationally to apply to the thin films studied experimentally. We show here that the hybrid B3PW91 density functional yields GW-quality results for these systems at a computational cost comparable to PBE. The efficiency of our approach stems from the use of Gaussian basis functions instead of plane waves or augmented plane waves. This remarkable success without empirical corrections of any kind opens the door to computational studies of real chemistry involving the topological surface state, and our approach is expected to be applicable to other semiconductors with strong spin-orbit coupling.

  18. Monte Carlo model incorporating many-body effects for determining the gain spectra of quantum dot lasers

    NASA Astrophysics Data System (ADS)

    Peyvast, Negin; Shahid, Hifsa; Hogg, Richard A.; Childs, David T. D.

    2015-12-01

    We present a Monte Carlo model that simulates the gain spectra of a QD laser material that empirically includes free-carrier effects. We compare simulation results of both Fermi-Dirac and random carrier populations, and compare them with experimental data. The free-carrier effects are highlighted as being more important than the choice of carrier statistics, and routes to improve this simple model are discussed.

  19. A DPF Analysis Yields Quantum Mechanically Accurate Analytic Potential Energy Functions for the a ^1Σ^+ and X ^1Σ^+ States of NaH

    NASA Astrophysics Data System (ADS)

    Le Roy, Robert J.; Walji, Sadru; Sentjens, Katherine

    2013-06-01

    Alkali hydride diatomic molecules have long been the object of spectroscopic studies. However, their small reduced mass makes them species for which the conventional semiclassical-based methods of analysis tend to have the largest errors. To date, the only quantum-mechanically accurate direct-potential-fit (DPF) analysis for one of these molecules was the one for LiH reported by Coxon and Dickinson. The present paper extends this level of analysis to NaH, and reports a DPF analysis of all available spectroscopic data for the A ^1Σ^+-X ^1Σ^+ system of NaH which yields analytic potential energy functions for these two states that account for those data (on average) to within the experimental uncertainties. W.C. Stwalley, W.T. Zemke and S.C. Yang, J. Phys. Chem. Ref. Data {20}, 153-187 (1991). J.A. Coxon and C.S. Dickinson, J. Chem. Phys. {121}, 8378 (2004).

  20. Accurate quantum wave packet calculations for the F + HCl → Cl + HF reaction on the ground 1(2)A' potential energy surface.

    PubMed

    Bulut, Niyazi; Kłos, Jacek; Alexander, Millard H

    2012-03-14

    We present converged exact quantum wave packet calculations of reaction probabilities, integral cross sections, and thermal rate coefficients for the title reaction. Calculations have been carried out on the ground 1(2)A' global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged wave packet reaction probabilities at selected values of the total angular momentum up to a partial wave of J = 140 with the HCl reagent initially selected in the v = 0, j = 0-16 rovibrational states have been obtained for the collision energy range from threshold up to 0.8 eV. The present calculations confirm an important enhancement of reactivity with rotational excitation of the HCl molecule. First, accurate integral cross sections and rate constants have been calculated and compared with the available experimental data.

  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. 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.

  3. 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.

  4. A versatile ratiometric nanosensing approach for sensitive and accurate detection of Hg(2+) and biological thiols based on new fluorescent carbon quantum dots.

    PubMed

    Fu, Huili; Ji, Zhongyin; Chen, Xuejie; Cheng, Anwei; Liu, Shucheng; Gong, Peiwei; Li, Guoliang; Chen, Guang; Sun, Zhiwei; Zhao, Xianen; Cheng, Feng; You, Jinmao

    2017-03-01

    Herein, we first reported a facile synthesis method for fabrication of highly photoluminescent carbon quantum dots (CQDs) using sodium alginate as the carbon source and histidine as both the nitrogen source and functional monomer by one-pot hydrothermal synthesis. The as-prepared CQDs gave a high quantum yield of 32%. By employing the new CQDs and rhodamine B (RhB), we demonstrated a simple, facile, sensitive, and accurate ratiometric sensor for detection of Hg(2+) and biological thiols. The photoluminescence of CQDs in the ratiometric sensor can be selectively and intensively suppressed by Hg(2+) due to strong electrostatic interaction between the surface functional groups of the CQDs and Hg(2+). When glutathione (GSH) was introduced into the "Turn Off" CQDs-RhB-Hg(2+) sensing system, the fluorescence of the CQDs can be recovered rapidly due to the stronger affinity between thiol and Hg(2+), while the fluorescence of the RhB remained constant in this sensing process. Based on the above principle, the ratiometric strategy for detecting Hg(2+) and GSH can be achieved readily, and gives satisfactory limit of detections (LODs) of 30 and 20 nM for Hg(2+) and GSH, respectively. The dual-emission fluorescent CQDs-RhB sensor does not need the complicated molecular design and the synthesis of dual-emission fluorophores. Meanwhile, the feasibility of the proposed method for analysis of water samples, food samples, and biological samples (plasma from mice oxidative stress study) was investigated. The developed ratiometric nanosensor is proven to be facile, with less sample consumption, rapid, lost cost, highly sensitive, and very selective for Hg(2+) and biological thiol detection, which offers a new approach for environmental, food, and biological analysis. Graphical abstract Ratiometric nanosensing approach detection of Hg(2+) and biological thiols.

  5. Reaction mechanism and tautomeric equilibrium of 2-mercaptopyrimidine in the gas phase and in aqueous solution: a combined Monte Carlo and quantum mechanics study.

    PubMed

    Lima, Maria Carolina P; Coutinho, Kaline; Canuto, Sylvio; Rocha, Willian R

    2006-06-08

    A combined Monte Carlo and quantum mechanical study was carried out to analyze the tautomeric equilibrium of 2-mercaptopyrimidine in the gas phase and in aqueous solution. Second- and fourth-order Møller-Plesset perturbation theory calculations indicate that in the gas phase thiol (Pym-SH) is more stable than the thione (Pym-NH) by ca. 8 kcal/mol. In aqueous solution, thermodynamic perturbation theory implemented on a Monte Carlo NpT simulation indicates that both the differential enthalpy and Gibbs free energy favor the thione form. The calculated differential enthalpy is DeltaH(SH)(-->)(NH)(solv) = -1.7 kcal/mol and the differential Gibbs free energy is DeltaG(SH)(-->)(NH)(solv) = -1.9 kcal/mol. Analysis is made of the contribution of the solute-solvent hydrogen bonds and it is noted that the SH group in the thiol and NH group in the thione tautomers act exclusively as a hydrogen bond donor in aqueous solution. The proton transfer reaction between the tautomeric forms was also investigated in the gas phase and in aqueous solution. Two distinct mechanisms were considered: a direct intramolecular transfer and a water-assisted mechanism. In the gas phase, the intramolecular transfer leads to a large energy barrier of 34.4 kcal/mol, passing through a three-center transition state. The proton transfer with the assistance of one water molecule decreases the energy barrier to 17.2 kcal/mol. In solution, these calculated activation barriers are, respectively, 32.0 and 14.8 kcal/mol. The solvent effect is found to be sizable but it is considerably more important as a participant in the water-assisted mechanism than the solvent field of the solute-solvent interaction. Finally, the calculated total Gibbs free energy is used to estimate the equilibrium constant.

  6. 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.

  7. 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.

  8. High-energy anomaly in Nd2-xCexCuO4 investigated by angle-resolved photoemission spectroscopy and quantum Monte Carlo simulations

    NASA Astrophysics Data System (ADS)

    Schmitt, F.; Moritz, B.; Johnston, S.; Mo, S.-K.; Hashimoto, M.; Moore, R. G.; Lu, D.-H.; Motoyama, E.; Greven, M.; Devereaux, T. P.; Shen, Z.-X.

    2011-05-01

    Recent high-binding-energy angle-resolved photoemission spectroscopy (ARPES) experiments reveal a change in band dispersion in the high-temperature superconducting cuprates (HTSCs) known as the high-energy anomaly (HEA). Despite considerable experimental and theoretical attention, the origin of the HEA remains a topic of some controversy. In this paper we present systematic and comprehensive experimental evidence on the origin of the HEA from ARPES measurements on the electron-doped HTSC material Nd2-xCexCuO4 at a number of dopings across the phase diagram and over the entire Brillouin zone (BZ). Comparing these new experimental findings to quantum Monte Carlo simulations of the single-band Hubbard model across the BZ and for various dopings demonstrates that this simple model qualitatively reproduces the key experimental features of the HEA and points to significant self-energy and band renormalization effects accompanying strong electron correlations as its origin rather than coupling to any one emergent bosonic mode, e.g., antiferromagnetic spin fluctuations. We conclude from comparison to this simple model that the HEA in these systems should be regarded as a crossover from a coherent quasiparticle band at low binding energies, emergent from the upper Hubbard band in electron-doped HTSCs due to doping and modified by subsequent strong band renormalization effects, to oxygen valence bands at higher binding energy that would be revealed in simulations explicitly incorporating these important orbital degrees of freedom.

  9. What makes the Tc of monolayer FeSe on SrTiO3 so high: a sign-problem-free quantum Monte Carlo study.

    PubMed

    Li, Zi-Xiang; Wang, Fa; Yao, Hong; Lee, Dung-Hai

    Monolayer FeSe films grown on SrTiO3 (STO) substrate show superconducting gap-opening temperatures ([Formula: see text]) which are almost an order of magnitude higher than those of the bulk FeSe and are highest among all known Fe-based superconductors. Angle-resolved photoemission spectroscopy observed "replica bands" suggesting the importance of the interaction between FeSe electrons and STO phonons. These facts rejuvenated the quest for [Formula: see text] enhancement mechanisms in iron-based, especially iron-chalcogenide, superconductors. Here, we perform the first numerically-exact sign-problem-free quantum Monte Carlo simulations to iron-based superconductors. We (1) study the electronic pairing mechanism intrinsic to heavily electron doped FeSe films, and (2) examine the effects of electron-phonon interaction between FeSe and STO as well as nematic fluctuations on [Formula: see text]. Armed with these results, we return to the question "what makes the [Formula: see text] of monolayer FeSe on SrTiO3 so high?" in the conclusion and discussions.

  10. 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.

  11. 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.

  12. A quantum Monte Carlo study on electron correlation in all-metal aromatic clusters MAl4(-) (M = Li, Na, K, Rb, Cu, Ag and Au).

    PubMed

    Brito, Bráulio Gabriel A; Hai, G-Q; Teixeira Rabelo, J N; Cândido, Ladir

    2014-05-14

    Using fixed-node diffusion quantum Monte Carlo (FN-DMC) simulation we investigate the electron correlation in all-metal aromatic clusters MAl4(-) (with M = Li, Na, K, Rb, Cu, Ag and Au). The electron detachment energies and electron affinities of the clusters are obtained. The vertical electron detachment energies obtained from the FN-DMC calculations are in very good agreement with the available experimental results. Calculations are also performed within the Hartree-Fock approximation, density-functional theory (DFT), and the couple-cluster (CCSD(T)) method. From the obtained results, we analyse the impact of the electron correlation effects in these bimetallic clusters and find that the correlation of the valence electrons contributes significantly to the detachment energies and electron affinities, varying between 20% and 50% of their total values. Furthermore, we discuss the electron correlation effects on the stability of the clusters as well as the accuracy of the DFT and CCSD(T) calculations in the present systems.

  13. A study of H+H2 and several H-bonded molecules by phaseless auxiliary-field quantum Monte Carlo with plane wave and Gaussian basis sets.

    PubMed

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

    2007-05-21

    The authors present phaseless auxiliary-field (AF) quantum Monte Carlo (QMC) calculations of the ground states of some hydrogen-bonded systems. These systems were selected to test and benchmark different aspects of the new phaseless AF QMC method. They include the transition state of H+H(2) near the equilibrium geometry and in the van der Walls limit, as well as the H(2)O, OH, and H(2)O(2) molecules. Most of these systems present significant challenges for traditional independent-particle electronic structure approaches, and many also have exact results available. The phaseless AF QMC method is used either with a plane wave basis with pseudopotentials or with all-electron Gaussian basis sets. For some systems, calculations are done with both to compare and characterize the performance of AF QMC under different basis sets and different Hubbard-Stratonovich decompositions. Excellent results are obtained using as input single Slater determinant wave functions taken from independent-particle calculations. Comparisons of the Gaussian based AF QMC results with exact full configuration interaction show that the errors from controlling the phase problem with the phaseless approximation are small. At the large basis-size limit, the AF QMC results using both types of basis sets are in good agreement with each other and with experimental values.

  14. Momentum distribution and non-Fermi-liquid behavior in low-doped two-orbital model: Finite-size cluster quantum Monte Carlo approach

    NASA Astrophysics Data System (ADS)

    Kashurnikov, Vladimir A.; Krasavin, Andrey V.; Zhumagulov, Yaroslav V.

    2016-12-01

    The two-dimensional two-orbital Hubbard model is studied with the use of a finite-size cluster world-line quantum Monte Carlo algorithm. This model is widely used for simulation of the band structure of FeAs clusters, which are structure elements of Fe-based high-temperature superconductors. The choice of a special basis set of hypersites allowed us to take into account four-fermion operator terms and to overcome partly the sign problem. Spectral functions and the density of states for various parameters of the model are obtained in the undoped and low-doped regimes. The correlated distortion of the spectral density with the change of doping is observed, and the applicability of the "hard-band" approximation in the doped regime is demonstrated. Profiles of the momentum distribution are obtained for the first Brillouin zone; they have pronounced jump near the Fermi level, which decreases with the growth of the strength of the interaction. The invariance of the Fermi surface with respect to the strength of the interaction is testified. Nesting is found in the case of electron and hole doping. Fermi-liquid parameters of the model are derived. The Z factor grows sharply with the increasing of the level of doping and monotonously decreases with the growth of the strength of the interaction. Moreover, electron-hole doping asymmetry of the Z factor is revealed. The non-Fermi-liquid behavior and the deviation from Luttinger theorem are observed.

  15. Discovery of a general method of solving the Schrödinger and dirac equations that opens a way to accurately predictive quantum chemistry.

    PubMed

    Nakatsuji, Hiroshi

    2012-09-18

    Just as Newtonian law governs classical physics, the Schrödinger equation (SE) and the relativistic Dirac equation (DE) rule the world of chemistry. So, if we can solve these equations accurately, we can use computation to predict chemistry precisely. However, for approximately 80 years after the discovery of these equations, chemists believed that they could not solve SE and DE for atoms and molecules that included many electrons. This Account reviews ideas developed over the past decade to further the goal of predictive quantum chemistry. Between 2000 and 2005, I discovered a general method of solving the SE and DE accurately. As a first inspiration, I formulated the structure of the exact wave function of the SE in a compact mathematical form. The explicit inclusion of the exact wave function's structure within the variational space allows for the calculation of the exact wave function as a solution of the variational method. Although this process sounds almost impossible, it is indeed possible, and I have published several formulations and applied them to solve the full configuration interaction (CI) with a very small number of variables. However, when I examined analytical solutions for atoms and molecules, the Hamiltonian integrals in their secular equations diverged. This singularity problem occurred in all atoms and molecules because it originates from the singularity of the Coulomb potential in their Hamiltonians. To overcome this problem, I first introduced the inverse SE and then the scaled SE. The latter simpler idea led to immediate and surprisingly accurate solution for the SEs of the hydrogen atom, helium atom, and hydrogen molecule. The free complement (FC) method, also called the free iterative CI (free ICI) method, was efficient for solving the SEs. In the FC method, the basis functions that span the exact wave function are produced by the Hamiltonian of the system and the zeroth-order wave function. These basis functions are called complement

  16. Dynamics of the Anderson model for dilute magnetic alloys: A quantum Monte Carlo and maximum entropy study

    SciTech Connect

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

    1990-01-01

    In this article we describe the results of a new method for calculating the dynamical properties of the Anderson model. QMC generates data about the Matsubara Green's functions in imaginary time. To obtain dynamical properties, one must analytically continue these data to real time. This is an extremely ill-posed inverse problem similar to the inversion of a Laplace transform from incomplete and noisy data. Our method is a general one, applicable to the calculation of dynamical properties from a wide variety of quantum simulations. We use Bayesian methods of statistical inference to determine the dynamical properties based on both the QMC data and any prior information we may have such as sum rules, symmetry, high frequency limits, etc. This provides a natural means of combining perturbation theory and numerical simulations in order to understand dynamical many-body problems. Specifically we use the well-established maximum entropy (ME) method for image reconstruction. We obtain the spectral density and transport coefficients over the entire range of model parameters accessible by QMC, with data having much larger statistical error than required by other proposed analytic continuation methods.

  17. Quantum simulated annealing

    NASA Astrophysics Data System (ADS)

    Boixo, Sergio; Somma, Rolando; Barnum, Howard

    2008-03-01

    We develop a quantum algorithm to solve combinatorial optimization problems through quantum simulation of a classical annealing process. Our algorithm combines techniques from quantum walks and quantum phase estimation, and can be viewed as the quantum analogue of the discrete-time Markov Chain Monte Carlo implementation of classical simulated annealing.

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

    PubMed

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

    2015-06-07

    We study the ionization energy, electron affinity, and the π → π(∗) ((1)La) 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 (1)La 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 (1)La 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.

  19. 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.

  20. 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.

  1. 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.

  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. Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals.

    PubMed

    Vanícek, Jirí

    2011-01-01

    Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.

  5. Inequivalent electron densities derived from an approximate correlated ground-state wave function using the Hiller-Sucher-Feinberg identity: Comparisons with quantum Monte Carlo densities for He and Ne atoms

    NASA Astrophysics Data System (ADS)

    Amovilli, Claudio; March, Norman H.

    The Hiller-Sucher-Feinberg (HSF) identity is combined with the three-parameter correlated wave function of Chandrasekhar in order to generate an alternative electron density ρ(r) for the He atom. This and the conventional "local" operator form of ρ(r) are then compared with a diffusion quantum Monte Carlo density. An exact limiting relation is also presented, via HSF identity, between the one-particle density matrix and the pair density in a many-electron atom, which transcends its Hartree-Fock counterpart and has no N-representability difficulties. For the Ne atom, the accuracy of the semiempirical correlated electron density recently obtained by Cordero et al. (Phys. Rev. A 2007, 75, 052502) using fine-tuning of Hartree-Fock theory was assessed by appealing to the ground-state density from diffusion quantum Monte Carlo. The high accuracy of the Cordero et al. density was thereby confirmed. A HSF calculation on neon, with a correlated many-body wave function as starting point, is a worthwhile future aim.

  6. Bold diagrammatic Monte Carlo method applied to fermionized frustrated spins.

    PubMed

    Kulagin, S A; Prokof'ev, N; Starykh, O A; Svistunov, B; Varney, C N

    2013-02-15

    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.

  7. Fully Coriolis-coupled quantum studies of the H + O2 (upsilon i = 0-2, j i = 0,1) --> OH + O reaction on an accurate potential energy surface: integral cross sections and rate constants.

    PubMed

    Lin, Shi Ying; Sun, Zhigang; Guo, Hua; Zhang, Dong Hui; Honvault, Pascal; Xie, Daiqian; Lee, Soo-Y

    2008-01-31

    We present accurate quantum calculations of the integral cross section and rate constant for the H + O2 --> OH + O combustion reaction on a recently developed ab initio potential energy surface using parallelized time-dependent and Chebyshev wavepacket methods. Partial wave contributions up to J = 70 were computed with full Coriolis coupling, which enabled us to obtain the initial state-specified integral cross sections up to 2.0 eV of the collision energy and thermal rate constants up to 3000 K. The integral cross sections show a large reaction threshold due to the quantum endothermicity of the reaction, and they monotonically increase with the collision energy. As a result, the temperature dependence of the rate constant is of the Arrhenius type. In addition, it was found that reactivity is enhanced by reactant vibrational excitation. The calculated thermal rate constant shows a significant improvement over that obtained on the DMBE IV potential, but it still underestimates the experimental consensus.

  8. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    DOE PAGES

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

  9. Virial theorem in the Kohn-Sham density-functional theory formalism: accurate calculation of the atomic quantum theory of atoms in molecules energies.

    PubMed

    Rodríguez, Juan I; Ayers, Paul W; Götz, Andreas W; Castillo-Alvarado, F L

    2009-07-14

    A new approach for computing the atom-in-molecule [quantum theory of atoms in molecule (QTAIM)] energies in Kohn-Sham density-functional theory is presented and tested by computing QTAIM energies for a set of representative molecules. In the new approach, the contribution for the correlation-kinetic energy (T(c)) is computed using the density-functional theory virial relation. Based on our calculations, it is shown that the conventional approach where atomic energies are computed using only the noninteracting part of the kinetic energy might be in error by hundreds of kJ/mol.

  10. MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO{sup +}(H{sub 2}O) cluster using accurate potential energy and dipole moment surfaces

    SciTech Connect

    Homayoon, Zahra

    2014-09-28

    A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO{sup +}(H{sub 2}O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO{sup +}(H{sub 2}O) and NO{sup +}(D{sub 2}O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO{sup +}(H{sub 2}O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water “antisymmetric” stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

  11. 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.

  12. Enhanced Constraints for Accurate Lower Bounds on Many-Electron Quantum Energies from Variational Two-Electron Reduced Density Matrix Theory.

    PubMed

    Mazziotti, David A

    2016-10-07

    A central challenge of physics is the computation of strongly correlated quantum systems. The past ten years have witnessed the development and application of the variational calculation of the two-electron reduced density matrix (2-RDM) without the wave function. In this Letter we present an orders-of-magnitude improvement in the accuracy of 2-RDM calculations without an increase in their computational cost. The advance is based on a low-rank, dual formulation of an important constraint on the 2-RDM, the T2 condition. Calculations are presented for metallic chains and a cadmium-selenide dimer. The low-scaling T2 condition will have significant applications in atomic and molecular, condensed-matter, and nuclear physics.

  13. Enhanced Constraints for Accurate Lower Bounds on Many-Electron Quantum Energies from Variational Two-Electron Reduced Density Matrix Theory

    NASA Astrophysics Data System (ADS)

    Mazziotti, David A.

    2016-10-01

    A central challenge of physics is the computation of strongly correlated quantum systems. The past ten years have witnessed the development and application of the variational calculation of the two-electron reduced density matrix (2-RDM) without the wave function. In this Letter we present an orders-of-magnitude improvement in the accuracy of 2-RDM calculations without an increase in their computational cost. The advance is based on a low-rank, dual formulation of an important constraint on the 2-RDM, the T 2 condition. Calculations are presented for metallic chains and a cadmium-selenide dimer. The low-scaling T 2 condition will have significant applications in atomic and molecular, condensed-matter, and nuclear physics.

  14. State-to-state rotational phase coherence effect on the vibration-rotation band shape - An accurate quantum calculation for CO-He

    NASA Technical Reports Server (NTRS)

    Boissoles, J.; Boulet, C.; Robert, D.; Green, S.

    1989-01-01

    Accurate coupled state calculations of line coupling are performed for infrared lines of carbon monoxide perturbed by helium. Such calculations lead to both real and imaginary line couplings. For the first time, the effect of this imaginary line couplings, connected with state-to-state rotational phase coherences, on infrared band shape, is analyzed. An extension of detailed balance principle to the complex plane is suggested from the present computed off-diagonal cross sections. This allows us to understand the physical mechanism underlying the weak effect of phase coherences on CO-He infrared band shape.

  15. XModeScore: a novel method for accurate protonation/tautomer-state determination using quantum-mechanically driven macromolecular X-ray crystallographic refinement

    PubMed Central

    Borbulevych, Oleg; Martin, Roger I.; Tickle, Ian J.; Westerhoff, Lance M.

    2016-01-01

    Gaining an understanding of the protein–ligand complex structure along with the proper protonation and explicit solvent effects can be important in obtaining meaningful results in structure-guided drug discovery and structure-based drug discovery. Unfortunately, protonation and tautomerism are difficult to establish with conventional methods because of difficulties in the experimental detection of H atoms owing to the well known limitations of X-ray crystallography. In the present work, it is demonstrated that semiempirical, quantum-mechanics-based macromolecular crystallographic refinement is sensitive to the choice of a protonation-state/tautomer form of ligands and residues, and can therefore be used to explore potential states. A novel scoring method, called XModeScore, is described which enumerates the possible protomeric/tautomeric modes, refines each mode against X-ray diffraction data with the semiempirical quantum-mechanics (PM6) Hamiltonian and scores each mode using a combination of energetic strain (or ligand strain) and rigorous statistical analysis of the difference electron-density distribution. It is shown that using XModeScore it is possible to consistently distinguish the correct bound protomeric/tautomeric modes based on routine X-ray data, even at lower resolutions of around 3 Å. These X-ray results are compared with the results obtained from much more expensive and laborious neutron diffraction studies for three different examples: tautomerism in the acetazolamide ligand of human carbonic anhydrase II (PDB entries 3hs4 and 4k0s), tautomerism in the 8HX ligand of urate oxidase (PDB entries 4n9s and 4n9m) and the protonation states of the catalytic aspartic acid found within the active site of an aspartic protease (PDB entry 2jjj). In each case, XModeScore applied to the X-ray diffraction data is able to determine the correct protonation state as defined by the neutron diffraction data. The impact of QM-based refinement versus conventional

  16. XModeScore: a novel method for accurate protonation/tautomer-state determination using quantum-mechanically driven macromolecular X-ray crystallographic refinement.

    PubMed

    Borbulevych, Oleg; Martin, Roger I; Tickle, Ian J; Westerhoff, Lance M

    2016-04-01

    Gaining an understanding of the protein-ligand complex structure along with the proper protonation and explicit solvent effects can be important in obtaining meaningful results in structure-guided drug discovery and structure-based drug discovery. Unfortunately, protonation and tautomerism are difficult to establish with conventional methods because of difficulties in the experimental detection of H atoms owing to the well known limitations of X-ray crystallography. In the present work, it is demonstrated that semiempirical, quantum-mechanics-based macromolecular crystallographic refinement is sensitive to the choice of a protonation-state/tautomer form of ligands and residues, and can therefore be used to explore potential states. A novel scoring method, called XModeScore, is described which enumerates the possible protomeric/tautomeric modes, refines each mode against X-ray diffraction data with the semiempirical quantum-mechanics (PM6) Hamiltonian and scores each mode using a combination of energetic strain (or ligand strain) and rigorous statistical analysis of the difference electron-density distribution. It is shown that using XModeScore it is possible to consistently distinguish the correct bound protomeric/tautomeric modes based on routine X-ray data, even at lower resolutions of around 3 Å. These X-ray results are compared with the results obtained from much more expensive and laborious neutron diffraction studies for three different examples: tautomerism in the acetazolamide ligand of human carbonic anhydrase II (PDB entries 3hs4 and 4k0s), tautomerism in the 8HX ligand of urate oxidase (PDB entries 4n9s and 4n9m) and the protonation states of the catalytic aspartic acid found within the active site of an aspartic protease (PDB entry 2jjj). In each case, XModeScore applied to the X-ray diffraction data is able to determine the correct protonation state as defined by the neutron diffraction data. The impact of QM-based refinement versus conventional

  17. Accurate macromolecular crystallographic refinement: incorporation of the linear scaling, semiempirical quantum-mechanics program DivCon into the PHENIX refinement package.

    PubMed

    Borbulevych, Oleg Y; Plumley, Joshua A; Martin, Roger I; Merz, Kenneth M; Westerhoff, Lance M

    2014-05-01

    Macromolecular crystallographic refinement relies on sometimes dubious stereochemical restraints and rudimentary energy functionals to ensure the correct geometry of the model of the macromolecule and any covalently bound ligand(s). The ligand stereochemical restraint file (CIF) requires a priori understanding of the ligand geometry within the active site, and creation of the CIF is often an error-prone process owing to the great variety of potential ligand chemistry and structure. Stereochemical restraints have been replaced with more robust functionals through the integration of the linear-scaling, semiempirical quantum-mechanics (SE-QM) program DivCon with the PHENIX X-ray refinement engine. The PHENIX/DivCon package has been thoroughly validated on a population of 50 protein-ligand Protein Data Bank (PDB) structures with a range of resolutions and chemistry. The PDB structures used for the validation were originally refined utilizing various refinement packages and were published within the past five years. PHENIX/DivCon does not utilize CIF(s), link restraints and other parameters for refinement and hence it does not make as many a priori assumptions about the model. Across the entire population, the method results in reasonable ligand geometries and low ligand strains, even when the original refinement exhibited difficulties, indicating that PHENIX/DivCon is applicable to both single-structure and high-throughput crystallography.

  18. Accurate macromolecular crystallographic refinement: incorporation of the linear scaling, semiempirical quantum-mechanics program DivCon into the PHENIX refinement package

    PubMed Central

    Borbulevych, Oleg Y.; Plumley, Joshua A.; Martin, Roger I.; Merz, Kenneth M.; Westerhoff, Lance M.

    2014-01-01

    Macromolecular crystallographic refinement relies on sometimes dubious stereochemical restraints and rudimentary energy functionals to ensure the correct geometry of the model of the macromolecule and any covalently bound ligand(s). The ligand stereochemical restraint file (CIF) requires a priori understanding of the ligand geometry within the active site, and creation of the CIF is often an error-prone process owing to the great variety of potential ligand chemistry and structure. Stereochemical restraints have been replaced with more robust functionals through the integration of the linear-scaling, semiempirical quantum-mechanics (SE-QM) program DivCon with the PHENIX X-ray refinement engine. The PHENIX/DivCon package has been thoroughly validated on a population of 50 protein–ligand Protein Data Bank (PDB) structures with a range of resolutions and chemistry. The PDB structures used for the validation were originally refined utilizing various refinement packages and were published within the past five years. PHENIX/DivCon does not utilize CIF(s), link restraints and other parameters for refinement and hence it does not make as many a priori assumptions about the model. Across the entire population, the method results in reasonable ligand geometries and low ligand strains, even when the original refinement exhibited difficulties, indicating that PHENIX/DivCon is applicable to both single-structure and high-throughput crystallography. PMID:24816093

  19. 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.

  20. Structural transformations and melting in neon clusters: quantum versus classical mechanics.

    PubMed

    Frantsuzov, Pavel A; Meluzzi, Dario; Mandelshtam, Vladimir A

    2006-03-24

    The extraordinary complexity of Lennard-Jones (LJ) clusters, which exhibit numerous structures and "phases" when their size or temperature is varied, presents a great challenge for accurate numerical simulations, even without accounting for quantum effects. To study the latter, we utilize the variational Gaussian wave packet method in conjunction with the exchange Monte Carlo sampling technique. We show that the quantum nature of neon clusters has a substantial effect on their size-temperature "phase diagrams," particularly the critical parameters of certain structural transformations. We also give a numerical confirmation that none of the nonicosahedral structures observed for some classical LJ clusters are favorable in the quantum case.

  1. Prediction of {sup 2}D Rydberg energy levels of {sup 6}Li and {sup 7}Li based on very accurate quantum mechanical calculations performed with explicitly correlated Gaussian functions

    SciTech Connect

    Bubin, Sergiy; Sharkey, Keeper L.; Adamowicz, Ludwik

    2013-04-28

    Very accurate variational nonrelativistic finite-nuclear-mass calculations employing all-electron explicitly correlated Gaussian basis functions are carried out for six Rydberg {sup 2}D states (1s{sup 2}nd, n= 6, Horizontal-Ellipsis , 11) of the {sup 7}Li and {sup 6}Li isotopes. The exponential parameters of the Gaussian functions are optimized using the variational method with the aid of the analytical energy gradient determined with respect to these parameters. The experimental results for the lower states (n= 3, Horizontal-Ellipsis , 6) and the calculated results for the higher states (n= 7, Horizontal-Ellipsis , 11) fitted with quantum-defect-like formulas are used to predict the energies of {sup 2}D 1s{sup 2}nd states for {sup 7}Li and {sup 6}Li with n up to 30.

  2. Effect of surface corrugation on low temperature phases of adsorbed (p-H2)7: A quantum path integral Monte Carlo study

    NASA Astrophysics Data System (ADS)

    Cruz, Anthony; López, Gustavo E.

    2014-04-01

    By using path integral Monte Carlo simulations coupled to Replica Exchange algorithms, various phases of (p-H2)7 physically adsorbed on a model graphite surface were identified at low temperatures. At T=0.5 K, the expected superfluid phase was observed for flat and slightly corrugated surfaces. At intermediate and high corrugations, a "supersolid" phase in C7/16 registry and a solid phase in C1/3 registry were observed, respectively. At higher temperatures, the superfluid is converted to a fluid and the "supersolid" to a solid.

  3. Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State (17)O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds.

    PubMed

    Rorick, Amber; Michael, Matthew A; Yang, Liu; Zhang, Yong

    2015-09-03

    Oxygen is an important element in most biologically significant molecules, and experimental solid-state (17)O NMR studies have provided numerous useful structural probes to study these systems. However, computational predictions of solid-state (17)O NMR chemical shift tensor properties are still challenging in many cases, and in particular, each of the prior computational works is basically limited to one type of oxygen-containing system. This work provides the first systematic study of the effects of geometry refinement, method, and basis sets for metal and nonmetal elements in both geometry optimization and NMR property calculations of some biologically relevant oxygen-containing compounds with a good variety of XO bonding groups (X = H, C, N, P, and metal). The experimental range studied is of 1455 ppm, a major part of the reported (17)O NMR chemical shifts in organic and organometallic compounds. A number of computational factors toward relatively general and accurate predictions of (17)O NMR chemical shifts were studied to provide helpful and detailed suggestions for future work. For the studied kinds of oxygen-containing compounds, the best computational approach results in a theory-versus-experiment correlation coefficient (R(2)) value of 0.9880 and a mean absolute deviation of 13 ppm (1.9% of the experimental range) for isotropic NMR shifts and an R(2) value of 0.9926 for all shift-tensor properties. These results shall facilitate future computational studies of (17)O NMR chemical shifts in many biologically relevant systems, and the high accuracy may also help the refinement and determination of active-site structures of some oxygen-containing substrate-bound proteins.

  4. Quantum mechanics/molecular mechanics minimum free-energy path for accurate reaction energetics in solution and enzymes: Sequential sampling and optimization on the potential of mean force surface

    NASA Astrophysics Data System (ADS)

    Hu, Hao; Lu, Zhenyu; Parks, Jerry M.; Burger, Steven K.; Yang, Weitao

    2008-01-01

    To accurately determine the reaction path and its energetics for enzymatic and solution-phase reactions, we present a sequential sampling and optimization approach that greatly enhances the efficiency of the ab initio quantum mechanics/molecular mechanics minimum free-energy path (QM/MM-MFEP) method. In the QM/MM-MFEP method, the thermodynamics of a complex reaction system is described by the potential of mean force (PMF) surface of the quantum mechanical (QM) subsystem with a small number of degrees of freedom, somewhat like describing a reaction process in the gas phase. The main computational cost of the QM/MM-MFEP method comes from the statistical sampling of conformations of the molecular mechanical (MM) subsystem required for the calculation of the QM PMF and its gradient. In our new sequential sampling and optimization approach, we aim to reduce the amount of MM sampling while still retaining the accuracy of the results by first carrying out MM phase-space sampling and then optimizing the QM subsystem in the fixed-size ensemble of MM conformations. The resulting QM optimized structures are then used to obtain more accurate sampling of the MM subsystem. This process of sequential MM sampling and QM optimization is iterated until convergence. The use of a fixed-size, finite MM conformational ensemble enables the precise evaluation of the QM potential of mean force and its gradient within the ensemble, thus circumventing the challenges associated with statistical averaging and significantly speeding up the convergence of the optimization process. To further improve the accuracy of the QM/MM-MFEP method, the reaction path potential method developed by Lu and Yang [Z. Lu and W. Yang, J. Chem. Phys. 121, 89 (2004)] is employed to describe the QM/MM electrostatic interactions in an approximate yet accurate way with a computational cost that is comparable to classical MM simulations. The new method was successfully applied to two example reaction processes, the

  5. Quantum mechanics/molecular mechanics minimum free-energy path for accurate reaction energetics in solution and enzymes: Sequential sampling and optimization on the potential of mean force surface

    SciTech Connect

    Hu Hao; Lu Zhenyu; Parks, Jerry M.; Burger, Steven K.; Yang Weitao

    2008-01-21

    To accurately determine the reaction path and its energetics for enzymatic and solution-phase reactions, we present a sequential sampling and optimization approach that greatly enhances the efficiency of the ab initio quantum mechanics/molecular mechanics minimum free-energy path (QM/MM-MFEP) method. In the QM/MM-MFEP method, the thermodynamics of a complex reaction system is described by the potential of mean force (PMF) surface of the quantum mechanical (QM) subsystem with a small number of degrees of freedom, somewhat like describing a reaction process in the gas phase. The main computational cost of the QM/MM-MFEP method comes from the statistical sampling of conformations of the molecular mechanical (MM) subsystem required for the calculation of the QM PMF and its gradient. In our new sequential sampling and optimization approach, we aim to reduce the amount of MM sampling while still retaining the accuracy of the results by first carrying out MM phase-space sampling and then optimizing the QM subsystem in the fixed-size ensemble of MM conformations. The resulting QM optimized structures are then used to obtain more accurate sampling of the MM subsystem. This process of sequential MM sampling and QM optimization is iterated until convergence. The use of a fixed-size, finite MM conformational ensemble enables the precise evaluation of the QM potential of mean force and its gradient within the ensemble, thus circumventing the challenges associated with statistical averaging and significantly speeding up the convergence of the optimization process. To further improve the accuracy of the QM/MM-MFEP method, the reaction path potential method developed by Lu and Yang [Z. Lu and W. Yang, J. Chem. Phys. 121, 89 (2004)] is employed to describe the QM/MM electrostatic interactions in an approximate yet accurate way with a computational cost that is comparable to classical MM simulations. The new method was successfully applied to two example reaction processes, the

  6. 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.

  7. Monte Carlo Benchmark

    SciTech Connect

    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.

  8. Ab Initio Geometry and Bright Excitation of Carotenoids: Quantum Monte Carlo and Many Body Green’s Function Theory Calculations on Peridinin

    PubMed Central

    Coccia, Emanuele; Varsano, Daniele; Guidoni, Leonardo

    2016-01-01

    In this letter, we report the singlet ground state structure of the full carotenoid peridinin by means of variational Monte Carlo (VMC) calculations. The VMC relaxed geometry has an average bond length alternation of 0.1165(10) Å, larger than the values obtained by DFT (PBE, B3LYP, and CAM-B3LYP) and shorter than that calculated at the Hartree–Fock (HF) level. TDDFT and EOM-CCSD calculations on a reduced peridinin model confirm the HOMO–LUMO major contribution of the Bu+-like (S2) bright excited state. Many Body Green’s Function Theory (MBGFT) calculations of the vertical excitation energy of the Bu+-like state for the VMC structure (VMC/MBGFT) provide an excitation energy of 2.62 eV, in agreement with experimental results in n-hexane (2.72 eV). The dependence of the excitation energy on the bond length alternation in the MBGFT and TDDFT calculations with different functionals is discussed. PMID:26580027

  9. 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.

  10. A semiempirical surface scattering model for quantum corrected full-band Monte-Carlo simulation of biaxially strained Si/SiGe NMOSFETs

    NASA Astrophysics Data System (ADS)

    Pham, A. T.; Nguyen, C. D.; Jungemann, C.; Meinerzhagen, B.

    2006-04-01

    A new semiempirical surface scattering model for electrons in strained Si devices including a quantum correction has been developed and implemented into our FBMC simulator. The strain is assumed to be consistent with pseudomorphic growth on a relaxed SiGe buffer. By introducing a few additional terms into the physical scattering rates which depend on the Ge-content in the SiGe buffer, the new surface scattering model can excellently reproduce low-field inversion layer mobility measurements for a wide range of Ge-content (0-30%) and substrate doping levels (10 16-5.5 × 10 18 cm -3). As a device example, an NMOSFET with 23 nm gate length with and without a strained Si channel has been simulated by the new FBMC model.

  11. Semistochastic Projector Monte Carlo Method

    NASA Astrophysics Data System (ADS)

    Petruzielo, F. R.; Holmes, A. A.; Changlani, Hitesh J.; Nightingale, M. P.; Umrigar, C. J.

    2012-12-01

    We introduce a semistochastic implementation of the power method to compute, for very large matrices, the dominant eigenvalue and expectation values involving the corresponding eigenvector. The method is semistochastic in that the matrix multiplication is partially implemented numerically exactly and partially stochastically with respect to expectation values only. Compared to a fully stochastic method, the semistochastic approach significantly reduces the computational time required to obtain the eigenvalue to a specified statistical uncertainty. This is demonstrated by the application of the semistochastic quantum Monte Carlo method to systems with a sign problem: the fermion Hubbard model and the carbon dimer.

  12. Ground State Geometries of Polyacetylene Chains from Many-Particle Quantum Mechanics.

    PubMed

    Barborini, Matteo; Guidoni, Leonardo

    2015-09-08

    Due to the crucial role played by electron correlation, the accurate determination of ground state geometries of π-conjugated molecules is still a challenge for many quantum chemistry methods. Because of the high parallelism of the algorithms and their explicit treatment of electron correlation effects, Quantum Monte Carlo calculations can offer an accurate and reliable description of the electronic states and of the geometries of such systems, competing with traditional quantum chemistry approaches. Here, we report the structural properties of polyacetylene chains H-(C₂H₂)(N)-H up to N = 12 acetylene units, by means of Variational Monte Carlo (VMC) calculations based on the multi-determinant Jastrow Antisymmetrized Geminal Power (JAGP) wave function. This compact ansatz can provide for such systems an accurate description of the dynamical electronic correlation as recently detailed for the 1,3-butadiene molecule [J. Chem. Theory Comput. 2015 11 (2), 508-517]. The calculated Bond Length Alternation (BLA), namely the difference between the single and double carbon bonds, extrapolates, for N → ∞, to a value of 0.0910(7) Å, compatible with the experimental data. An accurate analysis was able to distinguish between the influence of the multi-determinantal AGP expansion and of the Jastrow factor on the geometrical properties of the fragments. Our size-extensive and self-interaction-free results provide new and accurate ab initio references for the structures of the ground state of polyenes.

  13. Monte Carlo Example Programs

    SciTech Connect

    Kalos, M.

    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.

  14. 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.

  15. A versatile phenomenological model for the S-shaped temperature dependence of photoluminescence energy for an accurate determination of the exciton localization energy in bulk and quantum well structures

    NASA Astrophysics Data System (ADS)

    Dixit, V. K.; Porwal, S.; Singh, S. D.; Sharma, T. K.; Ghosh, Sandip; Oak, S. M.

    2014-02-01

    Temperature dependence of the photoluminescence (PL) peak energy of bulk and quantum well (QW) structures is studied by using a new phenomenological model for including the effect of localized states. In general an anomalous S-shaped temperature dependence of the PL peak energy is observed for many materials which is usually associated with the localization of excitons in band-tail states that are formed due to potential fluctuations. Under such conditions, the conventional models of Varshni, Viña and Passler fail to replicate the S-shaped temperature dependence of the PL peak energy and provide inconsistent and unrealistic values of the fitting parameters. The proposed formalism persuasively reproduces the S-shaped temperature dependence of the PL peak energy and provides an accurate determination of the exciton localization energy in bulk and QW structures along with the appropriate values of material parameters. An example of a strained InAs0.38P0.62/InP QW is presented by performing detailed temperature and excitation intensity dependent PL measurements and subsequent in-depth analysis using the proposed model. Versatility of the new formalism is tested on a few other semiconductor materials, e.g. GaN, nanotextured GaN, AlGaN and InGaN, which are known to have a significant contribution from the localized states. A quantitative evaluation of the fractional contribution of the localized states is essential for understanding the temperature dependence of the PL peak energy of bulk and QW well structures having a large contribution of the band-tail states.

  16. 3D electro-thermal Monte Carlo study of transport in confined silicon devices

    NASA Astrophysics Data System (ADS)

    Mohamed, Mohamed Y.

    The simultaneous explosion of portable microelectronics devices and the rapid shrinking of microprocessor size have provided a tremendous motivation to scientists and engineers to continue the down-scaling of these devices. For several decades, innovations have allowed components such as transistors to be physically reduced in size, allowing the famous Moore's law to hold true. As these transistors approach the atomic scale, however, further reduction becomes less probable and practical. As new technologies overcome these limitations, they face new, unexpected problems, including the ability to accurately simulate and predict the behavior of these devices, and to manage the heat they generate. This work uses a 3D Monte Carlo (MC) simulator to investigate the electro-thermal behavior of quasi-one-dimensional electron gas (1DEG) multigate MOSFETs. In order to study these highly confined architectures, the inclusion of quantum correction becomes essential. To better capture the influence of carrier confinement, the electrostatically quantum-corrected full-band MC model has the added feature of being able to incorporate subband scattering. The scattering rate selection introduces quantum correction into carrier movement. In addition to the quantum effects, scaling introduces thermal management issues due to the surge in power dissipation. Solving these problems will continue to bring improvements in battery life, performance, and size constraints of future devices. We have coupled our electron transport Monte Carlo simulation to Aksamija's phonon transport so that we may accurately and efficiently study carrier transport, heat generation, and other effects at the transistor level. This coupling utilizes anharmonic phonon decay and temperature dependent scattering rates. One immediate advantage of our coupled electro-thermal Monte Carlo simulator is its ability to provide an accurate description of the spatial variation of self-heating and its effect on non

  17. 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.

  18. Self-learning Monte Carlo method

    NASA Astrophysics Data System (ADS)

    Liu, Junwei; Qi, Yang; Meng, Zi Yang; Fu, Liang

    2017-01-01

    Monte Carlo simulation is an unbiased numerical tool for studying classical and quantum many-body systems. One of its bottlenecks is the lack of a general and efficient update algorithm for large size systems close to the phase transition, for which local updates perform badly. In this Rapid Communication, we propose a general-purpose Monte Carlo method, dubbed self-learning Monte Carlo (SLMC), in which an efficient update algorithm is first learned from the training data generated in trial simulations and then used to speed up the actual simulation. We demonstrate the efficiency of SLMC in a spin model at the phase transition point, achieving a 10-20 times speedup.

  19. Equation of state of metallic hydrogen from coupled electron-ion Monte Carlo simulations.

    PubMed

    Morales, Miguel A; Pierleoni, Carlo; Ceperley, D M

    2010-02-01

    We present a study of hydrogen at pressures higher than molecular dissociation using the coupled electron-ion Monte Carlo method. These calculations use the accurate reptation quantum Monte Carlo method to estimate the electronic energy and pressure while doing a Monte Carlo simulation of the protons. In addition to presenting simulation results for the equation of state over a large region of the phase diagram, we report the free energy obtained by thermodynamic integration. We find very good agreement with density-functional theory based molecular-dynamics calculations for pressures beyond 600 GPa and densities above rho=1.4 g/cm(3) , both for thermodynamic and structural properties. This agreement provides a strong support to the different approximations employed in the density-functional treatment of the system, specifically the approximate exchange-correlation potential and the use of pseudopotentials for the range of densities considered. We find disagreement with chemical models, which suggests that a reinvestigation of planetary models--previously constructed using the Saumon-Chabrier-Van Horn equations of state--might be needed.

  20. A quantum-quantum Metropolis algorithm.

    PubMed

    Yung, Man-Hong; Aspuru-Guzik, Alán

    2012-01-17

    The classical Metropolis sampling method is a cornerstone of many statistical modeling applications that range from physics, chemistry, and biology to economics. This method is particularly suitable for sampling the thermal distributions of classical systems. The challenge of extending this method to the simulation of arbitrary quantum systems is that, in general, eigenstates of quantum Hamiltonians cannot be obtained efficiently with a classical computer. However, this challenge can be overcome by quantum computers. Here, we present a quantum algorithm which fully generalizes the classical Metropolis algorithm to the quantum domain. The meaning of quantum generalization is twofold: The proposed algorithm is not only applicable to both classical and quantum systems, but also offers a quantum speedup relative to the classical counterpart. Furthermore, unlike the classical method of quantum Monte Carlo, this quantum algorithm does not suffer from the negative-sign problem associated with fermionic systems. Applications of this algorithm include the study of low-temperature properties of quantum systems, such as the Hubbard model, and preparing the thermal states of sizable molecules to simulate, for example, chemical reactions at an arbitrary temperature.

  1. Calculating potential energy curves with fixed-node diffusion Monte Carlo: CO and N2

    NASA Astrophysics Data System (ADS)

    Powell, Andrew D.; Dawes, Richard

    2016-12-01

    This study reports on the prospect for the routine use of Quantum Monte Carlo (QMC) for the electronic structure problem, applying fixed-node Diffusion Monte Carlo (DMC) to generate highly accurate Born-Oppenheimer potential energy curves (PECs) for small molecular systems. The singlet ground electronic states of CO and N2 were used as test cases. The PECs obtained by DMC employing multiconfigurational trial wavefunctions were compared with those obtained by conventional high-accuracy electronic structure methods such as multireference configuration interaction and/or the best available empirical spectroscopic curves. The goal was to test whether a straightforward procedure using available QMC codes could be applied robustly and reliably. Results obtained with DMC codes were found to be in close agreement with the benchmark PECs, and the n3 scaling with the number of electrons (compared with n7 or worse for conventional high-accuracy quantum chemistry) could be advantageous depending on the system size. Due to a large pre-factor in the scaling, for the small systems tested here, it is currently still much more computationally intensive to compute PECs with QMC. Nevertheless, QMC algorithms are particularly well-suited to large-scale parallelization and are therefore likely to become more relevant for future massively parallel hardware architectures.

  2. Thermodynamics and renormalized quasiparticles in the vicinity of the dilute Bose gas quantum critical point in two dimensions

    NASA Astrophysics Data System (ADS)

    Krieg, Jan; Strassel, Dominik; Streib, Simon; Eggert, Sebastian; Kopietz, Peter

    2017-01-01

    We use the functional renormalization group (FRG) to derive analytical expressions for thermodynamic observables (density, pressure, entropy, and compressibility) as well as for single-particle properties (wave-function renormalization and effective mass) of interacting bosons in two dimensions as a function of temperature T and chemical potential μ . We focus on the quantum disordered and the quantum critical regime close to the dilute Bose gas quantum critical point. Our approach is based on a truncated vertex expansion of the hierarchy of FRG flow equations and the decoupling of the two-body contact interaction in the particle-particle channel using a suitable Hubbard-Stratonovich transformation. Our analytic FRG results extend previous analytical renormalization-group calculations for thermodynamic observables at μ =0 to finite values of μ . To confirm the validity of our FRG approach, we have also performed quantum Monte Carlo simulations to obtain the magnetization, susceptibility, and correlation length of the two-dimensional spin-1 /2 quantum X Y model with coupling J in a regime where its quantum critical behavior is controlled by the dilute Bose gas quantum critical point. We find that our analytical results describe the Monte Carlo data for μ ≤0 rather accurately up to relatively high temperatures T ≲0.1 J .

  3. Multi-Subband Ensemble Monte Carlo simulation of bulk MOSFETs for the 32 nm-node and beyond

    NASA Astrophysics Data System (ADS)

    Sampedro, C.; Gámiz, F.; Godoy, A.; Valín, R.; García-Loureiro, A.; Rodríguez, N.; Tienda-Luna, I. M.; Martinez-Carricondo, F.; Biel, B.

    2011-11-01

    With the 32 nm node in mass production, simulation tools have to include quantum effects to correctly describe the behavior of the devices. The Multi-Subband Ensemble Monte Carlo (MSB-EMC) approach constitutes today's most accurate method for the study of nanodevices with important applications to SOI devices. However, the study of bulk devices with MSB-EMC codes presents practical limitations arising from the device geometry and the existence of a semi-infinite quantum well. This work presents a in-depth study of such issues to properly apply the Multi-Subband approach to bulk devices. The developed simulator has been used to study bulk-nMOSFETs for the 32 nm technological node and beyond which still constitutes the mainstream technology in commercial ICs and to compare them to their SOI counterparts.

  4. 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.

  5. Few-body route to one-dimensional quantum liquids

    NASA Astrophysics Data System (ADS)

    Valiente, Manuel; Öhberg, Patrik

    2016-11-01

    Gapless many-body quantum systems in one spatial dimension are universally described by the Luttinger liquid effective theory at low energies. Essentially, only two parameters enter the effective low-energy description, namely, the speed of sound and the Luttinger parameter. These are highly system dependent and their calculation requires accurate nonperturbative solutions of the many-body problem. Here we present a simple theoretical method that only uses collisional information to extract the low-energy properties of spinless one-dimensional systems. Our results are in remarkable agreement with available results for integrable models and from large-scale Monte Carlo simulations of one-dimensional helium and hydrogen isotopes. Moreover, we estimate theoretically the critical point for spinodal decomposition in one-dimensional 4He and show that the exponent governing the divergence of the Luttinger parameter near the critical point is exactly 1/2, in excellent agreement with Monte Carlo simulations.

  6. Quantum Ice : Experimental Signatures

    NASA Astrophysics Data System (ADS)

    Shannon, Nic; Benton, Owen; Sikora, Olga; Penc, Karlo; McClarty, Paul; Pollmann, Frank; Moessner, Roderich; Fulde, Peter

    2012-02-01

    ``Quantum Spin Ice'' materials have attracted considerable attention as three-dimensional examples of quantum spin liquids. Recently, we have used zero-temperature Quantum Monte Carlo simulation to explore one possible scenario for these materials, confirming the possibility of a ``quantum ice'' state driven by quantum tunnelling between an extensive number of different spin-ice configurations [1]. Here we address the simple question : what would such a quantum ice look like in experiment ? We focus in particular on the fate of ``pinch point'' singularities seen in neutron scattering experiments on spin ice materials, showing how these are suppressed and ultimately eliminated as the system is cooled to its ground state [1,2]. [4pt] [1] N. Shannon et al., arXiv:1105.4196[0pt] [2] O. Benton et al., in preparation.

  7. 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.

  8. Computer simulation of liquid-vapor coexistence of confined quantum fluids.

    PubMed

    Trejos, Víctor M; Gil-Villegas, Alejandro; Martinez, Alejandro

    2013-11-14

    The liquid-vapor coexistence (LV) of bulk and confined quantum fluids has been studied by Monte Carlo computer simulation for particles interacting via a semiclassical effective pair potential Veff(r) = VLJ + VQ, where VLJ is the Lennard-Jones 12-6 potential (LJ) and VQ is the first-order Wigner-Kirkwood (WK-1) quantum potential, that depends on β = 1∕kT and de Boer's quantumness parameter Λ=h/σ√mε, where k and h are the Boltzmann's and Planck's constants, respectively, m is the particle's mass, T is the temperature of the system, and σ and ε are the LJ potential parameters. The non-conformal properties of the system of particles interacting via the effective pair potential Veff(r) are due to Λ, since the LV phase diagram is modified by varying Λ. We found that the WK-1 system gives an accurate description of the LV coexistence for bulk phases of several quantum fluids, obtained by the Gibbs Ensemble Monte Carlo method (GEMC). Confinement effects were introduced using the Canonical Ensemble (NVT) to simulate quantum fluids contained within parallel hard walls separated by a distance Lp, within the range 2σ ≤ Lp ≤ 6σ. The critical temperature of the system is reduced by decreasing Lp and increasing Λ, and the liquid-vapor transition is not longer observed for Lp∕σ < 2, in contrast to what has been observed for the classical system.

  9. Variational Monte Carlo method in the presence of spin-orbit interaction and its application to Kitaev and Kitaev-Heisenberg models

    NASA Astrophysics Data System (ADS)

    Kurita, Moyuru; Yamaji, Youhei; Morita, Satoshi; Imada, Masatoshi

    2015-07-01

    We propose an accurate variational Monte Carlo method applicable in the presence of the strong spin-orbit interactions. The algorithm is applicable even in a wider class of Hamiltonians that do not have the spin-rotational symmetry. Our variational wave functions consist of generalized Pfaffian-Slater wave functions that involve mixtures of singlet and triplet Cooper pairs, Jastrow-Gutzwiller-type projections, and quantum number projections. The generalized wave functions allow describing states including a wide class of symmetry-broken states, ranging from magnetic and/or charge ordered states to superconducting states and their fluctuations, on equal footing without any ad hoc ansatz for variational wave functions. We detail our optimization scheme for the generalized Pfaffian-Slater wave functions with complex-number variational parameters. Generalized quantum number projections are also introduced, which imposes the conservation of not only the momentum quantum number but also Wilson loops. As a demonstration of the capability of the present variational Monte Carlo method, the accuracy and efficiency is tested for the Kitaev and Kitaev-Heisenberg models, which lack the SU(2) spin-rotational symmetry except at the Heisenberg limit. The Kitaev model serves as a critical benchmark of the present method: The exact ground state of the model is a typical gapless quantum spin liquid far beyond the reach of simple mean-field wave functions. The newly introduced quantum number projections precisely reproduce the ground state degeneracy of the Kitaev spin liquids, in addition to their ground state energy. An application to a closely related itinerant model described by a multiorbital Hubbard model with the spin-orbit interaction also shows promising benchmark results. The strong-coupling limit of the multiorbital Hubbard model is indeed described by the Kitaev model. Our framework offers accurate solutions for the systems where strong electron correlation and spin

  10. Quantum Simulations for Dense Matter

    SciTech Connect

    Ceperley, David M

    2010-06-07

    High pressure systems are important, for example, to understand the interiors of giant planets (Jupiter and Saturn), for experiments at NIF (the National Ignition Facility at Livermore) related to inertially confined fusion and for other interests of DOE. In this project, we are developing innovative simulation methods (Quantum Monte Carlo methods) to allow more accurate calculation of properties of systems under extreme conditions of pressure and temperature. These methods can use the power of current day supercomputers made of very many processors, starting from the basic equations of physics to model quantum phenomena important at the microscopic scale. During the grant period, we have settled two important questions of the physics of hydrogen and helium under extreme conditions. We have found the pressures and temperatures when hydrogen and helium mix together; this is important to understand the difference of the interiors of the planets Jupiter and Saturn. Secondly, we have shown that there exists a sharp transition as a function of pressure between molecular and atomic liquid hydrogen at temperatures below 2000K. This prediction can be confirmed with high pressure experiments.

  11. Fermionic path-integral Monte Carlo results for the uniform electron gas at finite temperature.

    PubMed

    Filinov, V S; Fortov, V E; Bonitz, M; Moldabekov, Zh

    2015-03-01

    The uniform electron gas (UEG) at finite temperature has recently attracted substantial interest due to the experimental progress in the field of warm dense matter. To explain the experimental data, accurate theoretical models for high-density plasmas are needed that depend crucially on the quality of the thermodynamic properties of the quantum degenerate nonideal electrons and of the treatment of their interaction with the positive background. Recent fixed-node path-integral Monte Carlo (RPIMC) data are believed to be the most accurate for the UEG at finite temperature, but they become questionable at high degeneracy when the Brueckner parameter rs=a/aB--the ratio of the mean interparticle distance to the Bohr radius--approaches 1. The validity range of these simulations and their predictive capabilities for the UEG are presently unknown. This is due to the unknown quality of the used fixed nodes and of the finite-size scaling from N=33 simulated particles (per spin projection) to the macroscopic limit. To analyze these questions, we present alternative direct fermionic path integral Monte Carlo (DPIMC) simulations that are independent from RPIMC. Our simulations take into account quantum effects not only in the electron system but also in their interaction with the uniform positive background. Also, we use substantially larger particle numbers (up to three times more) and perform an extrapolation to the macroscopic limit. We observe very good agreement with RPIMC, for the polarized electron gas, up to moderate densities around rs=4, and larger deviations for the unpolarized case, for low temperatures. For higher densities (high electron degeneracy), rs≲1.5, both RPIMC and DPIMC are problematic due to the increased fermion sign problem.

  12. Robust, frequency-stable and accurate mid-IR laser spectrometer based on frequency comb metrology of quantum cascade lasers up-converted in orientation-patterned GaAs.

    PubMed

    Hansen, Michael G; Ernsting, Ingo; Vasilyev, Sergey V; Grisard, Arnaud; Lallier, Eric; Gérard, Bruno; Schiller, Stephan

    2013-11-04

    We demonstrate a robust and simple method for measurement, stabilization and tuning of the frequency of cw mid-infrared (MIR) lasers, in particular of quantum cascade lasers. The proof of principle is performed with a quantum cascade laser at 5.4 µm, which is upconverted to 1.2 µm by sum-frequency generation in orientation-patterned GaAs with the output of a standard high-power cw 1.5 µm fiber laser. Both the 1.2 µm and the 1.5 µm waves are measured by a standard Er:fiber frequency comb. Frequency measurement at the 100 kHz-level, stabilization to sub-10 kHz level, controlled frequency tuning and long-term stability are demonstrated.

  13. Quantum-instanton evaluation of the kinetic isotope effects.

    PubMed

    Vanícek, Jirí; Miller, William H; Castillo, Jesús F; Aoiz, F Javier

    2005-08-01

    A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum-instanton approximation for the rate constant and on the path-integral Metropolis-Monte Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method should be more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single tunneling path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H + H2 --> H2 + H. In all seven test cases, for temperatures between 250 and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than approximately 10%.

  14. Quantum instanton evaluation of the kinetic isotope effects

    SciTech Connect

    Vanicek, Jiri; Miller, William H.; Castillo, Jesus F.; Aoiz, F.Javier

    2005-04-19

    A general quantum-mechanical method for computing kinetic isotope effects is presented. The method is based on the quantum instanton approximation for the rate constant and on the path integral Metropolis Monte-Carlo evaluation of the Boltzmann operator matrix elements. It computes the kinetic isotope effect directly, using a thermodynamic integration with respect to the mass of the isotope, thus avoiding the more computationally expensive process of computing the individual rate constants. The method is more accurate than variational transition-state theories or the semiclassical instanton method since it does not assume a single reaction path and does not use a semiclassical approximation of the Boltzmann operator. While the general Monte-Carlo implementation makes the method accessible to systems with a large number of atoms, we present numerical results for the Eckart barrier and for the collinear and full three-dimensional isotope variants of the hydrogen exchange reaction H+H{sub 2} {yields} H{sub 2}+H. In all seven test cases, for temperatures between 250 K and 600 K, the error of the quantum instanton approximation for the kinetic isotope effects is less than {approx}10%.

  15. Variational study of the quantum phase transition in the bilayer Heisenberg model with bosonic RVB wavefunction.

    PubMed

    Liao, Haijun; Li, Tao

    2011-11-30

    We study the ground state phase diagram of the bilayer Heisenberg model on a square lattice with a bosonic resonating valence bond (RVB) wavefunction. The wavefunction has the form of a Gutzwiller projected Schwinger boson mean-field ground state and involves two variational parameters. We find the wavefunction provides an accurate description of the system on both sides of the quantum phase transition. In particular, through the analysis of the spin structure factor, ground state fidelity susceptibility and the Binder moment ratio Q(2), a continuous transition from the antiferromagnetic ordered state to the quantum disordered state is found at the critical coupling of α(c) = J(⊥)/J(∥) ≈ 2.62, in good agreement with the result of quantum Monte Carlo simulation. The critical exponent estimated from the finite size scaling analysis (1/ν ≈ 1.4) is consistent with that of the classical 3D Heisenberg universality class.

  16. Global quantum discord and quantum phase transition in XY model

    SciTech Connect

    Liu, Si-Yuan; Zhang, Yu-Ran; Yang, Wen-Li; Fan, Heng

    2015-11-15

    We study the relationship between the behavior of global quantum correlations and quantum phase transitions in XY model. We find that the two kinds of phase transitions in the studied model can be characterized by the features of global quantum discord (GQD) and the corresponding quantum correlations. We demonstrate that the maximum of the sum of all the nearest neighbor bipartite GQDs is effective and accurate for signaling the Ising quantum phase transition, in contrast, the sudden change of GQD is very suitable for characterizing another phase transition in the XY model. This may shed lights on the study of properties of quantum correlations in different quantum phases.

  17. Accurate Finite Difference Algorithms

    NASA Technical Reports Server (NTRS)

    Goodrich, John W.

    1996-01-01

    Two families of finite difference algorithms for computational aeroacoustics are presented and compared. All of the algorithms are single step explicit methods, they have the same order of accuracy in both space and time, with examples up to eleventh order, and they have multidimensional extensions. One of the algorithm families has spectral like high resolution. Propagation with high order and high resolution algorithms can produce accurate results after O(10(exp 6)) periods of propagation with eight grid points per wavelength.

  18. Accurate monotone cubic interpolation

    NASA Technical Reports Server (NTRS)

    Huynh, Hung T.

    1991-01-01

    Monotone piecewise cubic interpolants are simple and effective. They are generally third-order accurate, except near strict local extrema where accuracy degenerates to second-order due to the monotonicity constraint. Algorithms for piecewise cubic interpolants, which preserve monotonicity as well as uniform third and fourth-order accuracy are presented. The gain of accuracy is obtained by relaxing the monotonicity constraint in a geometric framework in which the median function plays a crucial role.

  19. Quantum Universe

    NASA Astrophysics Data System (ADS)

    Mukhanov, V. F.

    2016-10-01

    In March 2013, following an accurate processing of available measurement data, the Planck Scientific Collaboration published the highest-resolution photograph ever of the early Universe when it was only a few hundred thousand years old. The photograph showed galactic seeds in sufficient detail to test some nontrivial theoretical predictions made more than thirty years ago. Most amazing was that all predictions were confirmed to be remarkably accurate. With no exaggeration, we may consider it established experimentally that quantum physics, which is normally assumed to be relevant on the atomic and subatomic scale, also works on the scale of the entire Universe, determining its structure with all its galaxies, stars, and planets.

  20. Possible calcium centers for hydrogen storage applications: An accurate many-body study by AFQMC calculations with large basis sets

    NASA Astrophysics Data System (ADS)

    Purwanto, Wirawan; Krakauer, Henry; Zhang, Shiwei; Virgus, Yudistira

    2011-03-01

    Weak H2 physisorption energies present a significant challenge to first-principle theoretical modeling and prediction of materials for H storage. There has been controversy regarding the accuracy of DFT on systems involving Ca cations. We use the auxiliary-field quantum Monte Carlo (AFQMC) method to accurately predict the binding energy of Ca + , - 4{H}2 . AFQMC scales as Nbasis3and has demonstrated accuracy similar to or better than the gold-standard coupled cluster CCSD(T) method. We apply a modified Cholesky decomposition to achieve efficient Hubbard-Stratonovich transformation in AFQMC at large basis sizes. We employ the largest correlation consistent basis sets available, up to Ca/cc-pCV5Z, to extrapolate to the complete basis limit. The calculated potential energy curve exhibits binding with a double-well structure. Supported by DOE and NSF. Calculations were performed at OLCF Jaguar and CPD.

  1. Toward an accurate and efficient semiclassical surface hopping procedure for nonadiabatic problems.

    PubMed

    Herman, Michael F

    2005-10-20

    The derivation of a semiclassical surface hopping procedure from a formally exact solution of the Schrodinger equation is discussed. The fact that the derivation proceeds from an exact solution guarantees that all phase terms are completely and accurately included. Numerical evidence shows the method to be highly accurate. A Monte Carlo implementation of this method is considered, and recent work to significantly improve the statistical accuracy of the Monte Carlo approach is discussed.

  2. Photon beam description in PEREGRINE for Monte Carlo dose calculations

    SciTech Connect

    Cox, L. J., LLNL

    1997-03-04

    Goal of PEREGRINE is to provide capability for accurate, fast Monte Carlo calculation of radiation therapy dose distributions for routine clinical use and for research into efficacy of improved dose calculation. An accurate, efficient method of describing and sampling radiation sources is needed, and a simple, flexible solution is provided. The teletherapy source package for PEREGRINE, coupled with state-of-the-art Monte Carlo simulations of treatment heads, makes it possible to describe any teletherapy photon beam to the precision needed for highly accurate Monte Carlo dose calculations in complex clinical configurations that use standard patient modifiers such as collimator jaws, wedges, blocks, and/or multi-leaf collimators. Generic beam descriptions for a class of treatment machines can readily be adjusted to yield dose calculation to match specific clinical sites.

  3. 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.

  4. Quantum thermodynamics of general quantum processes.

    PubMed

    Binder, Felix; Vinjanampathy, Sai; Modi, Kavan; Goold, John

    2015-03-01

    Accurately describing work extraction from a quantum system is a central objective for the extension of thermodynamics to individual quantum systems. The concepts of work and heat are surprisingly subtle when generalizations are made to arbitrary quantum states. We formulate an operational thermodynamics suitable for application to an open quantum system undergoing quantum evolution under a general quantum process by which we mean a completely positive and trace-preserving map. We derive an operational first law of thermodynamics for such processes and show consistency with the second law. We show that heat, from the first law, is positive when the input state of the map majorizes the output state. Moreover, the change in entropy is also positive for the same majorization condition. This makes a strong connection between the two operational laws of thermodynamics.

  5. Monte Carlo Reliability Analysis.

    DTIC Science & Technology

    1987-10-01

    to Stochastic Processes , Prentice-Hall, Englewood Cliffs, NJ, 1975. (5) R. E. Barlow and F. Proscham, Statistical TheorX of Reliability and Life...Lewis and Z. Tu, "Monte Carlo Reliability Modeling by Inhomogeneous ,Markov Processes, Reliab. Engr. 16, 277-296 (1986). (4) E. Cinlar, Introduction

  6. Full-dimensional quantum calculations of vibrational levels of NH4+ and isotopomers on an accurate ab initio potential energy surface

    SciTech Connect

    Hua -Gen Yu; Han, Huixian; Guo, Hua

    2016-03-29

    Vibrational energy levels of the ammonium cation (NH4+) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4+ and ND4+ exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. As a result, the low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm–1.

  7. Excited Rotational States in Doped {4} He Clusters: a Diffusion Monte Carlo Analysis

    NASA Astrophysics Data System (ADS)

    Coccia, Emanuele

    2017-03-01

    We report an extension of diffusion Monte Carlo (DMC) to the calculation of the molecular rotational energies by means of the generalized, symmetry-adapted, imaginary-time correlation functions (SAITCFs) originally introduced in the reptation quantum Monte Carlo (RQMC) framework (Škrbić in J Phys Chem A 111:12749, 2007). We studied the a-type and b-type rotational lines of the CO(4 He)N clusters with N= 1-8 that correlate, in the dimer limit, with the end-over-end and free-rotor transitions. We compare the SAITCF-DMC results with accurate DVR (for the dimer case), RQMC and other DMC data, and with reference experimental findings (Surin in Phys Rev Lett 101:233401, 2008). A good agreement is generally found, but a systematic underestimation of the SAITCF-DMC rotational energies of the b-type series is observed. Sources of inaccuracy in our theoretical approach and in the computational protocol are discussed and analyzed in detail.

  8. Exploiting Locality in Quantum Computation for Quantum Chemistry.

    PubMed

    McClean, Jarrod R; Babbush, Ryan; Love, Peter J; Aspuru-Guzik, Alán

    2014-12-18

    Accurate prediction of chemical and material properties from first-principles quantum chemistry is a challenging task on traditional computers. Recent developments in quantum computation offer a route toward highly accurate solutions with polynomial cost; however, this solution still carries a large overhead. In this Perspective, we aim to bring together known results about the locality of physical interactions from quantum chemistry with ideas from quantum computation. We show that the utilization of spatial locality combined with the Bravyi-Kitaev transformation offers an improvement in the scaling of known quantum algorithms for quantum chemistry and provides numerical examples to help illustrate this point. We combine these developments to improve the outlook for the future of quantum chemistry on quantum computers.

  9. Fission Matrix Capability for MCNP Monte Carlo

    NASA Astrophysics Data System (ADS)

    Brown, Forrest; Carney, Sean; Kiedrowski, Brian; Martin, William

    2014-06-01

    We describe recent experience and results from implementing a fission matrix capability into the MCNP Monte Carlo code. The fission matrix can be used to provide estimates of the fundamental mode fission distribution, the dominance ratio, the eigenvalue spectrum, and higher mode forward and adjoint eigenfunctions of the fission neutron source distribution. It can also be used to accelerate the convergence of the power method iterations and to provide basis functions for higher-order perturbation theory. The higher-mode fission sources can be used in MCNP to determine higher-mode forward fluxes and tallies, and work is underway to provide higher-mode adjoint-weighted fluxes and tallies. Past difficulties and limitations of the fission matrix approach are overcome with a new sparse representation of the matrix, permitting much larger and more accurate fission matrix representations. The new fission matrix capabilities provide a significant advance in the state-of-the-art for Monte Carlo criticality calculations.

  10. 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.

  11. Accurate study on the quantum dynamics of the He + HeH(+) (X1Σ+) reaction on a new ab initio potential energy surface for the lowest 1(1)A' electronic singlet state.

    PubMed

    Xu, Wenwu; Zhang, Peiyu

    2013-02-21

    A time-dependent quantum wave packet method is used to investigate the dynamics of the He + HeH(+)(X(1)Σ(+)) reaction based on a new potential energy surface [Liang et al., J. Chem. Phys.2012, 136, 094307]. The coupled channel (CC) and centrifugal-sudden (CS) reaction probabilities as well as the total integral cross sections are calculated. A comparison of the results with and without Coriolis coupling revealed that the number of K states N(K) (K is the projection of the total angular momentum J on the body-fixed z axis) significantly influences the reaction threshold. The effective potential energy profiles of each N(K) for the He + HeH(+) reaction in a collinear geometry indicate that the barrier height gradually decreased with increased N(K). The calculated time evolution of CC and CS probability density distribution over the collision energy of 0.27-0.36 eV at total angular momentum J = 50 clearly suggests a lower reaction threshold of CC probabilities. The CC cross sections are larger than the CS results within the entire energy range, demonstrating that the Coriolis coupling effect can effectively promote the He + HeH(+) reaction.

  12. BIOACCESSIBILITY TESTS ACCURATELY ESTIMATE ...

    EPA Pesticide Factsheets

    Hazards of soil-borne Pb to wild birds may be more accurately quantified if the bioavailability of that Pb is known. To better understand the bioavailability of Pb to birds, we measured blood Pb concentrations in Japanese quail (Coturnix japonica) fed diets containing Pb-contaminated soils. Relative bioavailabilities were expressed by comparison with blood Pb concentrations in quail fed a Pb acetate reference diet. Diets containing soil from five Pb-contaminated Superfund sites had relative bioavailabilities from 33%-63%, with a mean of about 50%. Treatment of two of the soils with P significantly reduced the bioavailability of Pb. The bioaccessibility of the Pb in the test soils was then measured in six in vitro tests and regressed on bioavailability. They were: the “Relative Bioavailability Leaching Procedure” (RBALP) at pH 1.5, the same test conducted at pH 2.5, the “Ohio State University In vitro Gastrointestinal” method (OSU IVG), the “Urban Soil Bioaccessible Lead Test”, the modified “Physiologically Based Extraction Test” and the “Waterfowl Physiologically Based Extraction Test.” All regressions had positive slopes. Based on criteria of slope and coefficient of determination, the RBALP pH 2.5 and OSU IVG tests performed very well. Speciation by X-ray absorption spectroscopy demonstrated that, on average, most of the Pb in the sampled soils was sorbed to minerals (30%), bound to organic matter 24%, or present as Pb sulfate 18%. Ad

  13. 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.

  14. Fundamentals of Monte Carlo

    SciTech Connect

    Wollaber, Allan Benton

    2016-06-16

    This is a powerpoint presentation which serves as lecture material for the Parallel Computing summer school. It goes over the fundamentals of the Monte Carlo calculation method. The material is presented according to the following outline: Introduction (background, a simple example: estimating π), Why does this even work? (The Law of Large Numbers, The Central Limit Theorem), How to sample (inverse transform sampling, rejection), and An example from particle transport.

  15. Monte Carlo eikonal scattering

    NASA Astrophysics Data System (ADS)

    Gibbs, W. R.; Dedonder, J. P.

    2012-08-01

    Background: The eikonal approximation is commonly used to calculate heavy-ion elastic scattering. However, the full evaluation has only been done (without the use of Monte Carlo techniques or additional approximations) for α-α scattering.Purpose: Develop, improve, and test the Monte Carlo eikonal method for elastic scattering over a wide range of nuclei, energies, and angles.Method: Monte Carlo evaluation is used to calculate heavy-ion elastic scattering for heavy nuclei including the center-of-mass correction introduced in this paper and the Coulomb interaction in terms of a partial-wave expansion. A technique for the efficient expansion of the Glauber amplitude in partial waves is developed.Results: Angular distributions are presented for a number of nuclear pairs over a wide energy range using nucleon-nucleon scattering parameters taken from phase-shift analyses and densities from independent sources. We present the first calculations of the Glauber amplitude, without further approximation, and with realistic densities for nuclei heavier than helium. These densities respect the center-of-mass constraints. The Coulomb interaction is included in these calculations.Conclusion: The center-of-mass and Coulomb corrections are essential. Angular distributions can be predicted only up to certain critical angles which vary with the nuclear pairs and the energy, but we point out that all critical angles correspond to a momentum transfer near 1 fm-1.

  16. Accurate spectral color measurements

    NASA Astrophysics Data System (ADS)

    Hiltunen, Jouni; Jaeaeskelaeinen, Timo; Parkkinen, Jussi P. S.

    1999-08-01

    Surface color measurement is of importance in a very wide range of industrial applications including paint, paper, printing, photography, textiles, plastics and so on. For a demanding color measurements spectral approach is often needed. One can measure a color spectrum with a spectrophotometer using calibrated standard samples as a reference. Because it is impossible to define absolute color values of a sample, we always work with approximations. The human eye can perceive color difference as small as 0.5 CIELAB units and thus distinguish millions of colors. This 0.5 unit difference should be a goal for the precise color measurements. This limit is not a problem if we only want to measure the color difference of two samples, but if we want to know in a same time exact color coordinate values accuracy problems arise. The values of two instruments can be astonishingly different. The accuracy of the instrument used in color measurement may depend on various errors such as photometric non-linearity, wavelength error, integrating sphere dark level error, integrating sphere error in both specular included and specular excluded modes. Thus the correction formulas should be used to get more accurate results. Another question is how many channels i.e. wavelengths we are using to measure a spectrum. It is obvious that the sampling interval should be short to get more precise results. Furthermore, the result we get is always compromise of measuring time, conditions and cost. Sometimes we have to use portable syste or the shape and the size of samples makes it impossible to use sensitive equipment. In this study a small set of calibrated color tiles measured with the Perkin Elmer Lamda 18 and the Minolta CM-2002 spectrophotometers are compared. In the paper we explain the typical error sources of spectral color measurements, and show which are the accuracy demands a good colorimeter should have.

  17. Quantum-classical path integral. I. Classical memory and weak quantum nonlocality.

    PubMed

    Lambert, Roberto; Makri, Nancy

    2012-12-14

    We consider rigorous path integral descriptions of the dynamics of a quantum system coupled to a polyatomic environment, assuming that the latter is well approximated by classical trajectories. Earlier work has derived semiclassical or purely classical expressions for the influence functional from the environment, which should be sufficiently accurate for many situations, but the evaluation of quantum-(semi)classical path integral (QCPI) expressions has not been practical for large-scale simulation because the interaction with the environment introduces couplings nonlocal in time. In this work, we analyze the nature of the effects on a system from its environment in light of the observation [N. Makri, J. Chem. Phys. 109, 2994 (1998)] that true nonlocality in the path integral is a strictly quantum mechanical phenomenon. If the environment is classical, the path integral becomes local and can be evaluated in a stepwise fashion along classical trajectories of the free solvent. This simple "classical path" limit of QCPI captures fully the decoherence of the system via a classical mechanism. Small corrections to the classical path QCPI approximation may be obtained via an inexpensive random hop QCPI model, which accounts for some "back reaction" effects. Exploiting the finite length of nonlocality, we argue that further inclusion of quantum decoherence is possible via an iterative evaluation of the path integral. Finally, we show that the sum of the quantum amplitude factors with respect to the system paths leads to a smooth integrand as a function of trajectory initial conditions, allowing the use of Monte Carlo methods for the multidimensional phase space integral.

  18. Monte Carlo Simulation of an Arc Therapy Treatment by Means of a PC Distribution Model

    NASA Astrophysics Data System (ADS)

    Leal, A.; Sánchez-Doblado, F.; Perucha, M.; Rincón, M.; Arráns, R.; Bernal, C.; Carrasco, E.

    It would be always desirable to have an independent assessment of a planning system. Monte Carlo (MC) offers an accurate way of checking dose distribution in non homogeneous volumes. Nevertheless, its main drawback is the long processing times needed.

  19. Monte Carlo simulation by computer for life-cycle costing

    NASA Technical Reports Server (NTRS)

    Gralow, F. H.; Larson, W. J.

    1969-01-01

    Prediction of behavior and support requirements during the entire life cycle of a system enables accurate cost estimates by using the Monte Carlo simulation by computer. The system reduces the ultimate cost to the procuring agency because it takes into consideration the costs of initial procurement, operation, and maintenance.

  20. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.