Science.gov

Sample records for coupled cluster singles

  1. Coupled cluster Green function: Model involving single and double excitations

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol; Shelton, William A.

    2016-04-14

    In this paper we report on the parallel implementation of the coupled-cluster (CC) Green function formulation (GF-CC) employing single and double excitations in the cluster operator (GF-CCSD). The detailed description of the underlying algorithm is provided, including the structure of ionization-potential- and electron-affinity-type intermediate tensors which enable to formulate GF-CC approach in a computationally feasible form. Several examples including calculations of ionization-potentials and electron a*ffinities for benchmark systems, which are juxtaposed against the experimental values, provide an illustration of the accuracies attainable in the GFCCSD simulations. We also discuss the structure of the CCSD self energies and discuss approximation that are geared to reduce the computational cost while maintaining the pole structure of the full GF-CCSD approach.

  2. Coupled-cluster singles and doubles for extended systems

    NASA Astrophysics Data System (ADS)

    Hirata, So; Podeszwa, Rafał; Tobita, Motoi; Bartlett, Rodney J.

    2004-02-01

    Coupled-cluster theory with connected single and double excitation operators (CCSD) and related approximations, such as linearized CCSD, quadratic configuration interaction with single and double excitation operators, coupled-cluster with connected double excitation operator (CCD), linearized CCD, approximate CCD, and second- and third-order many-body perturbation theories, are formulated and implemented for infinitely extended one-dimensional systems (polymers), on the basis of the periodic boundary conditions and distance-based screening of integrals, density matrix elements, and excitation amplitudes. The variation of correlation energies with the truncation radii of short- and long-range lattice sums and with the number of wave vector sampling points in the first Brillouin zone is examined for polyethylene, polyacetylene, and polyyne, and is shown to be a function of the degree of π-electron conjugation or the fundamental band gaps. The t2 and t1 amplitudes in the atomic orbital (AO) basis are obtained by first computing the t amplitudes in the Bloch-orbital basis and subsequently back-transforming them into the AO basis. The plot of these AO-based t amplitudes as a function of unit cells also indicates that the t2 amplitudes of polyacetylene and polyyne exhibit appreciably slower decay than those of polyethylene, although the asymptotic decay behavior is invariably 1/r3. The AO-based t1 amplitudes appear to correlate strongly with the electronic structure, and they decay seemingly exponentially for polyethylene whereas they stay at a constant magnitude across the seventh nearest neighbors of polyacetylene and polyyne, which attests to far reaching effects of nondynamical electron correlation mediated by orbital rotation. Nonetheless, the unit cell contributions to the correlation energies taper below 10-6 hartree after 15 Å for all three polymers. The basis set dependence of the decay behavior of t2 amplitudes is also examined for linear hydrogen fluoride

  3. Alternative single-reference coupled cluster approaches for multireference problems: the simpler, the better.

    PubMed

    Evangelista, Francesco A

    2011-06-14

    We report a general implementation of alternative formulations of single-reference coupled cluster theory (extended, unitary, and variational) with arbitrary-order truncation of the cluster operator. These methods are applied to compute the energy of Ne and the equilibrium properties of HF and C(2). Potential energy curves for the dissociation of HF and the BeH(2) model computed with the extended, variational, and unitary coupled cluster approaches are compared to those obtained from the multireference coupled cluster approach of Mukherjee et al. [J. Chem. Phys. 110, 6171 (1999)] and the internally contracted multireference coupled cluster approach [F. A. Evangelista and J. Gauss, J. Chem. Phys. 134, 114102 (2011)]. In the case of Ne, HF, and C(2), the alternative coupled cluster approaches yield almost identical bond length, harmonic vibrational frequency, and anharmonic constant, which are more accurate than those from traditional coupled cluster theory. For potential energy curves, the alternative coupled cluster methods are found to be more accurate than traditional coupled cluster theory, but are three to ten times less accurate than multireference coupled cluster approaches. The most challenging benchmark, the BeH(2) model, highlights the strong dependence of the alternative coupled cluster theories on the choice of the Fermi vacuum. When evaluated by the accuracy to cost ratio, the alternative coupled cluster methods are not competitive with respect to traditional CC theory, in other words, the simplest theory is found to be the most effective one.

  4. Analytic gradients for the state-specific multireference coupled cluster singles and doubles model

    NASA Astrophysics Data System (ADS)

    Prochnow, Eric; Evangelista, Francesco A.; Schaefer, Henry F.; Allen, Wesley D.; Gauss, Jürgen

    2009-08-01

    The general theory of analytic energy gradients is presented for the state-specific multireference coupled cluster method introduced by Mukherjee and co-workers [Mol. Phys. 94, 157 (1998)], together with an implementation within the singles and doubles approximation, restricted to two closed-shell determinants and Hartree-Fock orbitals. Expressions for the energy gradient are derived based on a Lagrangian formalism and cast in a density-matrix notation suitable for implementation in standard quantum-chemical program packages. In the present implementation, we exploit a decomposition of the multireference coupled cluster gradient expressions, i.e., lambda equations and the corresponding density matrices, into a so-called single-reference part for each reference determinant and a coupling term. Our implementation exhibits the proper scaling, i.e., O(dN6) with d as the number of reference determinants and N as the number of orbitals, and it is thus suitable for large-scale applications. The applicability of our multireference coupled cluster gradients is illustrated by computations for the equilibrium geometry of the 2,6-isomers of pyridyne and the pyridynium cation. The results are compared to those from single-reference coupled cluster calculations and are discussed with respect to the future perspectives of multireference coupled cluster theory.

  5. Analytic gradients for the state-specific multireference coupled cluster singles and doubles model.

    PubMed

    Prochnow, Eric; Evangelista, Francesco A; Schaefer, Henry F; Allen, Wesley D; Gauss, Jürgen

    2009-08-14

    The general theory of analytic energy gradients is presented for the state-specific multireference coupled cluster method introduced by Mukherjee and co-workers [Mol. Phys. 94, 157 (1998)], together with an implementation within the singles and doubles approximation, restricted to two closed-shell determinants and Hartree-Fock orbitals. Expressions for the energy gradient are derived based on a Lagrangian formalism and cast in a density-matrix notation suitable for implementation in standard quantum-chemical program packages. In the present implementation, we exploit a decomposition of the multireference coupled cluster gradient expressions, i.e., lambda equations and the corresponding density matrices, into a so-called single-reference part for each reference determinant and a coupling term. Our implementation exhibits the proper scaling, i.e., O(dN6) with d as the number of reference determinants and N as the number of orbitals, and it is thus suitable for large-scale applications. The applicability of our multireference coupled cluster gradients is illustrated by computations for the equilibrium geometry of the 2,6-isomers of pyridyne and the pyridynium cation. The results are compared to those from single-reference coupled cluster calculations and are discussed with respect to the future perspectives of multireference coupled cluster theory.

  6. Bridging single and multireference coupled cluster theories with universal state selective formalism.

    PubMed

    Bhaskaran-Nair, Kiran; Kowalski, Karol

    2013-05-28

    The universal state selective (USS) multireference approach is used to construct new energy functionals which offer a possibility of bridging single and multireference coupled cluster theories (SR/MRCC). These functionals, which can be used to develop iterative and non-iterative approaches, utilize a special form of the trial wavefunctions, which assure additive separability (or size-consistency) of the USS energies in the non-interacting subsystem limit. When the USS formalism is combined with approximate SRCC theories, the resulting formalism can be viewed as a size-consistent version of the method of moments of coupled cluster equations employing a MRCC trial wavefunction. Special cases of the USS formulations, which utilize single reference state specific CC [V. V. Ivanov, D. I. Lyakh, and L. Adamowicz, Phys. Chem. Chem. Phys. 11, 2355 (2009)] and tailored CC [T. Kinoshita, O. Hino, and R. J. Bartlett, J. Chem. Phys. 123, 074106 (2005)] expansions are also discussed.

  7. Bridging single and multireference coupled cluster theories with universal state selective formalism

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol

    2013-05-28

    The universal state selective (USS) multireference approach is used to construct new energy functionals which offers a unique possibility of bridging single and multireference coupled cluster theories (SR/MRCC). These functionals, which can be used to develop iterative and non-iterative approaches, utilize a special form of the trial wavefunctions, which assure additive separability (or size-consistency) of the USS energies in the non-interacting subsystem limit. When the USS formalism is combined with approximate SRCC theories, the resulting formalism can be viewed as a size-consistent version of the method of moments of coupled cluster equations (MMCC) employing a MRCC trial wavefunction. Special cases of the USS formulations, which utilize single reference state specific CC (V.V. Ivanov, D.I. Lyakh, L. Adamowicz, Phys. Chem. Chem. Phys. 11, 2355 (2009)) and tailored CC (T. Kinoshita, O. Hino, R.J. Bartlett, J. Chem. Phys. 123, 074106 (2005)) expansions are also discussed.

  8. Coupled Cluster Studies of Ionization Potentials and Electron Affinities of Single-Walled Carbon Nanotubes.

    PubMed

    Peng, Bo; Govind, Niranjan; Aprà, Edoardo; Klemm, Michael; Hammond, Jeff R; Kowalski, Karol

    2017-02-16

    In this paper, we apply equation-of-motion coupled cluster (EOM-CC) methods in the studies of the vertical ionization potentials (IPs) and electron affinities (EAs) for a series of single-walled carbon nanotubes (SWCNT). The EOM-CC formulations for IPs and EAs employing excitation manifolds spanned by single and double excitations (IP/EA-EOM-CCSD) are used to study the IPs and EAs of the SWCNTs as a function of the nanotube length. Several armchair nanotubes corresponding to C20nH20 models with n = 2-6 have been used in benchmark calculations. In agreement with previous studies, we demonstrate that the electronegativity of C20nH20 systems remains, to a large extent, independent of the nanotube length. We also compare IP/EA-EOM-CCSD results with those obtained with coupled cluster models with single and double excitations corrected by perturbative triples, CCSD(T), and density functional theory (DFT) using global and range-separated hybrid exchange-correlation functionals.

  9. A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD)

    DOE PAGES

    Baudin, Pablo; Bykov, Dmytro; Liakh, Dmitry I.; ...

    2017-02-22

    Here, the recently developed Local Framework for calculating Excitation energies (LoFEx) is extended to the coupled cluster singles and doubles (CCSD) model. In the new scheme, a standard CCSD excitation energy calculation is carried out within a reduced excitation orbital space (XOS), which is composed of localised molecular orbitals and natural transition orbitals determined from time-dependent Hartree–Fock theory. The presented algorithm uses a series of reduced second-order approximate coupled cluster singles and doubles (CC2) calculations to optimise the XOS in a black-box manner. This ensures that the requested CCSD excitation energies have been determined to a predefined accuracy compared tomore » a conventional CCSD calculation. We present numerical LoFEx-CCSD results for a set of medium-sized organic molecules, which illustrate the black-box nature of the approach and the computational savings obtained for transitions that are local compared to the size of the molecule. In fact, for such local transitions, the LoFEx-CCSD scheme can be applied to molecular systems where a conventional CCSD implementation is intractable.« less

  10. Universal state-selective corrections to multireference coupled-cluster theories with single and double excitations

    SciTech Connect

    Brabec, Jiri; van Dam, Hubertus JJ; Pittner, Jiri; Kowalski, Karol

    2012-03-28

    The recently proposed Universal State-Selective (USS) corrections [K. Kowalski, J. Chem. Phys. 134, 194107 (2011)] to approximate Multi-Reference Coupled Cluster (MRCC) energies can be commonly applied to any type of MRCC theory based on the Jeziorski-Monkhorst [B. Jeziorski, H.J. Monkhorst, Phys. Rev. A 24, 1668 (1981)] exponential Ansatz. In this letter we report on the performance of a simple USS correction to the Brillouin-Wigner MRCC (BW-MRCC) formalism employing single and double excitations (BW-MRCCSD). It is shown that the resulting formalism (USS-BW-MRCCSD), which uses the manifold of single and double excitations to construct the correction, can be related to a posteriori corrections utilized in routine BW-MRCCSD calculations. In several benchmark calculations we compare the results of the USS-BW-MRCCSD method with results of the BW-MRCCSD approach employing a posteriori corrections and with results obtained with the Full Configuration Interaction (FCI) method.

  11. Density-fitted singles and doubles coupled cluster on graphics processing units

    SciTech Connect

    Sherrill, David; Sumpter, Bobby G; DePrince, III, A. Eugene

    2014-01-01

    We adapt an algorithm for singles and doubles coupled cluster (CCSD) that uses density fitting (DF) or Cholesky decomposition (CD) in the construction and contraction of all electron repulsion integrals (ERI s) for use on heterogeneous compute nodes consisting of a multicore CPU and at least one graphics processing unit (GPU). The use of approximate 3-index ERI s ameliorates two of the major difficulties in designing scientific algorithms for GPU s: (i) the extremely limited global memory on the devices and (ii) the overhead associated with data motion across the PCI bus. For the benzene trimer described by an aug-cc-pVDZ basis set, the use of a single NVIDIA Tesla C2070 (Fermi) GPU accelerates a CD-CCSD computation by a factor of 2.1, relative to the multicore CPU-only algorithm that uses 6 highly efficient Intel core i7-3930K CPU cores. The use of two Fermis provides an acceleration of 2.89, which is comparable to that observed when using a single NVIDIA Kepler K20c GPU (2.73).

  12. Density-fitted singles and doubles coupled cluster on graphics processing units

    NASA Astrophysics Data System (ADS)

    DePrince, , A. Eugene, III; Kennedy, Matthew R.; Sumpter, Bobby G.; Sherrill, C. David

    2014-03-01

    We adapt an algorithm for singles and doubles coupled cluster (CCSD) that uses density fitting or Cholesky decomposition (CD) in the construction and contraction of all electron repulsion integrals (ERIs) for use on heterogeneous compute nodes consisting of a multicore central processing unit (CPU) and at least one graphics processing unit (GPU). The use of approximate three-index ERIs ameliorates two of the major difficulties in designing scientific algorithms for GPUs: (1) the extremely limited global memory on the devices and (2) the overhead associated with data motion across the bus. For the benzene trimer described by an aug-cc-pVDZ basis set, the use of a single NVIDIA Tesla C2070 (Fermi) GPU accelerates a CD-CCSD computation by a factor of 2.1, relative to the multicore CPU-only algorithm that uses six highly efficient Intel Core i7-3930K CPU cores. The use of two Fermi GPUs provides an acceleration of 2.89, which is comparable to that observed when using a single NVIDIA Kepler K20c GPU (2.73).

  13. Development and Application of Single-Referenced Perturbation and Coupled-Cluster Theories for Excited Electronic States

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    Recent work on the development of single-reference perturbation theories for the study of excited electronic states will be discussed. The utility of these methods will be demonstrated by comparison to linear-response coupled-cluster excitation energies. Results for some halogen molecules of interest in stratospheric chemistry will be presented.

  14. Development and Application of Single-Referenced Perturbation and Coupled-Cluster Theories for Excited Electronic States

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    Recent work on the development of single-reference perturbation theories for the study of excited electronic states will be discussed. The utility of these methods will be demonstrated by comparison to linear-response coupled-cluster excitation energies. Results for some halogen molecules of interest in stratospheric chemistry will be presented.

  15. Massively Parallel Implementation of Explicitly Correlated Coupled-Cluster Singles and Doubles Using TiledArray Framework.

    PubMed

    Peng, Chong; Calvin, Justus A; Pavošević, Fabijan; Zhang, Jinmei; Valeev, Edward F

    2016-12-29

    A new distributed-memory massively parallel implementation of standard and explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) with canonical O(N(6)) computational complexity is described. The implementation is based on the TiledArray tensor framework. Novel features of the implementation include (a) all data greater than O(N) is distributed in memory and (b) the mixed use of density fitting and integral-driven formulations that optionally allows to avoid storage of tensors with three and four unoccupied indices. Excellent strong scaling is demonstrated on a multicore shared-memory computer, a commodity distributed-memory computer, and a national-scale supercomputer. The performance on a shared-memory computer is competitive with the popular CCSD implementations in ORCA and Psi4. Moreover, the CCSD performance on a commodity-size cluster significantly improves on the state-of-the-art package NWChem. The large-scale parallel explicitly correlated coupled-cluster implementation makes routine accurate estimation of the coupled-cluster basis set limit for molecules with 20 or more atoms. Thus, it can provide valuable benchmarks for the merging reduced-scaling coupled-cluster approaches. The new implementation allowed us to revisit the basis set limit for the CCSD contribution to the binding energy of π-stacked uracil dimer, a challenging paradigm of π-stacking interactions from the S66 benchmark database. The revised value for the CCSD correlation binding energy obtained with the help of quadruple-ζ CCSD computations, -8.30 ± 0.02 kcal/mol, is significantly different from the S66 reference value, -8.50 kcal/mol, as well as other CBS limit estimates in the recent literature.

  16. Projected coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Qiu, Yiheng; Henderson, Thomas M.; Zhao, Jinmo; Scuseria, Gustavo E.

    2017-08-01

    Coupled cluster theory is the method of choice for weakly correlated systems. But in the strongly correlated regime, it faces a symmetry dilemma, where it either completely fails to describe the system or has to artificially break certain symmetries. On the other hand, projected Hartree-Fock theory captures the essential physics of many kinds of strong correlations via symmetry breaking and restoration. In this work, we combine and try to retain the merits of these two methods by applying symmetry projection to broken symmetry coupled cluster wave functions. The non-orthogonal nature of states resulting from the application of symmetry projection operators furnishes particle-hole excitations to all orders, thus creating an obstacle for the exact evaluation of overlaps. Here we provide a solution via a disentanglement framework theory that can be approximated rigorously and systematically. Results of projected coupled cluster theory are presented for molecules and the Hubbard model, showing that spin projection significantly improves unrestricted coupled cluster theory while restoring good quantum numbers. The energy of projected coupled cluster theory reduces to the unprojected one in the thermodynamic limit, albeit at a much slower rate than projected Hartree-Fock.

  17. Stochastic Coupled Cluster Theory

    NASA Astrophysics Data System (ADS)

    Thom, Alex J. W.

    2010-12-01

    We describe a stochastic coupled cluster theory which represents excitation amplitudes as discrete excitors in the space of excitation amplitudes. Reexpressing the coupled cluster (CC) equations as the dynamics of excitors in this space, we show that a simple set of rules suffices to evolve a distribution of excitors to sample the CC solution and correctly evaluate the CC energy. These rules are not truncation specific and this method can calculate CC solutions to an arbitrary level of truncation. We present results of calculation on the neon atom, and nitrogen and water molecules showing the ability to recover both truncated and full CC results.

  18. Communication: Acceleration of coupled cluster singles and doubles via orbital-weighted least-squares tensor hypercontraction

    SciTech Connect

    Parrish, Robert M.; Sherrill, C. David; Hohenstein, Edward G.; Kokkila, Sara I. L.; Martínez, Todd J.

    2014-05-14

    We apply orbital-weighted least-squares tensor hypercontraction decomposition of the electron repulsion integrals to accelerate the coupled cluster singles and doubles (CCSD) method. Using accurate and flexible low-rank factorizations of the electron repulsion integral tensor, we are able to reduce the scaling of the most vexing particle-particle ladder term in CCSD from O(N{sup 6}) to O(N{sup 5}), with remarkably low error. Combined with a T{sub 1}-transformed Hamiltonian, this leads to substantial practical accelerations against an optimized density-fitted CCSD implementation.

  19. A noniterative asymmetric triple excitation correction for the density-fitted coupled-cluster singles and doubles method: Preliminary applications

    NASA Astrophysics Data System (ADS)

    Bozkaya, Uǧur

    2016-04-01

    An efficient implementation of the asymmetric triples correction for the coupled-cluster singles and doubles [ΛCCSD(T)] method [S. A. Kucharski and R. J. Bartlett, J. Chem. Phys. 108, 5243 (1998); T. D. Crawford and J. F. Stanton, Int. J. Quantum Chem. 70, 601 (1998)] with the density-fitting [DF-ΛCCSD(T)] approach is presented. The computational time for the DF-ΛCCSD(T) method is compared with that of ΛCCSD(T). Our results demonstrate that the DF-ΛCCSD(T) method provide substantially lower computational costs than ΛCCSD(T). Further application results show that the ΛCCSD(T) and DF-ΛCCSD(T) methods are very beneficial for the study of single bond breaking problems as well as noncovalent interactions and transition states. We conclude that ΛCCSD(T) and DF-ΛCCSD(T) are very promising for the study of challenging chemical systems, where the coupled-cluster singles and doubles with perturbative triples method fails.

  20. Experimental synchronization of chaos in a large ring of mutually coupled single-transistor oscillators: Phase, amplitude, and clustering effects

    SciTech Connect

    Minati, Ludovico E-mail: ludovico.minati@unitn.it

    2014-12-01

    In this paper, experimental evidence of multiple synchronization phenomena in a large (n = 30) ring of chaotic oscillators is presented. Each node consists of an elementary circuit, generating spikes of irregular amplitude and comprising one bipolar junction transistor, one capacitor, two inductors, and one biasing resistor. The nodes are mutually coupled to their neighbours via additional variable resistors. As coupling resistance is decreased, phase synchronization followed by complete synchronization is observed, and onset of synchronization is associated with partial synchronization, i.e., emergence of communities (clusters). While component tolerances affect community structure, the general synchronization properties are maintained across three prototypes and in numerical simulations. The clusters are destroyed by adding long distance connections with distant notes, but are otherwise relatively stable with respect to structural connectivity changes. The study provides evidence that several fundamental synchronization phenomena can be reliably observed in a network of elementary single-transistor oscillators, demonstrating their generative potential and opening way to potential applications of this undemanding setup in experimental modelling of the relationship between network structure, synchronization, and dynamical properties.

  1. Experimental synchronization of chaos in a large ring of mutually coupled single-transistor oscillators: phase, amplitude, and clustering effects.

    PubMed

    Minati, Ludovico

    2014-12-01

    In this paper, experimental evidence of multiple synchronization phenomena in a large (n = 30) ring of chaotic oscillators is presented. Each node consists of an elementary circuit, generating spikes of irregular amplitude and comprising one bipolar junction transistor, one capacitor, two inductors, and one biasing resistor. The nodes are mutually coupled to their neighbours via additional variable resistors. As coupling resistance is decreased, phase synchronization followed by complete synchronization is observed, and onset of synchronization is associated with partial synchronization, i.e., emergence of communities (clusters). While component tolerances affect community structure, the general synchronization properties are maintained across three prototypes and in numerical simulations. The clusters are destroyed by adding long distance connections with distant notes, but are otherwise relatively stable with respect to structural connectivity changes. The study provides evidence that several fundamental synchronization phenomena can be reliably observed in a network of elementary single-transistor oscillators, demonstrating their generative potential and opening way to potential applications of this undemanding setup in experimental modelling of the relationship between network structure, synchronization, and dynamical properties.

  2. Implementation of transition moments between excited states in the approximate coupled-cluster singles and doubles model.

    PubMed

    Pabst, Mathias; Köhn, Andreas

    2008-12-07

    An implementation of transition moments between excited states for the approximate coupled-cluster singles and doubles model (CC2) using the resolution of the identity (RI) approximation is reported. The accuracy of the RI approximation is analyzed for a testset of 7 molecules and 76 transitions. The RI error is found to be very small for both transition moments and oscillator strengths. Furthermore, the performance of the CC2 model in comparison with coupled-cluster singles and doubles (CCSD) is studied for 40 transitions of the same testset, yielding deviations of about 12% for the transition moments and 24% for the oscillator strengths. In addition, for 13 transitions of the testset the behavior of the transition moments with respect to seven different basis sets (Dunnings xaug-cc-pVXZ, with x=0,1,2 for X=D,T and x=2 for X=5) is analyzed, showing a strong dependence on the degree of augmentation x and a rather small effect of the cardinal number X. First applications are presented for the triplet-triplet transition moments of benzene and polyacenes (naphthalene to pentacene), showing good agreement with experimental and theoretical results for transitions between single excitation dominated states. Somewhat problematic is the insufficient description of double-excitation dominated states by the CC2 model. As transitions to such states may be strongly allowed, unlike for excitations out of the ground state, important features of transient spectra may be missed. For triplet-triplet excitations the problem is less evident as the lowest doubly excited triplet states are expected at higher energies.

  3. Second-order many-body perturbation and coupled-cluster singles and doubles study of ice VIII

    SciTech Connect

    Gilliard, Kandis; Sode, Olaseni; Hirata, So

    2014-05-07

    The structure, equation of state, IR, Raman, and inelastic neutron scattering (INS) spectra of high-pressure, proton-ordered phase VIII of ice are calculated by the second-order many-body perturbation and coupled-cluster singles and doubles methods. Nearly all the observed features of the pressure-dependence of the structures and spectra are reproduced computationally up to 60 GPa insofar as the anharmonic effects can be neglected. The calculations display no sign of the hypothetical isostructural transition in 2–3 GPa to phase VIII{sup ′}, the existence of which has been a matter of controversy for over a decade, while they do not contradict the interpretation of the spectral anomaly at 10–14 GPa as a precursor of the VIII-X phase transition. The calculated INS spectra correct a systematic error in the peak positions of the observed spectra.

  4. Quartic scaling second-order approximate coupled cluster singles and doubles via tensor hypercontraction: THC-CC2

    NASA Astrophysics Data System (ADS)

    Hohenstein, Edward G.; Kokkila, Sara I. L.; Parrish, Robert M.; Martínez, Todd J.

    2013-03-01

    The second-order approximate coupled cluster singles and doubles method (CC2) is a valuable tool in electronic structure theory. Although the density fitting approximation has been successful in extending CC2 to larger molecules, it cannot address the steep O(N^5) scaling with the number of basis functions, N. Here, we introduce the tensor hypercontraction (THC) approximation to CC2 (THC-CC2), which reduces the scaling to O(N^4) and the storage requirements to O(N^2). We present an algorithm to efficiently evaluate the THC-CC2 correlation energy and demonstrate its quartic scaling. This implementation of THC-CC2 uses a grid-based least-squares THC (LS-THC) approximation to the density-fitted electron repulsion integrals. The accuracy of the CC2 correlation energy under these approximations is shown to be suitable for most practical applications.

  5. Profiling the binding motif between Be and Mg in the ground state via a single-reference coupled cluster method

    NASA Astrophysics Data System (ADS)

    Sinha Mahapatra, Uttam; Banerjee, Debi; Chaudhuri, Rajat K.; Chattopadhyay, Sudip

    2015-06-01

    We present a study on the performance of our iterative triples correction for the coupled cluster singles and doubles excitations (CCSDT-1a+d) method for computation of potential energy surface (PES), spectroscopic constants, and vibrational spectrum for the ground state (X1Σ+) BeMg, where the ostensible inadequacy of the CCSD and CCSD(T) methods is quite expected. We compare our results with those obtained using state-of-the-art multireference configuration interaction (MRCI) investigations reported earlier by Kerkines and Nicolaides. Our estimated dissociation energy (417.37 cm-1), equilibrium distance (3.285 Å), and vibrational frequency (82.32 cm-1) are in good agreement with recent results of advanced MRCI calculations for X1Σ+ BeMg PES, which exhibits a shallow well of 469.4 cm-1 with a minimum at 3.241 Å and a harmonic vibrational frequency of 85.7 cm-1. Very weakly bound nature of X1Σ+ BeMg is clearly reflected from these values. In accord with MRCI studies, a comparison of BeMg with iso-valence weakly bound ground-state species, Be2 and Mg2, suggests that its characteristics do not exhibit any resemblance to Be2 rather, it shows a close kinship to Mg2. The agreement of our derived vibrational levels with those obtained via the high-level MRCI calculations is very encouraging reflecting the potential of the suitably modified single-reference coupled cluster (SRCC) method, CCSDT-1a+d as a tool for the study of multireference van der Waals systems.

  6. The coupled cluster singles, doubles, and a hybrid treatment of connected triples based on the split virtual orbitals

    NASA Astrophysics Data System (ADS)

    Shen, Jun; Kou, Zhuangfei; Xu, Enhua; Li, Shuhua

    2012-01-01

    We have proposed a simple strategy for splitting the virtual orbitals with a large basis set into two subgroups (active and inactive) by taking a smaller basis set as an auxiliary basis set. With the split virtual orbitals (SVOs), triple or higher excitations can be partitioned into active and inactive subgroups (according to the number of active virtual orbitals involved), which can be treated with different electron correlation methods. In this work, the coupled cluster (CC) singles, doubles, and a hybrid treatment of connected triples based on the SVO [denoted as SVO-CCSD(T)-h], has been implemented. The present approach has been applied to study the bond breaking potential energy surfaces in three molecules (HF, F2, and N2), and the equilibrium properties in a number of open-shell diatomic molecules. For all systems under study, the SVO-CCSD(T)-h method based on the unrestricted Hartree-Fock (UHF) reference is an excellent approximation to the corresponding CCSDT (CC singles, doubles, and triples), and much better than the UHF-based CCSD(T) (CC singles, doubles, and perturbative triples). On the other hand, the SVO-CCSD(T)-h method based on the restricted HF (RHF) reference can also provide considerable improvement over the RHF-based CCSD(T).

  7. Rethinking linearized coupled-cluster theory.

    PubMed

    Taube, Andrew G; Bartlett, Rodney J

    2009-04-14

    Hermitian linearized coupled-cluster methods have several advantages over more conventional coupled-cluster methods including facile analytical gradients for searching a potential energy surface. A persistent failure of linearized methods, however, is the presence of singularities on the potential energy surface. A simple Tikhonov regularization procedure is introduced that can eliminate this singularity. Application of the regularized linearized coupled-cluster singles and doubles (CCSD) method to both equilibrium structures and transition states shows that it is competitive with or better than conventional CCSD, and is more amenable to parallelization.

  8. Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model

    SciTech Connect

    Gwaltney, Steven R.; Sherrill, C. David; Head-Gordon, Martin; Krylov, Anna I.

    2000-09-01

    We present a general perturbative method for correcting a singles and doubles coupled-cluster energy. The coupled-cluster wave function is used to define a similarity-transformed Hamiltonian, which is partitioned into a zeroth-order part that the reference problem solves exactly plus a first-order perturbation. Standard perturbation theory through second-order provides the leading correction. Applied to the valence optimized doubles (VOD) approximation to the full-valence complete active space self-consistent field method, the second-order correction, which we call (2), captures dynamical correlation effects through external single, double, and semi-internal triple and quadruple substitutions. A factorization approximation reduces the cost of the quadruple substitutions to only sixth order in the size of the molecule. A series of numerical tests are presented showing that VOD(2) is stable and well-behaved provided that the VOD reference is also stable. The second-order correction is also general to standard unwindowed coupled-cluster energies such as the coupled-cluster singles and doubles (CCSD) method itself, and the equations presented here fully define the corresponding CCSD(2) energy. (c) 2000 American Institute of Physics.

  9. Single string based global optimizer for geometry optimization in strongly coupled finite clusters: An adaptive mutation-driven strategy

    NASA Astrophysics Data System (ADS)

    Sarkar, Kanchan; Bhattacharyya, S. P.

    2013-08-01

    We propose and implement a simple adaptive heuristic to optimize the geometries of clusters of point charges or ions with the ability to find the global minimum energy configurations. The approach uses random mutations of a single string encoding the geometry and accepts moves that decrease the energy. Mutation probability and mutation intensity are allowed to evolve adaptively on the basis of continuous evaluation of past explorations. The resulting algorithm has been called Completely Adaptive Random Mutation Hill Climbing method. We have implemented this method to search through the complex potential energy landscapes of parabolically confined 3D classical Coulomb clusters of hundreds or thousands of charges—usually found in high frequency discharge plasmas. The energy per particle (EN/N) and its first and second differences, structural features, distribution of the oscillation frequencies of normal modes, etc., are analyzed as functions of confinement strength and the number of charges in the system. Certain magic numbers are identified. In order to test the feasibility of the algorithm in cluster geometry optimization on more complex energy landscapes, we have applied the algorithm for optimizing the geometries of MgO clusters, described by Coulomb-Born-Mayer potential and finding global minimum of some Lennard-Jones clusters. The convergence behavior of the algorithm compares favorably with those of other existing global optimizers.

  10. Single string based global optimizer for geometry optimization in strongly coupled finite clusters: An adaptive mutation-driven strategy.

    PubMed

    Sarkar, Kanchan; Bhattacharyya, S P

    2013-08-21

    We propose and implement a simple adaptive heuristic to optimize the geometries of clusters of point charges or ions with the ability to find the global minimum energy configurations. The approach uses random mutations of a single string encoding the geometry and accepts moves that decrease the energy. Mutation probability and mutation intensity are allowed to evolve adaptively on the basis of continuous evaluation of past explorations. The resulting algorithm has been called Completely Adaptive Random Mutation Hill Climbing method. We have implemented this method to search through the complex potential energy landscapes of parabolically confined 3D classical Coulomb clusters of hundreds or thousands of charges--usually found in high frequency discharge plasmas. The energy per particle (EN∕N) and its first and second differences, structural features, distribution of the oscillation frequencies of normal modes, etc., are analyzed as functions of confinement strength and the number of charges in the system. Certain magic numbers are identified. In order to test the feasibility of the algorithm in cluster geometry optimization on more complex energy landscapes, we have applied the algorithm for optimizing the geometries of MgO clusters, described by Coulomb-Born-Mayer potential and finding global minimum of some Lennard-Jones clusters. The convergence behavior of the algorithm compares favorably with those of other existing global optimizers.

  11. A fusion of the closed-shell coupled cluster singles and doubles method and valence-bond theory for bond breaking.

    PubMed

    Small, David W; Head-Gordon, Martin

    2012-09-21

    Closed-shell coupled cluster singles and doubles (CCSD) is among the most important of electronic-structure methods. However, it fails qualitatively when applied to molecular systems with more than two strongly correlated electrons, such as those with stretched or broken covalent bonds. We show that it is possible to modify the doubles amplitudes to obtain a closed-shell CCSD method that retains the computational cost and desirable features of standard closed-shell CCSD, e.g., correct spin symmetry, size extensivity, orbital invariance, etc., but produces greatly improved energies upon bond dissociation of multiple electron pairs; indeed, under certain conditions the dissociation energies are exact.

  12. Pair extended coupled cluster doubles

    SciTech Connect

    Henderson, Thomas M.; Scuseria, Gustavo E.; Bulik, Ireneusz W.

    2015-06-07

    The accurate and efficient description of strongly correlated systems remains an important challenge for computational methods. Doubly occupied configuration interaction (DOCI), in which all electrons are paired and no correlations which break these pairs are permitted, can in many cases provide an accurate account of strong correlations, albeit at combinatorial computational cost. Recently, there has been significant interest in a method we refer to as pair coupled cluster doubles (pCCD), a variant of coupled cluster doubles in which the electrons are paired. This is simply because pCCD provides energies nearly identical to those of DOCI, but at mean-field computational cost (disregarding the cost of the two-electron integral transformation). Here, we introduce the more complete pair extended coupled cluster doubles (pECCD) approach which, like pCCD, has mean-field cost and reproduces DOCI energetically. We show that unlike pCCD, pECCD also reproduces the DOCI wave function with high accuracy. Moreover, pECCD yields sensible albeit inexact results even for attractive interactions where pCCD breaks down.

  13. Accurate thermochemistry from a parameterized coupled-cluster singles and doubles model and a local pair natural orbital based implementation for applications to larger systems.

    PubMed

    Huntington, Lee M J; Hansen, Andreas; Neese, Frank; Nooijen, Marcel

    2012-02-14

    We have recently introduced a parameterized coupled-cluster singles and doubles model (pCCSD(α, β)) that consists of a bivariate parameterization of the CCSD equations and is inspired by the coupled electron pair approximations. In our previous work, it was demonstrated that the pCCSD(-1, 1) method is an improvement over CCSD for the calculation of geometries, harmonic frequencies, and potential energy surfaces for single bond-breaking. In this paper, we find suitable pCCSD parameters for applications in reaction thermochemistry and thermochemical kinetics. The motivation is to develop an accurate and economical methodology that, when coupled with a robust local correlation framework based on localized pair natural orbitals, is suitable for large-scale thermochemical applications for sizeable molecular systems. It is demonstrated that the original pCCSD(-1, 1) method and several other pCCSD methods are a significant improvement upon the standard CCSD approach and that these methods often approach the accuracy of CCSD(T) for the calculation of reaction energies and barrier heights. We also show that a local version of the pCCSD methodology, implemented within the local pair natural orbital (LPNO) based CCSD code in ORCA, is sufficiently accurate for wide-scale chemical applications. The LPNO based methodology allows us for routine applications to intermediate sized (20-100 atoms) molecular systems and is a significantly more accurate alternative to MP2 and density functional theory for the prediction of reaction energies and barrier heights.

  14. One-electron properties and electrostatic interaction energies from the expectation value expression and wave function of singles and doubles coupled cluster theory.

    PubMed

    Korona, Tatiana; Jeziorski, Bogumil

    2006-11-14

    One-electron density matrices resulting from the explicitly connected commutator expansion of the expectation value were implemented at the singles and doubles coupled cluster (CCSD) level. In the proposed approach the one-electron density matrix is obtained at a little extra cost in comparison to the calculation of the CCSD correlation energy. Therefore, in terms of the computational time the new method is significantly less demanding than the conventional linear-response CCSD theory which requires additionally an expensive calculation of the left-hand solution of the CCSD equations. The quality of the new density matrices was investigated by computing a set of one-electron properties for a series of molecules of varying sizes and comparing the results with data obtained using the full configuration interaction method or higher level coupled cluster theory. It has been found that the results obtained using the new approach are of the same quality as those predicted by the linear-response CCSD method. The novel one-electron density matrices have also been applied to study the energy of the electrostatic interaction for a number of van der Waals complexes, including the benzene and azulene dimers.

  15. Linked coupled cluster Monte Carlo

    SciTech Connect

    Franklin, R. S. T.; Zoccante, A.; Thom, A. J. W.; Spencer, J. S.

    2016-01-28

    We consider a new formulation of the stochastic coupled cluster method in terms of the similarity transformed Hamiltonian. We show that improvement in the granularity with which the wavefunction is represented results in a reduction in the critical population required to correctly sample the wavefunction for a range of systems and excitation levels and hence leads to a substantial reduction in the computational cost. This development has the potential to substantially extend the range of the method, enabling it to be used to treat larger systems with excitation levels not easily accessible with conventional deterministic methods.

  16. A truncation hierarchy of coupled cluster models of strongly correlated systems based on perfect-pairing references: The singles+doubles models

    NASA Astrophysics Data System (ADS)

    Parkhill, John A.; Head-Gordon, Martin

    2010-09-01

    Paired, active-space treatments of static correlation are augmented with additional amplitudes to produce a hierarchy of parsimonious and efficient cluster truncations that approximate the total energy. The number of parameters introduced in these models grow with system size in a tractable way: two powers larger than the static correlation model it is built upon: for instance cubic for the models built on perfect pairing, fourth order for a perfect quadruples (PQ) reference, and fifth order for the models built on perfect hextuples. These methods are called singles+doubles (SD) corrections to perfect pairing, PQ, perfect hextuples, and two variants are explored. An implementation of the SD methods is compared to benchmark results for F2 and H2O dissociation problems, the H4 and H8 model systems, and the insertion of beryllium into hydrogen. In the cases examined even the quartic number of parameters associated with PQSD is able to provide results which meaningfully improve on coupled-cluster singles doubles (CCSD) (which also has quartic amplitudes) and compete with existing multi-reference alternatives.

  17. Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

    DOE PAGES

    White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William; ...

    2017-06-21

    The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N 2 - , CO - , CO 2 - , and CH 2 O - . Analytic continuation of complex θ-trajectories is used to compute Siegert energies, and the θ-trajectories of energy differences are found to yield more consistent results than those of total energies. Furthermore, themore » ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.« less

  18. Fast coupled-cluster singles and doubles for extended systems: Application to the anharmonic vibrational frequencies of polyethylene in the Γ approximation

    NASA Astrophysics Data System (ADS)

    Keçeli, Murat; Hirata, So

    2010-09-01

    The mod- n scheme is introduced to the coupled-cluster singles and doubles (CCSD) and third-order Møller-Plesset perturbation (MP3) methods for extended systems of one-dimensional periodicity. By downsampling uniformly the wave vectors in Brillouin-zone integrations, this scheme accelerates these accurate but expensive correlation-energy calculations by two to three orders of magnitude while incurring negligible errors in their total and relative energies. To maintain this accuracy, the number of the nearest-neighbor unit cells included in the lattice sums must also be reduced by the same downsampling rate (n) . The mod- n CCSD and MP3 methods are applied to the potential-energy surface of polyethylene in anharmonic frequency calculations of its infrared- and Raman-active vibrations. The calculated frequencies are found to be within 46cm-1 (CCSD) and 78cm-1 (MP3) of the observed.

  19. Second order Møller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

    NASA Astrophysics Data System (ADS)

    White, Alec F.; Epifanovsky, Evgeny; McCurdy, C. William; Head-Gordon, Martin

    2017-06-01

    The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N2-, CO-, CO2-, and CH2O-. Analytic continuation of complex 𝜃 -trajectories is used to compute Siegert energies, and the 𝜃 -trajectories of energy differences are found to yield more consistent results than those of total energies. The ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.

  20. An efficient formulation and implementation of the analytic energy gradient method to the single and double excitation coupled-cluster wave function - Application to Cl2O2

    NASA Technical Reports Server (NTRS)

    Rendell, Alistair P.; Lee, Timothy J.

    1991-01-01

    The analytic energy gradient for the single and double excitation coupled-cluster (CCSD) wave function has been reformulated and implemented in a new set of programs. The reformulated set of gradient equations have a smaller computational cost than any previously published. The iterative solution of the linear equations and the construction of the effective density matrices are fully vectorized, being based on matrix multiplications. The new method has been used to investigate the Cl2O2 molecule, which has recently been postulated as an important intermediate in the destruction of ozone in the stratosphere. In addition to reporting computational timings, the CCSD equilibrium geometries, harmonic vibrational frequencies, infrared intensities, and relative energetics of three isomers of Cl2O2 are presented.

  1. An efficient formulation and implementation of the analytic energy gradient method to the single and double excitation coupled-cluster wave function - Application to Cl2O2

    NASA Technical Reports Server (NTRS)

    Rendell, Alistair P.; Lee, Timothy J.

    1991-01-01

    The analytic energy gradient for the single and double excitation coupled-cluster (CCSD) wave function has been reformulated and implemented in a new set of programs. The reformulated set of gradient equations have a smaller computational cost than any previously published. The iterative solution of the linear equations and the construction of the effective density matrices are fully vectorized, being based on matrix multiplications. The new method has been used to investigate the Cl2O2 molecule, which has recently been postulated as an important intermediate in the destruction of ozone in the stratosphere. In addition to reporting computational timings, the CCSD equilibrium geometries, harmonic vibrational frequencies, infrared intensities, and relative energetics of three isomers of Cl2O2 are presented.

  2. Magnetic anisotropy in single clusters

    NASA Astrophysics Data System (ADS)

    Jamet, Matthieu; Wernsdorfer, Wolfgang; Thirion, Christophe; Dupuis, Véronique; Mélinon, Patrice; Pérez, Alain; Mailly, Dominique

    2004-01-01

    The magnetic measurements on single cobalt and iron nanoclusters containing almost 1000 atoms are presented. Particles are directly buried within the superconducting film of a micro-SQUID (superconducting quantum interference device) which leads to the required sensitivity. The angular dependence of the switching field in three dimensions turns out to be in good agreement with a uniform rotation of cluster magnetization. The Stoner and Wohlfarth model yields therefore an estimation of magnetic anisotropy in a single cluster. In particular, uniaxial, biaxial, and cubic contributions can be separated. Results are interpreted on the basis of a simple atomic model in which clusters are assimilated to “giant spins.” We present an extension of the Néel model to clusters in order to estimate surface anisotropy. In the case of cobalt, this last contribution dominates and numerical simulations allow us to get the morphology of the investigated clusters.

  3. Singlet-paired coupled cluster theory for open shells.

    PubMed

    Gomez, John A; Henderson, Thomas M; Scuseria, Gustavo E

    2016-06-28

    Restricted single-reference coupled cluster theory truncated to single and double excitations accurately describes weakly correlated systems, but often breaks down in the presence of static or strong correlation. Good coupled cluster energies in the presence of degeneracies can be obtained by using a symmetry-broken reference, such as unrestricted Hartree-Fock, but at the cost of good quantum numbers. A large body of work has shown that modifying the coupled cluster ansatz allows for the treatment of strong correlation within a single-reference, symmetry-adapted framework. The recently introduced singlet-paired coupled cluster doubles (CCD0) method is one such model, which recovers correct behavior for strong correlation without requiring symmetry breaking in the reference. Here, we extend singlet-paired coupled cluster for application to open shells via restricted open-shell singlet-paired coupled cluster singles and doubles (ROCCSD0). The ROCCSD0 approach retains the benefits of standard coupled cluster theory and recovers correct behavior for strongly correlated, open-shell systems using a spin-preserving ROHF reference.

  4. Seniority zero pair coupled cluster doubles theory.

    PubMed

    Stein, Tamar; Henderson, Thomas M; Scuseria, Gustavo E

    2014-06-07

    Coupled cluster theory with single and double excitations accurately describes weak electron correlation but is known to fail in cases of strong static correlation. Fascinatingly, however, pair coupled cluster doubles (p-CCD), a simplified version of the theory limited to pair excitations that preserve the seniority of the reference determinant (i.e., the number of unpaired electrons), has mean field computational cost and is an excellent approximation to the full configuration interaction (FCI) of the paired space provided that the orbital basis defining the pairing scheme is adequately optimized. In previous work, we have shown that optimization of the pairing scheme in the seniority zero FCI leads to a very accurate description of static correlation. The same conclusion extends to p-CCD if the orbitals are optimized to make the p-CCD energy stationary. We here demonstrate these results with numerous examples. We also explore the contributions of different seniority sectors to the coupled cluster doubles (CCD) correlation energy using different orbital bases. We consider both Hartree-Fock and Brueckner orbitals, and the role of orbital localization. We show how one can pair the orbitals so that the role of the Brueckner orbitals at the CCD level is retained at the p-CCD level. Moreover, we explore ways of extending CCD to accurately describe strongly correlated systems.

  5. Toward open-shell nuclei with coupled-cluster theory

    SciTech Connect

    Jansen, G. R.; Hjorth-Jensen, M.; Hagen, G.; Papenbrock, T.

    2011-05-15

    We develop a method based on equation-of-motion coupled-cluster theory to describe properties of open-shell nuclei with A{+-}2 nucleons outside a closed shell. We perform proof-of-principle calculations for the ground states of the helium isotopes {sup 3-6}He and the first excited 2{sup +} state in {sup 6}He. The comparison with exact results from matrix diagonalization in small model spaces demonstrates the accuracy of the coupled-cluster methods. Three-particle-one-hole excitations of {sup 4}He play an important role for the accurate description of {sup 6}He. For the open-shell nucleus {sup 6}He, the computational cost of the method is comparable with the coupled-cluster singles-and-doubles approximation while its accuracy is similar to the coupled-cluster with singles, doubles, and triples excitations.

  6. Equation-of-motion coupled cluster perturbation theory revisited.

    PubMed

    Eriksen, Janus J; Jørgensen, Poul; Olsen, Jeppe; Gauss, Jürgen

    2014-05-07

    The equation-of-motion coupled cluster (EOM-CC) framework has been used for deriving a novel series of perturbative corrections to the coupled cluster singles and doubles energy that formally converges towards the full configuration interaction energy limit. The series is based on a Møller-Plesset partitioning of the Hamiltonian and thus size extensive at any order in the perturbation, thereby remedying the major deficiency inherent to previous perturbation series based on the EOM-CC ansatz.

  7. Equation-of-motion coupled cluster perturbation theory revisited

    SciTech Connect

    Eriksen, Janus J. Jørgensen, Poul; Olsen, Jeppe; Gauss, Jürgen

    2014-05-07

    The equation-of-motion coupled cluster (EOM-CC) framework has been used for deriving a novel series of perturbative corrections to the coupled cluster singles and doubles energy that formally converges towards the full configuration interaction energy limit. The series is based on a Møller-Plesset partitioning of the Hamiltonian and thus size extensive at any order in the perturbation, thereby remedying the major deficiency inherent to previous perturbation series based on the EOM-CC ansatz.

  8. Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: theory, implementation, and examples.

    PubMed

    Bravaya, Ksenia B; Zuev, Dmitry; Epifanovsky, Evgeny; Krylov, Anna I

    2013-03-28

    Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in atomic systems (He, H(-), and Be). The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveal that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one-electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, θ. Standard basis sets that are optimized for not-complex-scaled calculations (θ = 0) are not sufficiently flexible to describe the θ-dependence of the wave functions even when heavily augmented by additional sets.

  9. Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: Theory, implementation, and examples

    SciTech Connect

    Bravaya, Ksenia B.; Zuev, Dmitry; Epifanovsky, Evgeny; Krylov, Anna I.

    2013-03-28

    Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in atomic systems (He, H{sup -}, and Be). The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveal that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one-electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, {theta}. Standard basis sets that are optimized for not-complex-scaled calculations ({theta} = 0) are not sufficiently flexible to describe the {theta}-dependence of the wave functions even when heavily augmented by additional sets.

  10. Analytic energy gradients for the coupled-cluster singles and doubles with perturbative triples method with the density-fitting approximation

    NASA Astrophysics Data System (ADS)

    Bozkaya, Uǧur; Sherrill, C. David

    2017-07-01

    An efficient implementation of analytic gradients for the coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method with the density-fitting (DF) approximation, denoted as DF-CCSD(T), is reported. For the molecules considered, the DF approach substantially accelerates conventional CCSD(T) analytic gradients due to the reduced input/output time and the acceleration of the so-called "gradient terms": formation of particle density matrices (PDMs), computation of the generalized Fock-matrix (GFM), solution of the Z-vector equation, formation of the effective PDMs and GFM, back-transformation of the PDMs and GFM, from the molecular orbital to the atomic orbital (AO) basis, and computation of gradients in the AO basis. For the largest member of the molecular test set considered (C6H14), the computational times for analytic gradients (with the correlation-consistent polarized valence triple-ζ basis set in serial) are 106.2 [CCSD(T)] and 49.8 [DF-CCSD(T)] h, a speedup of more than 2-fold. In the evaluation of gradient terms, the DF approach completely avoids the use of four-index two-electron integrals. Similar to our previous studies on DF-second-order Møller-Plesset perturbation theory and DF-CCSD gradients, our formalism employs 2- and 3-index two-particle density matrices (TPDMs) instead of 4-index TPDMs. Errors introduced by the DF approximation are negligible for equilibrium geometries and harmonic vibrational frequencies.

  11. Analytic energy gradients for the coupled-cluster singles and doubles with perturbative triples method with the density-fitting approximation.

    PubMed

    Bozkaya, Uğur; Sherrill, C David

    2017-07-28

    An efficient implementation of analytic gradients for the coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method with the density-fitting (DF) approximation, denoted as DF-CCSD(T), is reported. For the molecules considered, the DF approach substantially accelerates conventional CCSD(T) analytic gradients due to the reduced input/output time and the acceleration of the so-called "gradient terms": formation of particle density matrices (PDMs), computation of the generalized Fock-matrix (GFM), solution of the Z-vector equation, formation of the effective PDMs and GFM, back-transformation of the PDMs and GFM, from the molecular orbital to the atomic orbital (AO) basis, and computation of gradients in the AO basis. For the largest member of the molecular test set considered (C6H14), the computational times for analytic gradients (with the correlation-consistent polarized valence triple-ζ basis set in serial) are 106.2 [CCSD(T)] and 49.8 [DF-CCSD(T)] h, a speedup of more than 2-fold. In the evaluation of gradient terms, the DF approach completely avoids the use of four-index two-electron integrals. Similar to our previous studies on DF-second-order Møller-Plesset perturbation theory and DF-CCSD gradients, our formalism employs 2- and 3-index two-particle density matrices (TPDMs) instead of 4-index TPDMs. Errors introduced by the DF approximation are negligible for equilibrium geometries and harmonic vibrational frequencies.

  12. Multi-level coupled cluster theory

    SciTech Connect

    Myhre, Rolf H.; Koch, Henrik; Sánchez de Merás, Alfredo M. J.

    2014-12-14

    We present a general formalism where different levels of coupled cluster theory can be applied to different parts of the molecular system. The system is partitioned into subsystems by Cholesky decomposition of the one-electron Hartree-Fock density matrix. In this way the system can be divided across chemical bonds without discontinuities arising. The coupled cluster wave function is defined in terms of cluster operators for each part and these are determined from a set of coupled equations. The total wave function fulfills the Pauli-principle across all borders and levels of electron correlation. We develop the associated response theory for this multi-level coupled cluster theory and present proof of principle applications. The formalism is an essential tool in order to obtain size-intensive complexity in the calculation of local molecular properties.

  13. Coupled-Cluster Theory for Nuclear Science

    NASA Astrophysics Data System (ADS)

    Dean, D. J.

    2003-10-01

    I discuss an initial implementation of the coupled-cluster method for nuclear structure calculations and apply our method to 4He. In this procedings I will discuss the effect of center-of-mass removal on our results.

  14. A new near-linear scaling, efficient and accurate, open-shell domain-based local pair natural orbital coupled cluster singles and doubles theory.

    PubMed

    Saitow, Masaaki; Becker, Ute; Riplinger, Christoph; Valeev, Edward F; Neese, Frank

    2017-04-28

    The Coupled-Cluster expansion, truncated after single and double excitations (CCSD), provides accurate and reliable molecular electronic wave functions and energies for many molecular systems around their equilibrium geometries. However, the high computational cost, which is well-known to scale as O(N(6)) with system size N, has limited its practical application to small systems consisting of not more than approximately 20-30 atoms. To overcome these limitations, low-order scaling approximations to CCSD have been intensively investigated over the past few years. In our previous work, we have shown that by combining the pair natural orbital (PNO) approach and the concept of orbital domains it is possible to achieve fully linear scaling CC implementations (DLPNO-CCSD and DLPNO-CCSD(T)) that recover around 99.9% of the total correlation energy [C. Riplinger et al., J. Chem. Phys. 144, 024109 (2016)]. The production level implementations of the DLPNO-CCSD and DLPNO-CCSD(T) methods were shown to be applicable to realistic systems composed of a few hundred atoms in a routine, black-box fashion on relatively modest hardware. In 2011, a reduced-scaling CCSD approach for high-spin open-shell unrestricted Hartree-Fock reference wave functions was proposed (UHF-LPNO-CCSD) [A. Hansen et al., J. Chem. Phys. 135, 214102 (2011)]. After a few years of experience with this method, a few shortcomings of UHF-LPNO-CCSD were noticed that required a redesign of the method, which is the subject of this paper. To this end, we employ the high-spin open-shell variant of the N-electron valence perturbation theory formalism to define the initial guess wave function, and consequently also the open-shell PNOs. The new PNO ansatz properly converges to the closed-shell limit since all truncations and approximations have been made in strict analogy to the closed-shell case. Furthermore, given the fact that the formalism uses a single set of orbitals, only a single PNO integral transformation is

  15. A coupled-cluster study of photodetachment cross sections of closed-shell anions.

    PubMed

    Cukras, Janusz; Decleva, Piero; Coriani, Sonia

    2014-11-07

    We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H(-), Li(-), Na(-), F(-), Cl(-), and OH(-). The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

  16. Coupled-cluster computations of atomic nuclei.

    PubMed

    Hagen, G; Papenbrock, T; Hjorth-Jensen, M; Dean, D J

    2014-09-01

    In the past decade, coupled-cluster theory has seen a renaissance in nuclear physics, with computations of neutron-rich and medium-mass nuclei. The method is efficient for nuclei with product-state references, and it describes many aspects of weakly bound and unbound nuclei. This report reviews the technical and conceptual developments of this method in nuclear physics, and the results of coupled-cluster calculations for nucleonic matter, and for exotic isotopes of helium, oxygen, calcium, and some of their neighbors.

  17. Seniority-based coupled cluster theory

    SciTech Connect

    Henderson, Thomas M.; Scuseria, Gustavo E.; Bulik, Ireneusz W.; Stein, Tamar

    2014-12-28

    Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling (N{sup 3}, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive for weakly correlated systems and often superior for the description of strongly correlated systems.

  18. Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra.

    PubMed

    Cukras, Janusz; Coriani, Sonia; Decleva, Piero; Christiansen, Ove; Norman, Patrick

    2013-09-07

    A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H2, H2O, NH3, HF, CO, and CO2.

  19. Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra

    SciTech Connect

    Cukras, Janusz; Coriani, Sonia; Decleva, Piero; Christiansen, Ove; Norman, Patrick

    2013-09-07

    A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H{sub 2}, H{sub 2}O, NH{sub 3}, HF, CO, and CO{sub 2}.

  20. Single-cluster dynamics for the random-cluster model

    NASA Astrophysics Data System (ADS)

    Deng, Youjin; Qian, Xiaofeng; Blöte, Henk W. J.

    2009-09-01

    We formulate a single-cluster Monte Carlo algorithm for the simulation of the random-cluster model. This algorithm is a generalization of the Wolff single-cluster method for the q -state Potts model to noninteger values q>1 . Its results for static quantities are in a satisfactory agreement with those of the existing Swendsen-Wang-Chayes-Machta (SWCM) algorithm, which involves a full-cluster decomposition of random-cluster configurations. We explore the critical dynamics of this algorithm for several two-dimensional Potts and random-cluster models. For integer q , the single-cluster algorithm can be reduced to the Wolff algorithm, for which case we find that the autocorrelation functions decay almost purely exponentially, with dynamic exponents zexp=0.07 (1), 0.521 (7), and 1.007 (9) for q=2 , 3, and 4, respectively. For noninteger q , the dynamical behavior of the single-cluster algorithm appears to be very dissimilar to that of the SWCM algorithm. For large critical systems, the autocorrelation function displays a range of power-law behavior as a function of time. The dynamic exponents are relatively large. We provide an explanation for this peculiar dynamic behavior.

  1. Single-cluster dynamics for the random-cluster model.

    PubMed

    Deng, Youjin; Qian, Xiaofeng; Blöte, Henk W J

    2009-09-01

    We formulate a single-cluster Monte Carlo algorithm for the simulation of the random-cluster model. This algorithm is a generalization of the Wolff single-cluster method for the q-state Potts model to noninteger values q>1. Its results for static quantities are in a satisfactory agreement with those of the existing Swendsen-Wang-Chayes-Machta (SWCM) algorithm, which involves a full-cluster decomposition of random-cluster configurations. We explore the critical dynamics of this algorithm for several two-dimensional Potts and random-cluster models. For integer q, the single-cluster algorithm can be reduced to the Wolff algorithm, for which case we find that the autocorrelation functions decay almost purely exponentially, with dynamic exponents z(exp)=0.07 (1), 0.521 (7), and 1.007 (9) for q=2, 3, and 4, respectively. For noninteger q, the dynamical behavior of the single-cluster algorithm appears to be very dissimilar to that of the SWCM algorithm. For large critical systems, the autocorrelation function displays a range of power-law behavior as a function of time. The dynamic exponents are relatively large. We provide an explanation for this peculiar dynamic behavior.

  2. Event-based cluster synchronization of coupled genetic regulatory networks

    NASA Astrophysics Data System (ADS)

    Yue, Dandan; Guan, Zhi-Hong; Li, Tao; Liao, Rui-Quan; Liu, Feng; Lai, Qiang

    2017-09-01

    In this paper, the cluster synchronization of coupled genetic regulatory networks with a directed topology is studied by using the event-based strategy and pinning control. An event-triggered condition with a threshold consisting of the neighbors' discrete states at their own event time instants and a state-independent exponential decay function is proposed. The intra-cluster states information and extra-cluster states information are involved in the threshold in different ways. By using the Lyapunov function approach and the theories of matrices and inequalities, we establish the cluster synchronization criterion. It is shown that both the avoidance of continuous transmission of information and the exclusion of the Zeno behavior are ensured under the presented triggering condition. Explicit conditions on the parameters in the threshold are obtained for synchronization. The stability criterion of a single GRN is also given under the reduced triggering condition. Numerical examples are provided to validate the theoretical results.

  3. Communication: A simplified coupled-cluster Lagrangian for polarizable embedding

    SciTech Connect

    Krause, Katharina; Klopper, Wim

    2016-01-28

    A simplified coupled-cluster Lagrangian, which is linear in the Lagrangian multipliers, is proposed for the coupled-cluster treatment of a quantum mechanical system in a polarizable environment. In the simplified approach, the amplitude equations are decoupled from the Lagrangian multipliers and the energy obtained from the projected coupled-cluster equation corresponds to a stationary point of the Lagrangian.

  4. A coupled-cluster study of photodetachment cross sections of closed-shell anions

    SciTech Connect

    Cukras, Janusz; Decleva, Piero; Coriani, Sonia

    2014-11-07

    We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H{sup −}, Li{sup −}, Na{sup −}, F{sup −}, Cl{sup −}, and OH{sup −}. The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

  5. Study of molecular vibration by coupled cluster method: Bosonic approach

    NASA Astrophysics Data System (ADS)

    Banik, Subrata; Pal, Sourav; Prasad, M. Durga

    2015-01-01

    The vibrational coupled cluster method in bosonic representation is formulated to describe the molecular anharmonic vibrational spectra. The vibrational coupled cluster formalism is based on Watson Hamiltonian in normal coordinates. The vibrational excited states are described using coupled cluster linear response theory (CCLRT). The quality of the coupled cluster wave function is analyzed. Specifically, the mean displacement values of the normal coordinates and expectation values of the square of the normal coordinates of different vibrational states are calculated. A good agreement between the converged full CI results and coupled cluster results is found for the lower lying vibrational states.

  6. Approximating electronically excited states with equation-of-motion linear coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Byrd, Jason N.; Rishi, Varun; Perera, Ajith; Bartlett, Rodney J.

    2015-10-01

    A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Møller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory equations and two new equation-of-motion methods based on the linear coupled-cluster doubles and linear coupled-cluster singles and doubles wavefunctions. These new methods are benchmarked against very accurate theoretical and experimental spectra from 25 small organic molecules. It is found that the proposed methods have excellent agreement with canonical equation-of-motion coupled-cluster singles and doubles state for state orderings and relative excited state energies as well as acceptable quantitative agreement for absolute excitation energies compared with the best estimate theory and experimental spectra.

  7. Approximating electronically excited states with equation-of-motion linear coupled-cluster theory

    SciTech Connect

    Byrd, Jason N. Rishi, Varun; Perera, Ajith; Bartlett, Rodney J.

    2015-10-28

    A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Møller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory equations and two new equation-of-motion methods based on the linear coupled-cluster doubles and linear coupled-cluster singles and doubles wavefunctions. These new methods are benchmarked against very accurate theoretical and experimental spectra from 25 small organic molecules. It is found that the proposed methods have excellent agreement with canonical equation-of-motion coupled-cluster singles and doubles state for state orderings and relative excited state energies as well as acceptable quantitative agreement for absolute excitation energies compared with the best estimate theory and experimental spectra.

  8. Aging and clustering in globally coupled oscillators.

    PubMed

    Daido, Hiroaki; Nakanishi, Kenji

    2007-05-01

    A population of coupled nonlinear oscillators may age in such a way that the fraction of non-self-oscillatory elements increases. Following our previous paper [Phys. Rev. Lett. 93, 104101 (2004)], we study the effect of aging in this sense mainly for globally coupled Stuart-Landau oscillators with the emphasis on the structure of the (K,p) phase diagram, where K is the coupling strength and p is the ratio of inactive oscillators. In addition to the aging transition reported previously, such a diagram is shown to be characterized by a hornlike region, which we call a "desynchronization horn," where active oscillators desynchronize to form a number of clusters, provided that uncoupled active oscillators are sufficiently nonisochronous. We also show that desynchronization in such a region can be captured as a type of diffusion-induced inhomogeneity based on a "swing-by mechanism." Our results suggest that the desynchronization horn with some curious properties may be a fairly common feature in aging systems of globally and diffusively coupled periodic oscillators.

  9. Optimized coordinates in vibrational coupled cluster calculations

    SciTech Connect

    Thomsen, Bo; Christiansen, Ove; Yagi, Kiyoshi

    2014-04-21

    The use of variationally optimized coordinates, which minimize the vibrational self-consistent field (VSCF) ground state energy with respect to orthogonal transformations of the coordinates, has recently been shown to improve the convergence of vibrational configuration interaction (VCI) towards the exact full VCI [K. Yagi, M. Keçeli, and S. Hirata, J. Chem. Phys. 137, 204118 (2012)]. The present paper proposes an incorporation of optimized coordinates into the vibrational coupled cluster (VCC), which has in the past been shown to outperform VCI in approximate calculations where similar restricted state spaces are employed in VCI and VCC. An embarrassingly parallel algorithm for variational optimization of coordinates for VSCF is implemented and the resulting coordinates and potentials are introduced into a VCC program. The performance of VCC in optimized coordinates (denoted oc-VCC) is examined through pilot applications to water, formaldehyde, and a series of water clusters (dimer, trimer, and hexamer) by comparing the calculated vibrational energy levels with those of the conventional VCC in normal coordinates and VCI in optimized coordinates. For water clusters, in particular, oc-VCC is found to gain orders of magnitude improvement in the accuracy, exemplifying that the combination of optimized coordinates localized to each monomer with the size-extensive VCC wave function provides a supreme description of systems consisting of weakly interacting sub-systems.

  10. Explicitly correlated coupled-cluster theory with Brueckner orbitals.

    PubMed

    Tew, David P

    2016-08-21

    Brueckner orbitals are the optimal orbitals for use in F12 explicitly correlated coupled-cluster (CC) treatments. A novel approach, Brueckner coupled-cluster doubles with perturbative triples BCCD(T)(F12*) is presented that avoids the expensive re-evaluation of F12 integrals throughout the orbital optimisation and includes a newly derived basis set correction to the Brueckner reference energy. The generalisation of F12 theory to arbitrary non-Hartree-Fock references and to Fock operators that include scalar relativistic effects is also presented. The performance of the new Brueckner F12 method is assessed for a test set of 50 open- and closed-shell reactions and for the ionisation potentials and electron affinities (EAs) of the first-row transition metal atoms. Benchmark basis set limit coupled-cluster singles, doubles and perturbative triples (CCSD(T)) and BCCD(T) values are reported for all energies in the test sets. BCCD(T)(F12*) performs systematically better than CCSD(T)(F12*) for electron affinities where orbital relaxation effects are significant.

  11. Single-particle levels in cluster potentials

    NASA Astrophysics Data System (ADS)

    Della Rocca, V.; Bijker, R.; Iachello, F.

    2017-10-01

    We calculate single-particle levels in potentials with Z2 (dumbbell), D3h (triangle) and Td (tetrahedral) symmetry, appropriate to the α-cluster structure of 8Be, 12C and 16O respectively. We suggest that these can be used to study, within the framework of a cluster shell model (CSM), kα + x nucleon structures, with k = 2 , 3 , 4 and x = 1 , 2 , …, in particular the single particle (x = 1) structures 9Be, 9B; 13C, 13N; 17O, 17F.

  12. Analytic energy gradients in closed-shell coupled-cluster theory with spin-orbit coupling.

    PubMed

    Wang, Fan; Gauss, Jürgen

    2008-11-07

    Gradients in closed-shell coupled-cluster (CC) theory with spin-orbit coupling included in the post Hartree-Fock treatment have been implemented at the CC singles and doubles (CCSD) level and at the CCSD level augmented by a perturbative treatment of triple excitations [CCSD(T)]. The additional computational effort required in analytic energy-gradient calculations is roughly the same as that for ground-state energy calculations in the case of CCSD, and it is about twice in the case of CCSD(T) calculations. The structures, harmonic frequencies, and dipole moments of some heavy-element compounds have been calculated using the present analytic energy-gradient techniques including spin-orbit coupling. The results show that spin-orbit coupling can have a significant influence on both the equilibrium structure and the harmonic vibrational frequencies and that its inclusion is essential to obtain reliable and accurate estimates for geometrical parameters of heavy-element compounds.

  13. Explicitly correlated ring-coupled-cluster-doubles theory

    SciTech Connect

    Hehn, Anna-Sophia; Klopper, Wim; Tew, David P.

    2015-05-21

    The connection between the random-phase approximation and the ring-coupled-cluster-doubles method bridges the gap between density-functional and wave-function theories and the importance of the random-phase approximation lies in both its broad applicability and this linking role in electronic-structure theory. In this contribution, we present an explicitly correlated approach to the random-phase approximation, based on the direct ring-coupled-cluster-doubles ansatz, which overcomes the problem of slow basis-set convergence, inherent to the random-phase approximation. Benchmark results for a test set of 106 molecules and a selection of 10 organic complexes from the S22 test set demonstrate that convergence to within 99% of the basis-set limit is reached for triple-zeta basis sets for atomisation energies, while quadruple-zeta basis sets are required for interaction energies. Corrections due to single excitations into the complementary auxiliary space reduce the basis-set incompleteness error by one order of magnitude, while contributions due to the coupling of conventional and geminal amplitudes are in general negligible. We find that a non-iterative explicitly correlated correction to first order in perturbation theory exhibits the best ratio of accuracy to computational cost.

  14. The coupled cluster method and entanglement in three fermion systems

    NASA Astrophysics Data System (ADS)

    Lévay, Péter; Nagy, Szilvia; Pipek, János; Sárosi, Gábor

    2017-01-01

    The Coupled Cluster (CC) and full CI expansions are studied for three fermions with six and seven modes. Surprisingly the CC expansion is tailor made to characterize the usual stochastic local operations and classical communication (SLOCC) entanglement classes. It means that the notion of a SLOCC transformation shows up quite naturally as a one relating the CC and CI expansions, and going from the CI expansion to the CC one is equivalent to obtaining a form for the state where the structure of the entanglement classes is transparent. In this picture, entanglement is characterized by the parameters of the cluster operators describing transitions from occupied states to singles, doubles, and triples of non-occupied ones. Using the CC parametrization of states in the seven-mode case, we give a simple formula for the unique SLOCC invariant J . Then we consider a perturbation problem featuring a state from the unique SLOCC class characterized by J ≠ 0 . For this state with entanglement generated by doubles, we investigate the phenomenon of changing the entanglement type due to the perturbing effect of triples. We show that there are states with real amplitudes such that their entanglement encoded into configurations of clusters of doubles is protected from errors generated by triples. Finally we put forward a proposal to use the parameters of the cluster operator describing transitions to doubles for entanglement characterization. Compared to the usual SLOCC classes, this provides a coarse grained approach to fermionic entanglement.

  15. Electromigration of single-layer clusters

    NASA Astrophysics Data System (ADS)

    Pierre-Louis, O.; Einstein, T. L.

    2001-05-01

    We describe the steady states, fluctuations, dynamics, and instabilities of atom and of vacancy single-layer-height islands during electromigration, assuming an isotropic medium. We emphasize the dependence on cluster size and on the three standard limiting cases of mass-transport mechanism: periphery diffusion (PD), terrace diffusion (TD), or evaporation-condensation (EC), as well as the differences between atom and vacancy clusters. A general model provides power laws describing the size dependence of the drift velocity in these limits, consistent with established (in the case of PD) results. For PD, atom and vacancy islands drift in opposite directions; otherwise they drift in the same direction. The validity of the widely used quasistatic limit is calculated. Linear stability analysis reveals a new type of morphological instability, not leading to island break-down. We find non-circular steady states for EC vacancy islands. Analytical calculations are corroborated by both Monte Carlo simulations and numerical integration. For weak electromigration the cluster responds isotropically for TD and PD but not EC. In EC, clusters elongate perpendicular to the drift axis. In PD a morphological instability at strong electromigration leads to cluster splitting, in contrast to destabilizing into slits in the other cases. TD or EC induces a new instability for vacancy clusters above a threshold. Using Langevin formalism, we derive the non-equilibrium cluster diffusion constant and study morphological fluctuations. Electromigration affects the diffusion coefficient of the cluster and morphological fluctuations, which diverge at the instability threshold. An instrinsic attachment-detachment bias displays the same scaling signature as PD in the drift velocity.

  16. Convergence of coupled cluster perturbation theory

    NASA Astrophysics Data System (ADS)

    Eriksen, Janus J.; Kristensen, Kasper; Matthews, Devin A.; Jørgensen, Poul; Olsen, Jeppe

    2016-12-01

    The convergence of a recently proposed coupled cluster (CC) family of perturbation series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)], in which the energetic difference between two CC models—a low-level parent and a high-level target model—is expanded in orders of the Møller-Plesset (MP) fluctuation potential, is investigated for four prototypical closed-shell systems (Ne, singlet CH2, distorted HF, and F-) in standard and augmented basis sets. In these investigations, energy corrections of the various series have been calculated to high orders and their convergence radii have been determined by probing for possible front- and back-door intruder states, the existence of which would make the series divergent. In summary, we conclude how it is primarily the choice of the target state, and not the choice of the parent state, which ultimately governs the convergence behavior of a given series. For example, restricting the target state to, say, triple or quadruple excitations might remove intruders present in series which target the full configuration interaction limit, such as the standard MP series. Furthermore, we find that whereas a CC perturbation series might converge within standard correlation consistent basis sets, it may start to diverge whenever these become augmented by diffuse functions, similar to the MP case. However, unlike for the MP case, such potential divergences are not found to invalidate the practical use of the low-order corrections of the CC perturbation series.

  17. Single mode lasing in coupled nanowires

    NASA Astrophysics Data System (ADS)

    Xiao, Yao; Meng, Chao; Wu, Xiaoqin; Tong, Limin

    2011-07-01

    We demonstrate single mode lasing in coupled CdSe nanowires. By coupling two 420 nm diameter CdSe nanowires to form an X-structure cavity, single-mode lasing emission around 734.3 nm is obtained with line width of 0.11 nm and lasing threshold of about 120 μJ/cm2. Mode selection in the lasing nanowire is realized via Vernier effect in the coupled cavities. Our results suggest a simple approach to single-mode nanowire lasers.

  18. Cluster synchronization induced by one-node clusters in networks with asymmetric negative couplings

    SciTech Connect

    Zhang, Jianbao; Ma, Zhongjun; Zhang, Gang

    2013-12-15

    This paper deals with the problem of cluster synchronization in networks with asymmetric negative couplings. By decomposing the coupling matrix into three matrices, and employing Lyapunov function method, sufficient conditions are derived for cluster synchronization. The conditions show that the couplings of multi-node clusters from one-node clusters have beneficial effects on cluster synchronization. Based on the effects of the one-node clusters, an effective and universal control scheme is put forward for the first time. The obtained results may help us better understand the relation between cluster synchronization and cluster structures of the networks. The validity of the control scheme is confirmed through two numerical simulations, in a network with no cluster structure and in a scale-free network.

  19. An accurate local model for triple substitutions in fourth order M[oslash]ller Plesset theory and in perturbative corrections to singles and doubles coupled cluster methods

    NASA Astrophysics Data System (ADS)

    Maslen, P. E.; Lee, M. S.; Head-Gordon, M.

    2000-03-01

    Two noniterative local models for evaluating the contribution of triple substitutions to the electron correlation energy (as needed in MP4 and CCSD(T)), are developed. The occupied space is spanned by a minimal basis, and the virtual space by an extended basis of atom-centered functions. The triple substitutions are truncated by an atomic criterion such that either zero or one electrons can be transferred between atoms. The covalent model asymptotically recovers 70% of the triples correlation energy for poly-ynes with a 6-31G* basis, while the singly-ionic model recovers 99%.

  20. Symmetry exploitation in closed-shell coupled-cluster theory with spin-orbit coupling.

    PubMed

    Tu, Zheyan; Yang, Dong-Dong; Wang, Fan; Guo, Jingwei

    2011-07-21

    In the present work, we report exploitation of spatial symmetry in calculations of ground state energy and analytic first derivatives of closed-shell molecules based on our previously developed coupled-cluster (CC) approach with spin-orbit coupling. Both time-reversal symmetry and spatial symmetry for D(2h) and its subgroups are exploited in the implementation. The symmetry of a certain spin case for the amplitude, intermediate, or density matrix is determined by the symmetry of the corresponding spin functions and the direct product decomposition method is employed in computations involving these quantities. The reduction in computational effort achieved through the use of spatial symmetry is larger than the order of the molecular single point group. Symmetry exploitation renders application of the CC approaches with spin-orbit coupling to larger closed-shell molecules containing heavy elements with high accuracy.

  1. Circuit electromechanics with single photon strong coupling

    SciTech Connect

    Xue, Zheng-Yuan Yang, Li-Na; Zhou, Jian

    2015-07-13

    In circuit electromechanics, the coupling strength is usually very small. Here, replacing the capacitor in circuit electromechanics by a superconducting flux qubit, we show that the coupling among the qubit and the two resonators can induce effective electromechanical coupling which can attain the strong coupling regime at the single photon level with feasible experimental parameters. We use dispersive couplings among two resonators and the qubit while the qubit is also driven by an external classical field. These couplings form a three-wave mixing configuration among the three elements where the qubit degree of freedom can be adiabatically eliminated, and thus results in the enhanced coupling between the two resonators. Therefore, our work constitutes the first step towards studying quantum nonlinear effect in circuit electromechanics.

  2. Analytic second derivatives in closed-shell coupled-cluster theory with spin-orbit coupling.

    PubMed

    Wang, Fan; Gauss, Jürgen

    2009-10-28

    The theory for geometrical second derivatives of the energy is outlined for the recently suggested two-component coupled-cluster approach using relativistic effective core potentials with spin-orbit coupling included in the post-Hartree-Fock treatment [F. Wang, J. Gauss, and C. van Wullen, J. Chem. Phys. 129, 064113 (2008)], and an implementation is reported at the coupled-cluster singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations [CCSD(T)]. The applicability of the developed analytic second-derivative techniques is demonstrated by computing harmonic and fundamental frequencies for PtH(2), PbH(2), and HgH(2) with the required cubic and semidiagonal quartic force fields obtained by numerical differentiation of the analytically evaluated quadratic force constants. Spin-orbit coupling effects are shown to be non-negligible for the three considered molecules and thus need to be considered in the case of high-accuracy predictions.

  3. Coupling single emitters to quantum plasmonic circuits

    NASA Astrophysics Data System (ADS)

    Huck, Alexander; Andersen, Ulrik L.

    2016-09-01

    In recent years, the controlled coupling of single-photon emitters to propagating surface plasmons has been intensely studied, which is fueled by the prospect of a giant photonic nonlinearity on a nanoscaled platform. In this article, we will review the recent progress on coupling single emitters to nanowires towards the construction of a new platform for strong light-matter interaction. The control over such a platform might open new doors for quantum information processing and quantum sensing at the nanoscale and for the study of fundamental physics in the ultrastrong coupling regime.

  4. Efficient open-shell coupled-cluster and perturbation theories

    SciTech Connect

    Lee, T.J.; Jayatilaka, D.

    1993-12-31

    A new spin orbital basis is employed in the development of efficient open-shell coupled-cluster and perturbation theories that are based on a restricted Hartree-Fock (RHF) reference function. The spin orbital basis is different from the standard one in the spin functions that are associated with the singly occupied spatial orbital. The occupied orbital (in the spin orbital basis) is assigned the {sigma}{sup +} = 1/{radical}2({alpha} + {beta}) spin function while the unoccupied orbital is assigned the {sigma}{sup {minus}} = 1/{radical}2({alpha} {minus} {beta}) spin function. The doubly occupied and unoccupied orbitals (in the reference function) are assigned the standard {alpha} and {beta} spin orbitals. The coupled-cluster and perturbation theory wave functions based on this set of {open_quotes}symmetric spin orbitals{close_quotes} exhibit much more symmetry than those based on the standard spin orbital basis. This, together with interacting space arguments, leads to a dramatic reduction in the computational cost.

  5. Pair-correlated coupled cluster theory: An alternative multireference coupled cluster method

    NASA Astrophysics Data System (ADS)

    Li, Shuhua; Ma, Jing; Jiang, Yuansheng

    2003-04-01

    We describe an alternative multireference coupled cluster (MRCC) method, pair-correlated coupled cluster (PCCC) theory, for treating the ground state of closed-shell systems with degeneracy or quasidegeneracy. With the separated electron pair (SEP) wave function as a reference, the PCCC wave function is truncated according to how many electron pairs are explicitly correlated. The inclusion of only two-pair correlation defines the PCCC2 scheme, and the inclusion of up to three-pair correlation gives the PCCC3 scheme. The PCCC theory is well defined within the natural orbital (of the SEP reference) description and size extensive. We present the formalism of the PCCC theory by taking the PCCC2 scheme as an example, and implement the PCCC2 and PCCC3 schemes at the ab initio level with various basis sets. Then illustrative applications are presented for systems such as the perpendicular insertion reaction path of Be into H2, the simultaneous bond stretching in AlH3 and H2O. The results show that the overall performance of PCCC methods is competitive to that of the RCCSD(T) or UCCSD(T) method at stretched geometries, but slightly inferior to that of the CCSD(T) method at the equilibrium geometry.

  6. Static polarizabilities for excited states within the spin-conserving and spin-flipping equation-of-motion coupled-cluster singles and doubles formalism: Theory, implementation, and benchmarks

    NASA Astrophysics Data System (ADS)

    Nanda, Kaushik D.; Krylov, Anna I.

    2016-11-01

    We present the theory and implementation for calculating static polarizabilities within the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) framework for electronically excited states and its spin-flip variant. We evaluate the second derivatives of the EOM-CCSD Lagrangian with respect to electric-field perturbations. The relaxation of reference molecular orbitals is not included. In our approach, the wave function amplitudes satisfy the 2n + 1 rule and the amplitude-response Lagrange multipliers satisfy the 2n + 2 rule. The new implementation is validated against finite-field and CCSD response-theory calculations of the excited-state polarizabilities of pyrimidine and s-tetrazine. We use the new method to compute static polarizabilities of different types of electronic states (valence, charge-transfer, singlets, and triplets) in open- and closed-shell systems (uracil, p-nitroaniline, methylene, and p-benzyne). We also present an alternative approach for calculating excited-state static polarizabilities as expectation values by using the EOM-CCSD wave functions and energies in the polarizability expression for an exact state. We find that this computationally less demanding approach may show differences up to ˜30 % relative to the excited-state polarizabilities computed using the analytic-derivative formalism.

  7. Static polarizabilities for excited states within the spin-conserving and spin-flipping equation-of-motion coupled-cluster singles and doubles formalism: Theory, implementation, and benchmarks.

    PubMed

    Nanda, Kaushik D; Krylov, Anna I

    2016-11-28

    We present the theory and implementation for calculating static polarizabilities within the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) framework for electronically excited states and its spin-flip variant. We evaluate the second derivatives of the EOM-CCSD Lagrangian with respect to electric-field perturbations. The relaxation of reference molecular orbitals is not included. In our approach, the wave function amplitudes satisfy the 2n + 1 rule and the amplitude-response Lagrange multipliers satisfy the 2n + 2 rule. The new implementation is validated against finite-field and CCSD response-theory calculations of the excited-state polarizabilities of pyrimidine and s-tetrazine. We use the new method to compute static polarizabilities of different types of electronic states (valence, charge-transfer, singlets, and triplets) in open- and closed-shell systems (uracil, p-nitroaniline, methylene, and p-benzyne). We also present an alternative approach for calculating excited-state static polarizabilities as expectation values by using the EOM-CCSD wave functions and energies in the polarizability expression for an exact state. We find that this computationally less demanding approach may show differences up to ∼30% relative to the excited-state polarizabilities computed using the analytic-derivative formalism.

  8. Coupled cluster algorithms for networks of shared memory parallel processors

    NASA Astrophysics Data System (ADS)

    Bentz, Jonathan L.; Olson, Ryan M.; Gordon, Mark S.; Schmidt, Michael W.; Kendall, Ricky A.

    2007-05-01

    As the popularity of using SMP systems as the building blocks for high performance supercomputers increases, so too increases the need for applications that can utilize the multiple levels of parallelism available in clusters of SMPs. This paper presents a dual-layer distributed algorithm, using both shared-memory and distributed-memory techniques to parallelize a very important algorithm (often called the "gold standard") used in computational chemistry, the single and double excitation coupled cluster method with perturbative triples, i.e. CCSD(T). The algorithm is presented within the framework of the GAMESS [M.W. Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert, M.S. Gordon, J.J. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, General atomic and molecular electronic structure system, J. Comput. Chem. 14 (1993) 1347-1363]. (General Atomic and Molecular Electronic Structure System) program suite and the Distributed Data Interface [M.W. Schmidt, G.D. Fletcher, B.M. Bode, M.S. Gordon, The distributed data interface in GAMESS, Comput. Phys. Comm. 128 (2000) 190]. (DDI), however, the essential features of the algorithm (data distribution, load-balancing and communication overhead) can be applied to more general computational problems. Timing and performance data for our dual-level algorithm is presented on several large-scale clusters of SMPs.

  9. Electromigration of single-layer clusters

    NASA Astrophysics Data System (ADS)

    Pierre-Louis, O.; Einstein, T. L.

    2000-11-01

    Single-layer atom or vacancy clusters in the presence of electromigration are studied theoretically assuming an isotropic medium. A variety of distinctive behaviors distinguish the response in the three standard limiting cases of periphery diffusion (PD), terrace diffusion, and evaporation-condensation. A general model provides power laws describing the size dependence of the drift velocity in these limits, consistent with established results in the case of PD. The validity of the widely used quasistatic limit is calculated. Atom and vacancy clusters drift in opposite directions in the PD limit but in the same direction otherwise. In absence of PD, linear stability analysis reveals a different type of morphological instability, not leading to island breakdown. For strong electromigration, Monte Carlo simulations show that clusters then destabilize into slits, in contrast to splitting in the PD limit. Electromigration affects the diffusion coefficient of the cluster and morphological fluctuations, the latter diverging at the instability threshold. An intrinsic attachment-detachment bias displays the same scaling signature as PD in the drift velocity.

  10. Delay-induced cluster patterns in coupled Cayley tree networks

    NASA Astrophysics Data System (ADS)

    Singh, A.; Jalan, S.

    2013-07-01

    We study effects of delay in diffusively coupled logistic maps on the Cayley tree networks. We find that smaller coupling values exhibit sensitiveness to value of delay, and lead to different cluster patterns of self-organized and driven types. Whereas larger coupling strengths exhibit robustness against change in delay values, and lead to stable driven clusters comprising nodes from last generation of the Cayley tree. Furthermore, introduction of delay exhibits suppression as well as enhancement of synchronization depending upon coupling strength values. To the end we discuss the importance of results to understand conflicts and cooperations observed in family business.

  11. High performance organic photovoltaics with plasmonic-coupled metal nanoparticle clusters.

    PubMed

    Park, Hyung Il; Lee, Seunghoon; Lee, Ju Min; Nam, Soo Ah; Jeon, Taewoo; Han, Sang Woo; Kim, Sang Ouk

    2014-10-28

    Performance enhancement of organic photovoltaics using plasmonic nanoparticles has been limited without interparticle plasmon coupling. We demonstrate high performance organic photovoltaics employing gold nanoparticle clusters with controlled morphology as a plasmonic component. Near-field coupling at the interparticle gaps of nanoparticle clusters gives rise to strong enhancement in localized electromagnetic field, which led to the significant improvement of exciton generation and dissociation in the active layer of organic solar cells. A power conversion efficiency of 9.48% is attained by employing gold nanoparticle clusters at the bottom of the organic active layer. This is one of the highest efficiency values reported thus far for the single active layer organic photovoltaics.

  12. Communication: Application of state-specific multireference coupled cluster methods to core-level excitations

    NASA Astrophysics Data System (ADS)

    Brabec, Jiří; Bhaskaran-Nair, Kiran; Govind, Niranjan; Pittner, Jiří; Kowalski, Karol

    2012-11-01

    The concept of the model space underlying multireference coupled-cluster (MRCC) formulations is a powerful tool to deal with complex correlation effects for various electronic states. Here, we demonstrate that iterative state-specific MRCC methods (SS-MRCC) based on properly defined model spaces can be used to describe core-level excited states even when Hartree-Fock orbitals are utilized. We show that the SS-MRCC models with single and double excitations are comparable in accuracy to high-level single reference equation-of-motion coupled cluster (EOMCC) formalism.

  13. Mutual synchronization and clustering in randomly coupled chaotic dynamical networks.

    PubMed

    Manrubia, S C; Mikhailov, A S

    1999-08-01

    We introduce and study systems of randomly coupled maps where the relevant parameter is the degree of connectivity in the system. Global (almost-) synchronized states are found (equivalent to the synchronization observed in globally coupled maps) until a certain critical threshold for the connectivity is reached. We further show that not only the average connectivity, but also the architecture of the couplings is responsible for the cluster structure observed. We analyze the different phases of the system and use various correlation measures in order to detect ordered nonsynchronized states. Finally, it is shown that the system displays a dynamical hierarchical clustering which allows the definition of emerging graphs.

  14. Coupled-Cluster in Real Space II: CC2 Excited States using Multi-Resolution Analysis.

    PubMed

    Kottmann, Jakob Siegfried; Bischoff, Florian Andreas

    2017-09-13

    We report a first quantized approach to calculate approximate coupled-cluster singles and doubles CC2 excitation energies in real space. The cluster functions are directly represented on an adaptive grid using multiresolution analysis. Virtual orbitals are neither calculated nor needed which leads to an improved formal scaling. The nuclear and electronic cusps are taken into account explicitly where our ansatz regularizes the corresponding equations exactly. First calculations on small molecules are in excellent agreement with the best available LCAO approaches.

  15. Analytic evaluation of the nonadiabatic coupling vector between excited states using equation-of-motion coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Tajti, Attila; Szalay, Péter G.

    2009-09-01

    Theory and implementation for evaluation of the nonadiabatic coupling vector between excited electronic states described by equation-of-motion excitation energy coupled-cluster singles and doubles (EOMEE-CCSD) method is presented. Problems arising from the non-Hermitian nature of the theory are discussed in detail. The performance of the new approach is demonstrated by the nice agreement of the nonadiabatic coupling curves for LiH obtained at the EOMEE-CCSD and MR-CISD levels. Using the tools developed we also present a computational procedure to evaluate the interstate coupling constants used in vibronic coupling theories. As an application of this part of the implementation we present simulation of the electronic absorption spectrum of the pyrazine molecule within the linear vibronic coupling model.

  16. Analytic evaluation of the nonadiabatic coupling vector between excited states using equation-of-motion coupled-cluster theory.

    PubMed

    Tajti, Attila; Szalay, Péter G

    2009-09-28

    Theory and implementation for evaluation of the nonadiabatic coupling vector between excited electronic states described by equation-of-motion excitation energy coupled-cluster singles and doubles (EOMEE-CCSD) method is presented. Problems arising from the non-Hermitian nature of the theory are discussed in detail. The performance of the new approach is demonstrated by the nice agreement of the nonadiabatic coupling curves for LiH obtained at the EOMEE-CCSD and MR-CISD levels. Using the tools developed we also present a computational procedure to evaluate the interstate coupling constants used in vibronic coupling theories. As an application of this part of the implementation we present simulation of the electronic absorption spectrum of the pyrazine molecule within the linear vibronic coupling model.

  17. On the calculations of the nuclear spin spin coupling constants in small water clusters

    NASA Astrophysics Data System (ADS)

    Cybulski, Hubert; Pecul, Magdalena; Sadlej, Joanna

    2006-08-01

    The calculations of the nuclear spin-spin coupling constants were carried out for small water clusters (H 2O) n, n = 2-6, 12, and 17, using density functional theory (DFT) and second-order polarization propagator method (SOPPA). A wide range of different standard and modified basis sets was tested to enable the choice of the possibly smallest and most flexible basis set. The changes in the oxygen-proton coupling constants upon the cluster formation between the nuclei involved in hydrogen bonding cover a range of ca. 13 Hz. The range of the calculated changes in intramolecular 1JOH couplings shows that the simple model of rigid water clusters seems to be sufficient to reproduce properly the sign and to estimate the magnitude of the gas-to-liquid shift. The sign of the complexation-induced changes in the intramolecular 2JHH coupling constant is different for molecules with a different coordination number. While the sign is positive for the molecules of the single donor-single acceptor (DA) and single donor-double acceptor (DAA) types, it is negative for the double donor-single acceptor (DDA) molecules. In the four-coordinated double donor-double acceptor (DDAA) molecules the sign of Δ 2JHH varies. The hydrogen-bond transmitted intermolecular coupling constants are substantial: 1hJOH spans the range from 2.8 to 8.4 Hz while 2hJOO varies from -0.6 to 7.5 Hz. The average intermolecular 1hJOH coupling constant decays slowly with the H⋯O distance in the cyclic clusters n = 2-6. The average 2hJOO coupling decreases exponentially with the O⋯O separation for the cyclic clusters n = 2-6.

  18. Structures and energetics of neutral and ionic silicon-germanium clusters: density functional theory and coupled cluster studies.

    PubMed

    Wang, Yi-Siang; Chao, Sheng D

    2011-03-10

    We have calculated the structural and energetic properties of neutral and ionic (singly charged anionic and cationic) semiconductor binary silicon-germanium clusters Si(m)Ge(n) for s = m + n ≤ 12 using the density functional theory (DFT-B3LYP) and coupled cluster [CCSD(T)] methods with Pople's 6-311++G(3df, 3pd) basis set. Neutral and anionic clusters share similar ground state structures for s = 3-7, independent of the stoichiometry and atom locations, but start to deviate at s = 8. The relative energetic stability of the calculated ground state structures among possible isomers has been analyzed through a bond strength propensity model where the pair interactions of Si-Si, Si-Ge, and Ge-Ge are competing. Electron affinities, ionization potentials, energy gaps between the highest and lowest occupied molecular orbitals (HOMO-LUMO gaps), and cluster mixing energies were calculated and analyzed. Overall, for a fixed s, the vertical ionization potential increases as the number of silicon atoms m increases, while the vertical electron affinity shows a dip at m = 2. As s increases, the ionization potentials increase from s = 2 to s = 3 and then decrease slowly to s = 8. The mixing energies for neutral and ionic clusters are all negative, indicating that the binary clusters are more stable than pure elemental clusters. Except for s = 4 and 8, cationic clusters are more stable than anionic ones and, thus, are more likely to be observed in experiments.

  19. Size to density coupling of supported metallic clusters.

    PubMed

    Gross, Elad; Asscher, Micha

    2009-01-28

    One of the difficulties in standard growth of metallic nano-clusters on oxide substrates as model catalysts is the strong coupling between clusters size and density. Employing multiple cycles, amorphous solid water-buffer layer assisted growth (ASW-BLAG) procedure, we demonstrate how the size to density coupling can be eliminated under certain conditions. In this study, gold clusters were deposited on a SiO2/Si(100) substrate in UHV, using ASW as a buffer layer assisting aggregation and growth. The clusters were imaged ex situ by tapping mode atomic force microscope (AFM) and high-resolution scanning electron microscope (HR-SEM). In situ Auger electron spectroscopy (AES) measurements have led to independent evaluation of the gold covered area. In order to increase the clusters density we have introduced a multiple BLAG procedure, in which, a BALG cycle is repeated up to 10 times. The cluster density can be increased this way by more than five fold without changing their size. Above a specific number of cycles, however, the cluster density reaches saturation and a gradual increase in clusters size is observed. Larger clusters correlate with lower saturation density following multiple BLAG cycles. This observation is explained in terms of long range cluster-cluster attraction between clusters already on the substrate and those approaching in the next BLAG cycle. This attraction is more pronounced as the clusters become larger. We have shown that at saturation density, inter-cluster distance can not be smaller than 20 nm for clusters 4 nm in diameter or larger. Employing two consecutive BLAG cycles, characterized by different parameters (metal dosage and buffer layer thickness) result in a bi-modal size distribution. Moreover, it is demonstrated that one can prepare this way co-adsorbed bi-metallic film of e.g. Au and Pd clusters, with specific density and size on the same substrate. The ASW-BLAG procedure is thus expected to introduce a new pathway for tailor made

  20. Report of a Workshop on Parallelization of Coupled Cluster Methods

    SciTech Connect

    Rodney J. Bartlett Erik Deumens

    2008-05-08

    The benchmark, ab initio quantum mechanical methods for molecular structure and spectra are now recognized to be coupled-cluster theory. To benefit from the transiiton to tera- and petascale computers, such coupled-cluster methods must be created to run in a scalable fashion. This Workshop, held as a aprt of the 48th annual Sanibel meeting, at St. Simns, Island, GA, addressed that issue. Representatives of all the principal scientific groups who are addressing this topic were in attendance, to exchange information about the problem and to identify what needs to be done in the future. This report summarized the conclusions of the workshop.

  1. Note: Excited State Studies of Ozone using State-Specific Multireference Coupled Cluster Methods

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol

    2012-12-07

    Vertical excitation energies obtained with state-specific multi-reference coupled cluster (MRCC) methods are reported for the ozone molecule. Using state-specific MRCC non-iterative methods with singles, doubles, and non-iterative triples (MRCCSD(T)) we obtain 4.40 eV for the challenging doubly excited 21A1 state when using a reliable model space. This estimate is in good agreement with experiment (4.5 eV). We also compare our MRCC results with the excitation energies obtained with high-order equation-of-motion coupled cluster methods

  2. Communication: Finite size correction in periodic coupled cluster theory calculations of solids.

    PubMed

    Liao, Ke; Grüneis, Andreas

    2016-10-14

    We present a method to correct for finite size errors in coupled cluster theory calculations of solids. The outlined technique shares similarities with electronic structure factor interpolation methods used in quantum Monte Carlo calculations. However, our approach does not require the calculation of density matrices. Furthermore we show that the proposed finite size corrections achieve chemical accuracy in the convergence of second-order Møller-Plesset perturbation and coupled cluster singles and doubles correlation energies per atom for insulating solids with two atomic unit cells using 2 × 2 × 2 and 3 × 3 × 3 k-point meshes only.

  3. Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods

    SciTech Connect

    Brabec, Jiri; Banik, Subrata; Kowalski, Karol; Pittner, Jiří

    2016-10-28

    The implementation details of the universal state-selective (USS) multi-reference coupled cluster (MRCC) formalism with singles and doubles (USS(2)) are discussed on the example of several benchmark systems. We demonstrate that the USS(2) formalism is capable of improving accuracies of state specific multi-reference coupled-cluster (MRCC) methods based on the Brillouin-Wigner and Mukherjee’s sufficiency conditions. Additionally, it is shown that the USS(2) approach significantly alleviates problems associated with the lack of invariance of MRCC theories upon the rotation of active orbitals. We also discuss the perturbative USS(2) formulations that significantly reduce numerical overhead of the full USS(2) method.

  4. Closed-shell coupled-cluster theory with spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Wang, Fan; Gauss, Jürgen; van Wüllen, Christoph

    2008-08-01

    A two-component closed-shell coupled-cluster (CC) approach using relativistic effective core potentials with spin-orbit coupling included in the post-Hartree-Fock treatment is proposed and implemented at the CC singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations [CCSD(T)]. The latter invokes as an additional approximation the neglect of the occupied-occupied and virtual-virtual blocks of the spin-orbit coupling matrix in order to avoid the iterative N7 steps in the treatment of triple excitations. The computational effort of the implemented two-component CC methods is about 10-15 times that of its corresponding nonrelativistic counterpart, which needs to be compared to the by a factor of 32 higher cost for fully relativistic schemes and schemes with spin-orbit coupling included already at the Hartree-Fock self-consistent field (HF-SCF) level. This substantial computational saving is due to the use of real molecular orbitals and real two-electron integrals. Results on 5p-, 6p-, and 7p-block element compounds show that the bond lengths and harmonic frequencies obtained with the present two-component CCSD method agree well with those computed with the CCSD approach including spin-orbit coupling at the HF-SCF level even for the 7p-block element compounds. As for the CCSD(T) approach, high accuracy for 5p- and 6p-block element compounds is retained. However, the difference in bond lengths and harmonic frequencies becomes somewhat more pronounced for the 7p-block element compounds.

  5. Closed-shell coupled-cluster theory with spin-orbit coupling.

    PubMed

    Wang, Fan; Gauss, Jürgen; van Wüllen, Christoph

    2008-08-14

    A two-component closed-shell coupled-cluster (CC) approach using relativistic effective core potentials with spin-orbit coupling included in the post-Hartree-Fock treatment is proposed and implemented at the CC singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations [CCSD(T)]. The latter invokes as an additional approximation the neglect of the occupied-occupied and virtual-virtual blocks of the spin-orbit coupling matrix in order to avoid the iterative N(7) steps in the treatment of triple excitations. The computational effort of the implemented two-component CC methods is about 10-15 times that of its corresponding nonrelativistic counterpart, which needs to be compared to the by a factor of 32 higher cost for fully relativistic schemes and schemes with spin-orbit coupling included already at the Hartree-Fock self-consistent field (HF-SCF) level. This substantial computational saving is due to the use of real molecular orbitals and real two-electron integrals. Results on 5p-, 6p-, and 7p-block element compounds show that the bond lengths and harmonic frequencies obtained with the present two-component CCSD method agree well with those computed with the CCSD approach including spin-orbit coupling at the HF-SCF level even for the 7p-block element compounds. As for the CCSD(T) approach, high accuracy for 5p- and 6p-block element compounds is retained. However, the difference in bond lengths and harmonic frequencies becomes somewhat more pronounced for the 7p-block element compounds.

  6. Linear-response theory for Mukherjee's multireference coupled-cluster method: excitation energies.

    PubMed

    Jagau, Thomas-C; Gauss, Jürgen

    2012-07-28

    The recently presented linear-response function for Mukherjee's multireference coupled-cluster method (Mk-MRCC) [T.-C. Jagau and J. Gauss, J. Chem. Phys. 137, 044115 (2012)] is employed to determine vertical excitation energies within the singles and doubles approximation (Mk-MRCCSD-LR) for ozone as well as for o-benzyne, m-benzyne, and p-benzyne, which display increasing multireference character in their ground states. In order to assess the impact of a multireference ground-state wavefunction on excitation energies, we compare all our results to those obtained at the single-reference coupled-cluster level of theory within the singles and doubles as well as within the singles, doubles, and triples approximation. Special attention is paid to the artificial splitting of certain excited states which arises from the redundancy intrinsic to Mk-MRCC theory and hinders the straightforward application of the Mk-MRCC-LR method.

  7. Merging symmetry projection methods with coupled cluster theory: Lessons from the Lipkin model Hamiltonian

    NASA Astrophysics Data System (ADS)

    Wahlen-Strothman, Jacob M.; Henderson, Thomas M.; Hermes, Matthew R.; Degroote, Matthias; Qiu, Yiheng; Zhao, Jinmo; Dukelsky, Jorge; Scuseria, Gustavo E.

    2017-02-01

    Coupled cluster and symmetry projected Hartree-Fock are two central paradigms in electronic structure theory. However, they are very different. Single reference coupled cluster is highly successful for treating weakly correlated systems but fails under strong correlation unless one sacrifices good quantum numbers and works with broken-symmetry wave functions, which is unphysical for finite systems. Symmetry projection is effective for the treatment of strong correlation at the mean-field level through multireference non-orthogonal configuration interaction wavefunctions, but unlike coupled cluster, it is neither size extensive nor ideal for treating dynamic correlation. We here examine different scenarios for merging these two dissimilar theories. We carry out this exercise over the integrable Lipkin model Hamiltonian, which despite its simplicity, encompasses non-trivial physics for degenerate systems and can be solved via diagonalization for a very large number of particles. We show how symmetry projection and coupled cluster doubles individually fail in different correlation limits, whereas models that merge these two theories are highly successful over the entire phase diagram. Despite the simplicity of the Lipkin Hamiltonian, the lessons learned in this work will be useful for building an ab initio symmetry projected coupled cluster theory that we expect to be accurate in the weakly and strongly correlated limits, as well as the recoupling regime.

  8. Coupled-cluster based basis sets for valence correlation calculations

    NASA Astrophysics Data System (ADS)

    Claudino, Daniel; Gargano, Ricardo; Bartlett, Rodney J.

    2016-03-01

    Novel basis sets are generated that target the description of valence correlation in atoms H through Ar. The new contraction coefficients are obtained according to the Atomic Natural Orbital (ANO) procedure from CCSD(T) (coupled-cluster singles and doubles with perturbative triples correction) density matrices starting from the primitive functions of Dunning et al. [J. Chem. Phys. 90, 1007 (1989); ibid. 98, 1358 (1993); ibid. 100, 2975 (1993)] (correlation consistent polarized valence X-tuple zeta, cc-pVXZ). The exponents of the primitive Gaussian functions are subject to uniform scaling in order to ensure satisfaction of the virial theorem for the corresponding atoms. These new sets, named ANO-VT-XZ (Atomic Natural Orbital Virial Theorem X-tuple Zeta), have the same number of contracted functions as their cc-pVXZ counterparts in each subshell. The performance of these basis sets is assessed by the evaluation of the contraction errors in four distinct computations: correlation energies in atoms, probing the density in different regions of space via (-3 ≤ n ≤ 3) in atoms, correlation energies in diatomic molecules, and the quality of fitting potential energy curves as measured by spectroscopic constants. All energy calculations with ANO-VT-QZ have contraction errors within "chemical accuracy" of 1 kcal/mol, which is not true for cc-pVQZ, suggesting some improvement compared to the correlation consistent series of Dunning and co-workers.

  9. Panic evacuation of single pedestrians and couples

    NASA Astrophysics Data System (ADS)

    Frank, G. A.; Dorso, C. O.

    2016-02-01

    Understanding the timing requirements for evacuation of people has focused primarily on independent pedestrians rather than pedestrians emotionally connected. However, the main statistical effects observed in crowds, the so-called “faster is slower”, “clever is not always better” and the “low visibility enhancement”, cannot explain the overall behavior of a crowd during an evacuation process when correlated pedestrians due to, for example feelings, are present. Our research addresses this issue and examines the statistical behavior of a mixture of individuals and couples during a (panic) escaping process. We found that the attractive feeling among couples plays an important role in the time delays during the evacuation of a single exit room.

  10. Mode couplings and resonance instabilities in dust clusters.

    PubMed

    Qiao, Ke; Kong, Jie; Oeveren, Eric Van; Matthews, Lorin S; Hyde, Truell W

    2013-10-01

    The normal modes for three to seven particle two-dimensional (2D) dust clusters in a complex plasma are investigated using an N-body simulation. The ion wakefield downstream of each particle is shown to induce coupling between horizontal and vertical modes. The rules of mode coupling are investigated by classifying the mode eigenvectors employing the Bessel and trigonometric functions indexed by order integers (m, n). It is shown that coupling only occurs between two modes with the same m and that horizontal modes having a higher shear contribution exhibit weaker coupling. Three types of resonances are shown to occur when two coupled modes have the same frequency. Discrete instabilities caused by both the first and third type of resonances are verified and instabilities caused by the third type of resonance are found to induce melting. The melting procedure is observed to go through a two-step process with the solid-liquid transition closely obeying the Lindemann criterion.

  11. Coupled-cluster reaction barriers of HO2+H2O+O3: An application of the coupled-cluster//Kohn-Sham density functional theory model chemistry.

    PubMed

    Viegas, Luís P; Varandas, António J C

    2014-03-15

    In this work, we report a theoretical investigation concerning the use of the popular coupled-cluster//Kohn-Sham density functional theory (CC//KS-DFT) model chemistry, here applied to study the entrance channel of the HO2+H2O+O3 reaction, namely by comparing CC//KS-DFT calculations with KS-DFT, MRPT2//CASSCF, and CC//CASSCF results from our previous investigations. This was done by performing single point energy calculations employing several coupled cluster methods and using KS-DFT geometries optimized with six different functionals, while conducting a detailed analysis of the barrier heights and topological features of the curves and surfaces here obtained. The quality of this model chemistry is critically discussed in the context of the title reaction and also in a wider context. Copyright © 2013 Wiley Periodicals, Inc.

  12. Single-Pass Clustering Algorithm Based on Storm

    NASA Astrophysics Data System (ADS)

    Fang, LI; Longlong, DAI; Zhiying, JIANG; Shunzi, LI

    2017-02-01

    The dramatically increasing volume of data makes the computational complexity of traditional clustering algorithm rise rapidly accordingly, which leads to the longer time. So as to improve the efficiency of the stream data clustering, a distributed real-time clustering algorithm (S-Single-Pass) based on the classic Single-Pass [1] algorithm and Storm [2] computation framework was designed in this paper. By employing this kind of method in the Topic Detection and Tracking (TDT) [3], the real-time performance of topic detection arises effectively. The proposed method splits the clustering process into two parts: one part is to form clusters for the multi-thread parallel clustering, the other part is to merge the generated clusters in the previous process and update the global clusters. Through the experimental results, the conclusion can be drawn that the proposed method have the nearly same clustering accuracy as the traditional Single-Pass algorithm and the clustering accuracy remains steady, computing rate increases linearly when increasing the number of cluster machines and nodes (processing threads).

  13. ClusterSculptor: Software for Expert-Steered Classification of Single Particle Mass Spectra

    SciTech Connect

    Zelenyuk, Alla; Imre, Dan G.; Nam, Eun Ju; Han, Yiping; Mueller, Klaus

    2008-08-01

    To take full advantage of the vast amount of highly detailed data acquired by single particle mass spectrometers requires that the data be organized according to some rules that have the potential to be insightful. Most commonly statistical tools are used to cluster the individual particle mass spectra on the basis of their similarity. Cluster analysis is a powerful strategy for the exploration of high-dimensional data in the absence of a-priori hypotheses or data classification models, and the results of cluster analysis can then be used to form such models. More often than not, when examining the data clustering results we find that many clusters contain particles of different types and that many particles of one type end up in a number of separate clusters. Our experience with cluster analysis shows that we have a vast amount of non-compiled knowledge and intuition that should be brought to bear in this effort. We will present new software we call ClusterSculptor that provides comprehensive and intuitive framework to aid scientists in data classification. ClusterSculptor uses k-means as the overall clustering engine, but allows tuning its parameters interactively, based on a non-distorted compact visual presentation of the inherent characteristics of the data in high-dimensional space. ClusterSculptor provides all the tools necessary for a high-dimensional activity we call cluster sculpting. ClusterSculptor is designed to be coupled to SpectraMiner, our data mining and visualization software package. The data are first visualized with SpectraMiner and identified problems are exported to ClusterSculptor, where the user steers the reclassification and recombination of clusters of tens of thousands particle mass spectra in real-time. The resulting sculpted clusters can be then imported back into SpectraMiner. Here we will greatly improved single particle chemical speciation in an example of application of this new tool to a number of particle types of atmospheric

  14. Spin-orbit coupling with approximate equation-of-motion coupled-cluster method for ionization potential and electron attachment

    NASA Astrophysics Data System (ADS)

    Cao, Zhanli; Wang, Fan; Yang, Mingli

    2016-10-01

    Various approximate approaches to calculate cluster amplitudes in equation-of-motion coupled-cluster (EOM-CC) approaches for ionization potentials (IP) and electron affinities (EA) with spin-orbit coupling (SOC) included in post self-consistent field (SCF) calculations are proposed to reduce computational effort. Our results indicate that EOM-CC based on cluster amplitudes from the approximate method CCSD-1, where the singles equation is the same as that in CCSD and the doubles amplitudes are approximated with MP2, is able to provide reasonable IPs and EAs when SOC is not present compared with CCSD results. It is an economical approach for calculating IPs and EAs and is not as sensitive to strong correlation as CC2. When SOC is included, the approximate method CCSD-3, where the same singles equation as that in SOC-CCSD is used and the doubles equation of scalar-relativistic CCSD is employed, gives rise to IPs and EAs that are in closest agreement with those of CCSD. However, SO splitting with EOM-CC from CC2 generally agrees best with that with CCSD, while that of CCSD-1 and CCSD-3 is less accurate. This indicates that a balanced treatment of SOC effects on both single and double excitation amplitudes is required to achieve reliable SO splitting.

  15. The use of gene clusters to infer functional coupling

    PubMed Central

    Overbeek, Ross; Fonstein, Michael; D’Souza, Mark; Pusch, Gordon D.; Maltsev, Natalia

    1999-01-01

    Previously, we presented evidence that it is possible to predict functional coupling between genes based on conservation of gene clusters between genomes. With the rapid increase in the availability of prokaryotic sequence data, it has become possible to verify and apply the technique. In this paper, we extend our characterization of the parameters that determine the utility of the approach, and we generalize the approach in a way that supports detection of common classes of functionally coupled genes (e.g., transport and signal transduction clusters). Now that the analysis includes over 30 complete or nearly complete genomes, it has become clear that this approach will play a significant role in supporting efforts to assign functionality to the remaining uncharacterized genes in sequenced genomes. PMID:10077608

  16. A nonperturbative light-front coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Hiller, J. R.

    2012-10-01

    The nonperturbative Hamiltonian eigenvalue problem for bound states of a quantum field theory is formulated in terms of Dirac's light-front coordinates and then approximated by the exponential-operator technique of the many-body coupled-cluster method. This approximation eliminates any need for the usual approximation of Fock-space truncation. Instead, the exponentiated operator is truncated, and the terms retained are determined by a set of nonlinear integral equations. These equations are solved simultaneously with an effective eigenvalue problem in the valence sector, where the number of constituents is small. Matrix elements can be calculated, with extensions of techniques from standard coupled-cluster theory, to obtain form factors and other observables.

  17. Energetics of H2 clusters from density functional and coupled cluster theories

    NASA Astrophysics Data System (ADS)

    Trail, J. R.; López Ríos, P.; Needs, R. J.

    2017-03-01

    We use coupled-cluster quantum chemical methods to calculate the energetics of molecular clusters cut out of periodic molecular hydrogen structures that model observed phases of solid hydrogen. The hydrogen structures are obtained from Kohn-Sham density functional theory (DFT) calculations at pressures of 150, 250, and 350 GPa, which are within the pressure range in which phases II, III, and IV are found to be stable. The calculated deviations in the DFT energies from the coupled-cluster data are reported for different functionals, and optimized functionals are generated which provide reduced errors. We give recommendations for semilocal and hybrid density functionals that are expected to provide an accurate description of hydrogen at high pressures.

  18. Orbital spaces in the divide-expand-consolidate coupled cluster method

    NASA Astrophysics Data System (ADS)

    Ettenhuber, Patrick; Baudin, Pablo; Kjærgaard, Thomas; Jørgensen, Poul; Kristensen, Kasper

    2016-04-01

    The theoretical foundation for solving coupled cluster singles and doubles (CCSD) amplitude equations to a desired precision in terms of independent fragment calculations using restricted local orbital spaces is reinvestigated with focus on the individual error sources. Four different error sources are identified theoretically and numerically and it is demonstrated that, for practical purposes, local orbital spaces for CCSD calculations can be identified from calculations at the MP2 level. The development establishes a solid theoretical foundation for local CCSD calculations for the independent fragments, and thus for divide-expand-consolidate coupled cluster calculations for large molecular systems with rigorous error control. Based on this theoretical foundation, we have developed an algorithm for determining the orbital spaces needed for obtaining the single fragment energies to a requested precision and numerically demonstrated the robustness and precision of this algorithm.

  19. Automatic active space selection for the similarity transformed equations of motion coupled cluster method

    NASA Astrophysics Data System (ADS)

    Dutta, Achintya Kumar; Nooijen, Marcel; Neese, Frank; Izsák, Róbert

    2017-02-01

    An efficient scheme for the automatic selection of an active space for similarity transformed equations of motion (STEOM) coupled cluster method is proposed. It relies on state averaged configuration interaction singles (CIS) natural orbitals and makes it possible to use STEOM as a black box method. The performance of the new scheme is tested for singlet and triplet valence, charge transfer, and Rydberg excited states.

  20. Critical slowing down of cluster algorithms for Ising models coupled to 2-d gravity

    NASA Astrophysics Data System (ADS)

    Bowick, Mark; Falcioni, Marco; Harris, Geoffrey; Marinari, Enzo

    1994-02-01

    We simulate single and multiple Ising models coupled to 2-d gravity using both the Swendsen-Wang and Wolff algorithms to update the spins. We study the integrated autocorrelation time and find that there is considerable critical slowing down, particularly in the magnetization. We argue that this is primarily due to the local nature of the dynamical triangulation algorithm and to the generation of a distribution of baby universes which inhibits cluster growth.

  1. Arrays of stochastic oscillators: Nonlocal coupling, clustering, and wave formation.

    PubMed

    Escaff, Daniel; Pinto, Italo'Ivo Lima Dias; Lindenberg, Katja

    2014-11-01

    We consider an array of units each of which can be in one of three states. Unidirectional transitions between these states are governed by Markovian rate processes. The interactions between units occur through a dependence of the transition rates of a unit on the states of the units with which it interacts. This coupling is nonlocal, that is, it is neither an all-to-all interaction (referred to as global coupling), nor is it a nearest neighbor interaction (referred to as local coupling). The coupling is chosen so as to disfavor the crowding of interacting units in the same state. As a result, there is no global synchronization. Instead, the resultant spatiotemporal configuration is one of clusters that move at a constant speed and that can be interpreted as traveling waves. We develop a mean field theory to describe the cluster formation and analyze this model analytically. The predictions of the model are compared favorably with the results obtained by direct numerical simulations.

  2. Ferromagnetic spin coupling in the chromium dimer cation: Measurements by photodissociation spectroscopy combined with coupled-cluster calculations

    SciTech Connect

    Egashira, Kazuhiro; Yamada, Yurika; Kita, Yukiumi; Tachikawa, Masanori

    2015-02-07

    The magnetic coupling of the chromium dimer cation, Cr{sub 2}{sup +}, has been an outstanding problem for decades. An optical absorption spectrum of Cr{sub 2}{sup +} has been obtained by photodissociation spectroscopy in the photon-energy range from 2.0 to 5.0 eV. Besides, calculations have been performed by the equation-of-motion coupled-cluster singles and doubles method for vertical excitation of the species. Their coincidence supports our assignment that the ground electronic state exhibits a ferromagnetic spin coupling, which is contrary to those of neutral and negatively charged dimers, Cr{sub 2} and Cr{sub 2}{sup −}, in their lowest spin states.

  3. Communication: spin densities within a unitary group based spin-adapted open-shell coupled-cluster theory: analytic evaluation of isotropic hyperfine-coupling constants for the combinatoric open-shell coupled-cluster scheme.

    PubMed

    Datta, Dipayan; Gauss, Jürgen

    2015-07-07

    We report analytical calculations of isotropic hyperfine-coupling constants in radicals using a spin-adapted open-shell coupled-cluster theory, namely, the unitary group based combinatoric open-shell coupled-cluster (COSCC) approach within the singles and doubles approximation. A scheme for the evaluation of the one-particle spin-density matrix required in these calculations is outlined within the spin-free formulation of the COSCC approach. In this scheme, the one-particle spin-density matrix for an open-shell state with spin S and MS = + S is expressed in terms of the one- and two-particle spin-free (charge) density matrices obtained from the Lagrangian formulation that is used for calculating the analytic first derivatives of the energy. Benchmark calculations are presented for NO, NCO, CH2CN, and two conjugated π-radicals, viz., allyl and 1-pyrrolyl in order to demonstrate the performance of the proposed scheme.

  4. Coexistence of Quantized, Time Dependent, Clusters in Globally Coupled Oscillators

    NASA Astrophysics Data System (ADS)

    Bi, Hongjie; Hu, Xin; Boccaletti, S.; Wang, Xingang; Zou, Yong; Liu, Zonghua; Guan, Shuguang

    2016-11-01

    We report on a novel collective state, occurring in globally coupled nonidentical oscillators in the proximity of the point where the transition from the system's incoherent to coherent phase converts from explosive to continuous. In such a state, the oscillators form quantized clusters, where neither their phases nor their instantaneous frequencies are locked. The oscillators' instantaneous speeds are different within the clusters, but they form a characteristic cusped pattern and, more importantly, they behave periodically in time so that their average values are the same. Given its intrinsic specular nature with respect to the recently introduced Chimera states, the phase is termed the Bellerophon state. We provide an analytical and numerical description of Bellerophon states, and furnish practical hints on how to seek them in a variety of experimental and natural systems.

  5. Communication: Improved pair approximations in local coupled-cluster methods

    NASA Astrophysics Data System (ADS)

    Schwilk, Max; Usvyat, Denis; Werner, Hans-Joachim

    2015-03-01

    In local coupled cluster treatments the electron pairs can be classified according to the magnitude of their energy contributions or distances into strong, close, weak, and distant pairs. Different approximations are introduced for the latter three classes. In this communication, an improved simplified treatment of close and weak pairs is proposed, which is based on long-range cancellations of individually slowly decaying contributions in the amplitude equations. Benchmark calculations for correlation, reaction, and activation energies demonstrate that these approximations work extremely well, while pair approximations based on local second-order Møller-Plesset theory can lead to errors that are 1-2 orders of magnitude larger.

  6. High-accuracy coupled cluster calculations of atomic properties

    NASA Astrophysics Data System (ADS)

    Borschevsky, A.; Yakobi, H.; Eliav, E.; Kaldor, U.

    2015-01-01

    The four-component Fock-space coupled cluster and intermediate Hamiltonian methods are implemented to evaluate atomic properties. The latter include the spectra of nobelium and lawrencium (elements 102 and 103) in the range 20000-30000 cm-1, the polarizabilities of elements 112-114 and 118, required for estimating their adsorption enthalpies on surfaces used to separate them in accelerators, and the nuclear quadrupole moments of some heavy atoms. The calculations on superheavy elements are supported by the very good agreement with experiment obtained for the lighter homologues.

  7. High-accuracy coupled cluster calculations of atomic properties

    SciTech Connect

    Borschevsky, A.; Yakobi, H.; Eliav, E.; Kaldor, U.

    2015-01-22

    The four-component Fock-space coupled cluster and intermediate Hamiltonian methods are implemented to evaluate atomic properties. The latter include the spectra of nobelium and lawrencium (elements 102 and 103) in the range 20000-30000 cm{sup −1}, the polarizabilities of elements 112-114 and 118, required for estimating their adsorption enthalpies on surfaces used to separate them in accelerators, and the nuclear quadrupole moments of some heavy atoms. The calculations on superheavy elements are supported by the very good agreement with experiment obtained for the lighter homologues.

  8. Perturbative triples corrections in state-specific multireference coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Evangelista, Francesco A.; Prochnow, Eric; Gauss, Jürgen; Schaefer, Henry F.

    2010-02-01

    We formulated and implemented a perturbative triples correction for the state-specific multireference coupled cluster approach with singles and doubles suggested by Mukherjee and co-workers, Mk-MRCCSD [Mol. Phys. 94, 157 (1998)]. Our derivation of the energy correction [Mk-MRCCSD(T)] is based on a constrained search for stationary points of the Mk-MRCC energy functional together with a perturbative expansion with respect to the appearing triples cluster operator. The Λ-Mk-MRCCSD(T) approach derived in this way consists in (1) a correction to the off-diagonal matrix elements of the effective Hamiltonian which is unique to coupled cluster methods based on the Jeziorski-Monkhorst ansatz, and (2) an asymmetric energy correction to the diagonal elements of the effective Hamiltonian. The Mk-MRCCSD(T) correction is obtained from the Λ-Mk-MRCCSD(T) method by approximating the singles and doubles Lagrange multipliers with the corresponding cluster amplitudes. We investigate the performance of the Mk-MRCCSD(T) method by applying it to the potential energy curve of the BeH2 model and F2 and the geometry and harmonic vibrational frequencies of ozone. Computation of the energy difference between the mono- and bicyclic forms of the 2,6-pyridyne diradical illustrates the potential of Mk-MRCCSD(T) as a tool for the study of realistic chemical problems requiring multireference zeroth-order wave functions.

  9. Perturbative triples corrections in state-specific multireference coupled cluster theory.

    PubMed

    Evangelista, Francesco A; Prochnow, Eric; Gauss, Jürgen; Schaefer, Henry F

    2010-02-21

    We formulated and implemented a perturbative triples correction for the state-specific multireference coupled cluster approach with singles and doubles suggested by Mukherjee and co-workers, Mk-MRCCSD [Mol. Phys. 94, 157 (1998)]. Our derivation of the energy correction [Mk-MRCCSD(T)] is based on a constrained search for stationary points of the Mk-MRCC energy functional together with a perturbative expansion with respect to the appearing triples cluster operator. The Lambda-Mk-MRCCSD(T) approach derived in this way consists in (1) a correction to the off-diagonal matrix elements of the effective Hamiltonian which is unique to coupled cluster methods based on the Jeziorski-Monkhorst ansatz, and (2) an asymmetric energy correction to the diagonal elements of the effective Hamiltonian. The Mk-MRCCSD(T) correction is obtained from the Lambda-Mk-MRCCSD(T) method by approximating the singles and doubles Lagrange multipliers with the corresponding cluster amplitudes. We investigate the performance of the Mk-MRCCSD(T) method by applying it to the potential energy curve of the BeH(2) model and F(2) and the geometry and harmonic vibrational frequencies of ozone. Computation of the energy difference between the mono- and bicyclic forms of the 2,6-pyridyne diradical illustrates the potential of Mk-MRCCSD(T) as a tool for the study of realistic chemical problems requiring multireference zeroth-order wave functions.

  10. Simulation of circularly polarized luminescence spectra using coupled cluster theory

    SciTech Connect

    McAlexander, Harley R.; Crawford, T. Daniel

    2015-04-21

    We report the first computations of circularly polarized luminescence (CPL) rotatory strengths at the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) level of theory. Using a test set of eight chiral ketones, we compare both dipole and rotatory strengths for absorption (electronic circular dichroism) and emission to the results from time-dependent density-functional theory (TD-DFT) and available experimental data for both valence and Rydberg transitions. For two of the compounds, we obtained optimized geometries of the lowest several excited states using both EOM-CCSD and TD-DFT and determined that structures and EOM-CCSD transition properties obtained with each structure were sufficiently similar that TD-DFT optimizations were acceptable for the remaining test cases. Agreement between EOM-CCSD and the Becke three-parameter exchange function and Lee-Yang-Parr correlation functional (B3LYP) corrected using the Coulomb attenuating method (CAM-B3LYP) is typically good for most of the transitions, though agreement with the uncorrected B3LYP functional is significantly worse for all reported properties. The choice of length vs. velocity representation of the electric dipole operator has little impact on the EOM-CCSD transition strengths for nearly all of the states we examined. For a pair of closely related β, γ-enones, (1R)-7-methylenebicyclo[2.2.1]heptan-2-one and (1S)-2-methylenebicyclo[2.2.1]heptan-7-one, we find that EOM-CCSD and CAM-B3LYP agree with the energetic ordering of the two possible excited-state conformations, resulting in good agreement with experimental rotatory strengths in both absorption and emission, whereas B3LYP yields a qualitatively incorrect result for the CPL signal of (1S)-2-methylenebicyclo[2.2.1]heptan-7-one. Finally, we predict that one of the compounds considered here, trans-bicyclo[3.3.0]octane-3,7-dione, is unique in that it exhibits an achiral ground state and a chiral first excited state, leading to a strong CPL

  11. Real or artifactual symmetry breaking in the BNB radical: A multireference coupled cluster viewpoint

    NASA Astrophysics Data System (ADS)

    Li, Xiangzhu; Paldus, Josef

    2007-06-01

    The ground state of the linear BNB radical has been examined via the recently developed reduced multireference coupled cluster method with singles and doubles that is perturbatively corrected for triples [RMR CCSD(T)] using the correlation consistent basis sets (cc-pVXZ, X =D, T, and Q). Similar to earlier results that were based on the single reference CCSD(T) and BD(T) approaches, the RMR CCSD(T) method also predicts an asymmetric structure with two BN bonds of unequal length, even though the MR effects significantly reduce the barrier height. The computed frequencies for the symmetric and antisymmetric stretching modes agree reasonably well with the experimental data.

  12. Predictive coupled-cluster isomer orderings for some SinCm (m, n ≤ 12) clusters: A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks.

    PubMed

    Byrd, Jason N; Lutz, Jesse J; Jin, Yifan; Ranasinghe, Duminda S; Montgomery, John A; Perera, Ajith; Duan, Xiaofeng F; Burggraf, Larry W; Sanders, Beverly A; Bartlett, Rodney J

    2016-07-14

    The accurate determination of the preferred Si12C12 isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for the opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies, and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC3 to Si12C12. It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and coupled-cluster theory with singles and doubles extrapolation with triple-ζ (T) correlation, the closo Si12C12 isomer is identified to be the preferred isomer in the support of previous calculations [X. F. Duan and L. W. Burggraf, J. Chem. Phys. 142, 034303 (2015)]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post-MBPT(2) correlation energy are found to be an excellent balance between efficiency and accuracy.

  13. Predictive coupled-cluster isomer orderings for some SinCm (m, n ≤ 12) clusters: A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks

    NASA Astrophysics Data System (ADS)

    Byrd, Jason N.; Lutz, Jesse J.; Jin, Yifan; Ranasinghe, Duminda S.; Montgomery, John A.; Perera, Ajith; Duan, Xiaofeng F.; Burggraf, Larry W.; Sanders, Beverly A.; Bartlett, Rodney J.

    2016-07-01

    The accurate determination of the preferred Si12C12 isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for the opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies, and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC3 to Si12C12. It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and coupled-cluster theory with singles and doubles extrapolation with triple-ζ (T) correlation, the closo Si12C12 isomer is identified to be the preferred isomer in the support of previous calculations [X. F. Duan and L. W. Burggraf, J. Chem. Phys. 142, 034303 (2015)]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post-MBPT(2) correlation energy are found to be an excellent balance between efficiency and accuracy.

  14. Analytic evaluation of the dipole Hessian matrix in coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Jagau, Thomas-C.; Gauss, Jürgen; Ruud, Kenneth

    2013-10-01

    The general theory required for the calculation of analytic third energy derivatives at the coupled-cluster level of theory is presented and connected to preceding special formulations for hyperpolarizabilities and polarizability gradients. Based on our theory, we have implemented a scheme for calculating the dipole Hessian matrix in a fully analytical manner within the coupled-cluster singles and doubles approximation. The dipole Hessian matrix is the second geometrical derivative of the dipole moment and thus a third derivative of the energy. It plays a crucial role in IR spectroscopy when taking into account anharmonic effects and is also essential for computing vibrational corrections to dipole moments. The superior accuracy of the analytic evaluation of third energy derivatives as compared to numerical differentiation schemes is demonstrated in some pilot calculations.

  15. Computational modelling of a large dimension wind farm cluster using domain coupling

    NASA Astrophysics Data System (ADS)

    da Costa Gomes, V. M. M. G.; Palma, J. M. L. M.

    2016-09-01

    The accuracy of Computational Fluid Dynamics (CFD) models for Atmospheric Boundary Layer (ABL) flows relies largely on the placement of the domain boundaries and the quality of the imposed flow conditions, the inlet boundary in particular. Exploiting the parabolic nature of many ABL flows and of CFD modelled ABL flow in particular, a precursor simulation is used as source of flow data to improve the target domain's inlet flow description over the standard synthetic boundary conditions, one-directionally coupling the solutions to the two simulations. Using the approach, a case of flow over a two wind farm offshore cluster is modelled using two small coupled simulations, matching the results of a single simulation including the full cluster at a significant computational time saving, in the order of 70%. Further savings were shown to be possible by reducing the resolution of the precursor simulation, with negligible impact on the results at the target domain.

  16. Ab initio calculations of spectroscopic properties of Cr5+ using coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Dutta, N. N.; Majumder, S.

    2016-04-01

    In this paper, we present ionization potentials, excitation energies, fine-structure splittings, and allowed and forbidden transition amplitudes of five-times-ionized chromium ion as calculated using the relativistic coupled-cluster theory. The wave functions of different single-valence electron configurations are generated using the Dirac-Coulomb-Gaunt Hamiltonian. Effects of electron correlation and Gaunt interaction in the calculations of these properties are studied explicitly. Contributions from different correlation terms associated with the coupled-cluster theory are reported in the calculations of the transition amplitudes. Using these amplitudes and the experimental wavelengths, we calculate astrophysically important transition parameters of several transition lines. Lifetime of the metastable state 3d^2D_{5/2} is found to be 111.66 s.

  17. Ferromagnetism in Silicon Single Crystals with Positively Charged Vacancy Clusters

    NASA Astrophysics Data System (ADS)

    Liu, Yu; Zhang, Xinghong; Yuan, Quan; Han, Jiecai; Zhou, Shengqiang; Song, Bo

    Defect-induced ferromagnetism provides an alternative for organic and semiconductor spintronics. Here, we investigated the magnetism in Silicon after neutron irradiation and try to correlate the observed magnetism to particular defects in Si. Commercially available p-type Si single crystal wafer is cut into pieces for performing neutron irradiations. The magnetic impurities are ruled out as they can not be detected by secondary ion mass spectroscopy. With positron annihilation lifetime spectroscopy, the positron trapping center corresponding to lifetime 375 ps is assigned to a kind of stable vacancy clusters of hexagonal rings (V6) and its concentration is enhanced by increasing neutron doses. After irradiation, the samples still show strong diamagnetism. The weak ferromagnetic signal in Si after irradiation enhances and then weakens with increasing irradiation doses. The saturation magnetization at room temperature is almost the same as that at 5 K. The X-ray magnetic circular dichroism further provides the direct evidence that Silicon is the origin of this ferromagnetism. Using first-principles calculations, it is found that positively charged V6 brings the spin polarization and the defects have coupling with each other. The work is financially supported by the Helmholtz Postdoc Programme (Initiative and Networking Fund, PD-146).

  18. Analytic gradients for Mukherjee's multireference coupled-cluster method using two-configurational self-consistent-field orbitals

    NASA Astrophysics Data System (ADS)

    Jagau, Thomas-C.; Prochnow, Eric; Evangelista, Francesco A.; Gauss, Jürgen

    2010-04-01

    Analytic gradients for the state-specific multireference coupled-cluster method suggested by Mahapatra et al. [Mol. Phys. 94, 157 (1998)] (Mk-MRCC) are reported within the singles and doubles approximation using two-configurational self-consistent field (TCSCF) orbitals. The present implementation extends our previous work on Mk-MRCC gradients [E. Prochnow et al., J. Chem. Phys. 131, 064109 (2009)] which is based on restricted Hartree-Fock orbitals and consequently the main focus of the present paper is on the treatment of orbital relaxation at the TCSCF level using coupled-perturbed TCSCF theory. Geometry optimizations on m-arynes and nitrenes are presented to illustrate the influence of the orbitals on the computed equilibrium structures. The results are compared to those obtained at the single-reference coupled-cluster singles and doubles and at the Mk-MRCC singles and doubles level of theory when using restricted Hartree-Fock orbitals.

  19. Quasiparticle Fock-space coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Stolarczyk, Leszek Z.; Monkhorst, Hendrik J.

    2010-11-01

    The quasiparticle Fock-space coupled-cluster (QFSCC) theory, introduced by us in 1985, is described. This is a theory of many-electron systems which uses the second-quantisation formalism based on the algebraic approximation: one chooses a finite spin-orbital basis, and builds a fermionic Fock space to represent all possible antisymmetric electronic states of a given system. The algebraic machinery is provided by the algebra of linear operators acting in the Fock space, generated by the fermion (creation and annihilation) operators. The Fock-space Hamiltonian operator then determines the system's stationary states and their energies. Within the QFSCC theory, the Fock space and its operator algebra are subject to a unitary transformation which effectively changes electrons into some fermionic quasiparticles. A generalisation of the coupled-cluster method is achieved by enforcing the principle of quasiparticle-number conservation. The emerging quasiparticle model of many-electron systems offers useful physical insights and computational effectiveness. The QFSCC theory requires a substantial reformulation of the traditional second-quantisation language, by making full use of the algebraic properties of the Fock space and its operator algebra. In particular, the role of operators not conserving the number of electrons (or quasiparticles) is identified.

  20. Bistable coupling states measured on single Co nanoclusters deposited on CoO(111).

    PubMed

    Le Roy, D; Morel, R; Pouget, S; Brenac, A; Notin, L; Crozes, T; Wernsdorfer, W

    2011-07-29

    We describe novel features of the induced magnetic anisotropy in Co nanoclusters coupled with a CoO(111) layer. Individual cluster magnetism was studied using new microbridge superconducting quantum interference devices. Intrinsically, the Co clusters are single domains with an effective anisotropy constant K(F)≈1.5×10(6) erg·cm(-3). A bistable state of the ferromagnetic-antiferromagnetic coupling is revealed, with a maximum bias systematically observed along CoO[10 ̅1] and an interfacial coupling energy of 0.9 erg·cm(-2). The small bias observed in cluster assembly results from an averaging over the two opposite stable states.

  1. Single Molecule Cluster Analysis dissects splicing pathway conformational dynamics.

    PubMed

    Blanco, Mario R; Martin, Joshua S; Kahlscheuer, Matthew L; Krishnan, Ramya; Abelson, John; Laederach, Alain; Walter, Nils G

    2015-11-01

    We report Single Molecule Cluster Analysis (SiMCAn), which utilizes hierarchical clustering of hidden Markov modeling-fitted single-molecule fluorescence resonance energy transfer (smFRET) trajectories to dissect the complex conformational dynamics of biomolecular machines. We used this method to study the conformational dynamics of a precursor mRNA during the splicing cycle as carried out by the spliceosome. By clustering common dynamic behaviors derived from selectively blocked splicing reactions, SiMCAn was able to identify the signature conformations and dynamic behaviors of multiple ATP-dependent intermediates. In addition, it identified an open conformation adopted late in splicing by a 3' splice-site mutant, invoking a mechanism for substrate proofreading. SiMCAn enables rapid interpretation of complex single-molecule behaviors and should prove useful for the comprehensive analysis of a plethora of dynamic cellular machines.

  2. Nonlinear mode coupling and vibrational energy transfer in Yukawa clusters

    NASA Astrophysics Data System (ADS)

    Qiao, Ke; Kong, Jie; Matthews, Lorin; Hyde, Truell

    2015-11-01

    Nonlinear mode coupling and the subsequent vibrational energy transfer that results is an important topic in chemical physics research, ranging from small molecules consisting of several atoms to macromolecules such as those found in proteins and DNA. Nonlinear mode coupling is recognized as the mechanism leading to ergodicity, which is a foundational tenet of statistical mechanics. Over the past two decades, Yukawa systems of particles such as those found in complex plasma, have been shown to be an effective model across a large number of physical systems. In this research, nonlinear mode coupling in Yukawa clusters consisting of 3-10 particles is examined via numerical simulation of the vibrational energy transfer between modes starting from an initial excited state. The relationship between the energy transfer process and the internal resonance between modes having a specified frequency ratio and the temporal evolution of the system to a state of equal energy across all modes, i.e., the state of ergodicity, will be discussed. Support from the NSF and the DOE (award numbers PHY-1262031 and PHY-1414523) is gratefully acknowledged.

  3. Coupled cluster calculations of neutron-rich nuclei

    NASA Astrophysics Data System (ADS)

    Hagen, Gaute

    2016-09-01

    In this talk I will present recent highlights from ab initio computations of atomic nuclei using coupled-cluster methods with state-of-the-art interactions from chiral effective field theory (EFT). The recent progress in computing nuclei from scratch is based on new optimizations of interactions from chiral EFT, and ab initio methods with a polynomial computational cost together with available super computing resources. The physics advancements I will discuss include: (i) accurate nuclear binding energies and radii of light and medium-mass nuclei, (ii) the neutron distribution and electric dipole polarizability of the nucleus 48Ca, (iii) and the structure of the rare nucleus 78Ni from first principles. All these quantities are currently targeted by precision measurements worldwide.

  4. Higher-order diagrammatic vibrational coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Faucheaux, Jacob A.; Hirata, So

    2015-10-01

    Diagrammatically size-consistent and basis-set-free vibrational coupled-cluster (XVCC) theory for both zero-point energies and transition frequencies of a molecule, the latter through the equation-of-motion (EOM) formalism, is defined for an nth-order Taylor-series potential energy surface (PES). Quantum-field-theoretical tools (the rules of normal-ordered second quantization and Feynman-Goldstone diagrams) for deriving their working equations are established. The equations of XVCC and EOM-XVCC including up to the mth-order excitation operators are derived and implemented with the aid of computer algebra in the range of 1 ≤ m ≤ 8. Algorithm optimizations known as strength reduction, intermediate reuse, and factorization are carried out before code generation, reducing the cost scaling of the mth-order XVCC and EOM-XVCC in an nth-order Taylor-series PES (m ≥ n) to the optimal value of O(Nm+⌊n/2⌋), where N is the number of modes. The calculated zero-point energies and frequencies of fundamentals, overtones, and combinations as well as Fermi-resonant modes display rapid and nearly monotonic convergence with m towards the exact values for the PES. The theory with the same excitation rank as the truncation order of the Taylor-series PES (m = n) seems to strike the best cost-accuracy balance, achieving the accuracy of a few tenths of cm-1 for transitions involving (m - 3) modes and of a few cm-1 for those involving (m - 2) modes. The relationships between XVCC and the vibrational coupled-cluster theories of Prasad and coworkers and of Christiansen and coworkers as well as the size-extensive vibrational self-consistent-field and many-body perturbation theories are also elucidated.

  5. Constraining ALP-photon coupling using galaxy clusters

    SciTech Connect

    Schlederer, Martin; Sigl, Günter E-mail: guenter.sigl@desy.de

    2016-01-01

    We study photon-ALP conversion by resonance effects in the magnetized plasma of galaxy clusters and compare the predicted distortion of the cosmic microwave background spectrum in the direction of such objects to measurements of the thermal Sunyaev-Zeldovich effect. Using galaxy cluster models based on current knowledge, we obtain upper limits on the photon-ALP coupling constant g of ∼< O(10{sup −11} GeV{sup −1}). The constraints apply to the mass range of 2 · 10{sup −14} eV ∼< m{sub ALP} ∼< 3 · 10{sup −12} eV in which resonant photon-ALP conversions can occur. These limits are slightly stronger than current limits, and furthermore provide an independent constraint. We find that a next generation PRISM-like experiment would allow limits down to g ≈ O (10{sup −14} GeV{sup −1}), two orders of magnitude stronger than the currently strongest limits in this mass range.

  6. Constraining ALP-photon coupling using galaxy clusters

    NASA Astrophysics Data System (ADS)

    Schlederer, Martin; Sigl, Günter

    2016-01-01

    We study photon-ALP conversion by resonance effects in the magnetized plasma of galaxy clusters and compare the predicted distortion of the cosmic microwave background spectrum in the direction of such objects to measurements of the thermal Sunyaev-Zeldovich effect. Using galaxy cluster models based on current knowledge, we obtain upper limits on the photon-ALP coupling constant g of lesssim Script O(10-11 GeV-1). The constraints apply to the mass range of 2 · 10-14 eV lesssim mALP lesssim 3 · 10-12 eV in which resonant photon-ALP conversions can occur. These limits are slightly stronger than current limits, and furthermore provide an independent constraint. We find that a next generation PRISM-like experiment would allow limits down to g ≈ Script O (10-14 GeV-1), two orders of magnitude stronger than the currently strongest limits in this mass range.

  7. Constraining ALP-photon coupling using galaxy clusters

    SciTech Connect

    Schlederer, Martin; Sigl, Günter

    2016-01-21

    We study photon-ALP conversion by resonance effects in the magnetized plasma of galaxy clusters and compare the predicted distortion of the cosmic microwave background spectrum in the direction of such objects to measurements of the thermal Sunyaev-Zeldovich effect. Using galaxy cluster models based on current knowledge, we obtain upper limits on the photon-ALP coupling constant g of ≲O(10{sup −11} GeV{sup −1}). The constraints apply to the mass range of 2⋅10{sup −14} eV ≲m{sub ALP}≲3⋅10{sup −12} eV in which resonant photon-ALP conversions can occur. These limits are slightly stronger than current limits, and furthermore provide an independent constraint. We find that a next generation PRISM-like experiment would allow limits down to g≈O(10{sup −14} GeV{sup −1}), two orders of magnitude stronger than the currently strongest limits in this mass range.

  8. Matrix elements in the coupled-cluster approach - With application to low-lying states in Li

    NASA Technical Reports Server (NTRS)

    Martensson-Pendrill, Ann-Marie; Ynnerman, Anders

    1990-01-01

    A procedure is suggested for evaluating matrix elements of an operator between wavefunctions in the coupled-cluster form. The use of the exponential ansatz leads to compact exponential expressions also for matrix elements. Algorithms are developed for summing all effects of one-particle clusters and certain chains of two-particle clusters (containing the well-known random-phase approximation as a subset). The treatment of one-particle perturbations in single valence states is investigated in detail. As examples the oscillator strength for the 2s-2p transition in Li as well as the hyperfine structure for the two states are studied and compared to earlier work.

  9. Phage cluster relationships identified through single gene analysis

    PubMed Central

    2013-01-01

    Background Phylogenetic comparison of bacteriophages requires whole genome approaches such as dotplot analysis, genome pairwise maps, and gene content analysis. Currently mycobacteriophages, a highly studied phage group, are categorized into related clusters based on the comparative analysis of whole genome sequences. With the recent explosion of phage isolation, a simple method for phage cluster prediction would facilitate analysis of crude or complex samples without whole genome isolation and sequencing. The hypothesis of this study was that mycobacteriophage-cluster prediction is possible using comparison of a single, ubiquitous, semi-conserved gene. Tape Measure Protein (TMP) was selected to test the hypothesis because it is typically the longest gene in mycobacteriophage genomes and because regions within the TMP gene are conserved. Results A single gene, TMP, identified the known Mycobacteriophage clusters and subclusters using a Gepard dotplot comparison or a phylogenetic tree constructed from global alignment and maximum likelihood comparisons. Gepard analysis of 247 mycobacteriophage TMP sequences appropriately recovered 98.8% of the subcluster assignments that were made by whole-genome comparison. Subcluster-specific primers within TMP allow for PCR determination of the mycobacteriophage subcluster from DNA samples. Using the single-gene comparison approach for siphovirus coliphages, phage groupings by TMP comparison reflected relationships observed in a whole genome dotplot comparison and confirm the potential utility of this approach to another widely studied group of phages. Conclusions TMP sequence comparison and PCR results support the hypothesis that a single gene can be used for distinguishing phage cluster and subcluster assignments. TMP single-gene analysis can quickly and accurately aid in mycobacteriophage classification. PMID:23777341

  10. Implementation of High-Order Multireference Coupled-Cluster Methods on Intel Many Integrated Core Architecture.

    PubMed

    Aprà, E; Kowalski, K

    2016-03-08

    In this paper we discuss the implementation of multireference coupled-cluster formalism with singles, doubles, and noniterative triples (MRCCSD(T)), which is capable of taking advantage of the processing power of the Intel Xeon Phi coprocessor. We discuss the integration of two levels of parallelism underlying the MRCCSD(T) implementation with computational kernels designed to offload the computationally intensive parts of the MRCCSD(T) formalism to Intel Xeon Phi coprocessors. Special attention is given to the enhancement of the parallel performance by task reordering that has improved load balancing in the noniterative part of the MRCCSD(T) calculations. We also discuss aspects regarding efficient optimization and vectorization strategies.

  11. Transition moments between excited electronic states from the Hermitian formulation of the coupled cluster quadratic response function

    NASA Astrophysics Data System (ADS)

    Tucholska, Aleksandra M.; Lesiuk, Michał; Moszynski, Robert

    2017-01-01

    We introduce a new method for the computation of the transition moments between the excited electronic states based on the expectation value formalism of the coupled cluster theory [B. Jeziorski and R. Moszynski, Int. J. Quantum Chem. 48, 161 (1993)]. The working expressions of the new method solely employ the coupled cluster operator T and an auxiliary operator S that is expressed as a finite commutator expansion in terms of T and T†. In the approximation adopted in the present paper, the cluster expansion is limited to single, double, and linear triple excitations. The computed dipole transition probabilities for the singlet-singlet and triplet-triplet transitions in alkali earth atoms agree well with the available theoretical and experimental data. In contrast to the existing coupled cluster response theory, the matrix elements obtained by using our approach satisfy the Hermitian symmetry even if the excitations in the cluster operator are truncated, but the operator S is exact. The Hermitian symmetry is slightly broken if the commutator series for the operator S are truncated. As a part of the numerical evidence for the new method, we report calculations of the transition moments between the excited triplet states which have not yet been reported in the literature within the coupled cluster theory. Slater-type basis sets constructed according to the correlation-consistency principle are used in our calculations.

  12. Transition moments between excited electronic states from the Hermitian formulation of the coupled cluster quadratic response function.

    PubMed

    Tucholska, Aleksandra M; Lesiuk, Michał; Moszynski, Robert

    2017-01-21

    We introduce a new method for the computation of the transition moments between the excited electronic states based on the expectation value formalism of the coupled cluster theory [B. Jeziorski and R. Moszynski, Int. J. Quantum Chem. 48, 161 (1993)]. The working expressions of the new method solely employ the coupled cluster operator T and an auxiliary operator S that is expressed as a finite commutator expansion in terms of T and T(†). In the approximation adopted in the present paper, the cluster expansion is limited to single, double, and linear triple excitations. The computed dipole transition probabilities for the singlet-singlet and triplet-triplet transitions in alkali earth atoms agree well with the available theoretical and experimental data. In contrast to the existing coupled cluster response theory, the matrix elements obtained by using our approach satisfy the Hermitian symmetry even if the excitations in the cluster operator are truncated, but the operator S is exact. The Hermitian symmetry is slightly broken if the commutator series for the operator S are truncated. As a part of the numerical evidence for the new method, we report calculations of the transition moments between the excited triplet states which have not yet been reported in the literature within the coupled cluster theory. Slater-type basis sets constructed according to the correlation-consistency principle are used in our calculations.

  13. Molecular dipole static polarisabilities and hyperpolarisabilities of conjugated oligomer chains calculated with the local π-electron coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Ivanov, Vladimir V.; Zakharov, Anton B.; Adamowicz, Ludwik

    2013-12-01

    A new semi-empirical π-electron local coupled cluster theory has been developed to calculate static dipole polarisabilities and hyperpolarisabilities of extended π-conjugated systems. The key idea of the approach is the use of the ethylene molecular orbitals as the orbital basis set for π-conjugated compounds (the method is termed the Covalent Unbonded Molecules of Ethylene method, cue). Test calculations of some small model organic conjugated compounds demonstrate high accuracy of the version of the cue local coupled cluster theory developed in this work in comparison with the π-electron full configuration interaction (FCI) method. Calculations of different conjugated carbon-based oligomer chains (polyenes, polyynes, polyacenes, polybenzocyclobutadiene, etc.) demonstrate fast convergence (per π-electron) of the polarisability and hyperpolarisability values in the calculations when more classes of orbital excitations are included in the coupled cluster single and double (CCSD) excitation operator. The results show qualitatively correct dependence on the system size.

  14. Relaxed active space: Fixing tailored-CC with high order coupled cluster. I

    NASA Astrophysics Data System (ADS)

    Melnichuk, Anna; Bartlett, Rodney J.

    2012-12-01

    Several single reference (SR-CC) coupled cluster methods are shown to work for traditionally multi-reference (MR) problems such as bond breaking subject to restricted Hartree-Fock (RHF) references. The correlated methods can successfully describe any MR problem with enough higher order clusters: singles and doubles (CCSD), singles, doubles and triples (CCSDT), singles, doubles, triples, and quadruples (CCSDTQ), etc. However, due to the steep increase in the computational cost, it is not practical to do larger systems or to use large basis sets without active space partitioning. In this study, the orbital space is partitioned into an active space subject to an unambiguous statistical criteria to span the MR behavior which defines an extended space to let the active space relax. The rest is considered the external space. The extended space is treated with CCSDT and the external space with CCSD. An automated scheme for determining the extended space is presented and evaluated. We build upon the tailored-CC scheme of Hino et al. and address its main shortcoming of neglecting the coupling between the active space and the rest of the orbital space which results in loss of accuracy as well as a pronounced nonparallelism error (NPE). The automated scheme makes it unnecessary for the user to judge whether a chosen active space is sufficient to correctly solve the problem. We illustrate this method for the hydrogen fluoride and fluorine molecule ground state dissociation potentials using the extended space partitioning methods. Experimental accuracy for the dissociation energy is achieved at a small fraction of the cost of doing a full CCSDT calculation. This approach is easily amendable to higher order clusters which are required for double and triple bond breaking and other strongly multi-reference systems.

  15. Communication: The performance of non-iterative coupled cluster quadruples models.

    PubMed

    Eriksen, Janus J; Matthews, Devin A; Jørgensen, Poul; Gauss, Jürgen

    2015-07-28

    We compare the numerical performance of various non-iterative coupled cluster (CC) quadruples models. The results collectively show how approaches that attempt to correct the CC singles and doubles energy for the combined effect of triple and quadruple excitations all fail at recovering the correlation energy of the full CC singles, doubles, triples, and quadruples (CCSDTQ) model to within sufficient accuracy. Such a level of accuracy is only achieved by models that make corrections to the full CC singles, doubles, and triples (CCSDT) energy for the isolated effect of quadruple excitations of which the CCSDT(Q-3) and CCSDT(Q-4) models of the Lagrangian-based CCSDT(Q-n) perturbation series are found to outperform alternative models that add either of the established [Q] and (Q) corrections to the CCSDT energy.

  16. Optimization of the Coupled Cluster Implementation in NWChem on Petascale Parallel Architectures

    SciTech Connect

    Anisimov, Victor; Bauer, Gregory H.; Chadalavada, Kalyana; Olson, Ryan M.; Glenski, Joseph W.; Kramer, William T.; Apra, Edoardo; Kowalski, Karol

    2014-09-04

    Coupled cluster singles and doubles (CCSD) algorithm has been optimized in NWChem software package. This modification alleviated the communication bottleneck and provided from 2- to 5-fold speedup in the CCSD iteration time depending on the problem size and available memory. Sustained 0.60 petaflop/sec performance on CCSD(T) calculation has been obtained on NCSA Blue Waters. This number included all stages of the calculation from initialization till termination, iterative computation of single and double excitations, and perturbative accounting for triple excitations. In the section of perturbative triples alone, the computation maintained 1.18 petaflop/sec performance level. CCSD computations have been performed on Guanine-Cytosine deoxydinucleotide monophosphate (GC-dDMP) to probe the conformational energy difference in DNA single strand in A- and B-conformations. The computation revealed significant discrepancy between CCSD and classical force fields in prediction of relative energy of A- and B-conformations of GC-dDMP.

  17. Calculation of excited-state properties using general coupled-cluster and configuration-interaction models.

    PubMed

    Kállay, Mihály; Gauss, Jürgen

    2004-11-15

    Using string-based algorithms excitation energies and analytic first derivatives for excited states have been implemented for general coupled-cluster (CC) models within CC linear-response (LR) theory which is equivalent to the equation-of-motion (EOM) CC approach for these quantities. Transition moments between the ground and excited states are also considered in the framework of linear-response theory. The presented procedures are applicable to both single-reference-type and multireference-type CC wave functions independently of the excitation manifold constituting the cluster operator and the space in which the effective Hamiltonian is diagonalized. The performance of different LR-CC/EOM-CC and configuration-interaction approaches for excited states is compared. The effect of higher excitations on excited-state properties is demonstrated in benchmark calculations for NH(2) and NH(3). As a first application, the stationary points of the S(1) surface of acetylene are characterized by high-accuracy calculations.

  18. Polarizable interaction potential for water from coupled cluster calculations. I. Analysis of dimer potential energy surface

    NASA Astrophysics Data System (ADS)

    Bukowski, Robert; Szalewicz, Krzysztof; Groenenboom, Gerrit C.; van der Avoird, Ad

    2008-03-01

    A six-dimensional interaction potential for the water dimer has been fitted to ab initio interaction energies computed at 2510 dimer configurations. These energies were obtained by combining the supermolecular second-order energies extrapolated to the complete basis set limit from up to quadruple-zeta quality basis sets with the contribution from the coupled-cluster method including single, double, and noniterative triple excitations computed in a triple-zeta quality basis set. All basis sets were augmented by diffuse functions and supplemented by midbond functions. The energies have been fitted using an analytic form with the induction component represented by a polarizable term, making the potential directly transferable to clusters and the bulk phase. Geometries and energies of stationary points on the potential surface agree well with the results of high-level ab initio geometry optimizations.

  19. Coupled Cluster Evaluation of the Stability of Atmospheric Acid-Base Clusters with up to 10 Molecules.

    PubMed

    Myllys, Nanna; Elm, Jonas; Halonen, Roope; Kurtén, Theo; Vehkamäki, Hanna

    2016-02-04

    We investigate the utilization of the domain local pair natural orbital coupled cluster (DLPNO-CCSD(T)) method for calculating binding energies of atmospherical molecular clusters. Applied to small complexes of atmospherical relevance we find that the DLPNO method significantly reduces the scatter in the binding energy, which is commonly present in DFT calculations. For medium sized clusters consisting of sulfuric acid and bases the DLPNO method yields a systematic underestimation of the binding energy compared to canonical coupled cluster results. The errors in the DFT binding energies appear to be more random, while the systematic nature of the DLPNO results allows the establishment of a scaling factor, to better mimic the canonical coupled cluster calculations. Based on the trends identified for the small and medium sized systems, we further extend the application of the DLPNO method to large acid - base clusters consisting of up to 10 molecules, which have previously been out of reach with accurate coupled cluster methods. Using the Atmospheric Cluster Dynamics Code (ACDC) we compare the sulfuric acid dimer formation based on the new DLPNO binding energies with previously published RI-CC2/aug-cc-pV(T+d)Z results. We also compare the simulated sulfuric acid dimer concentration as a function of the base concentration with measurement data from the CLOUD chamber and flow tube experiments. The DLPNO method, even after scaling, underpredicts the dimer concentration significantly. Reasons for this are discussed.

  20. Spin-orbit coupling and electron correlation in relativistic configuration interaction and coupled-cluster methods

    NASA Astrophysics Data System (ADS)

    Kim, Inkoo; Park, Young Choon; Kim, Hyungjun; Lee, Yoon Sup

    2012-02-01

    We studied convergence characteristics of relativistic effective core potential (RECP) based configuration interaction (CI) and coupled-cluster (CC) schemes in terms of spin-orbit coupling and electron correlation. The relativistic correlated methods can be divided into Kramers restricted (KR) and spin-orbit (SO) methods which differ by the stage of spin-orbit treatment: the KR method employs two-component Kramers restricted Hartree-Fock (HF) spinors as the one-electron basis in which spin-orbit coupling is included, whereas the SO method is based on one-component molecular orbitals generated from scalar relativistic HF and the spin-orbit interaction is then entered in post-HF step. The KR method is usually superior to the SO method for molecules containing heavy elements since spin-orbit coupling is included from the HF step. A performance calibration of the SO method against the KR method is performed by computations of the ground state energies and equilibrium bond lengths of MH (M = Tl, Pb, Bi, Po, and At). Spin-orbit coupling of each molecule was systematically increased by adjusting the spin-orbit operator of RECP to investigate its impact on the SO method. Although KRCI and SOCI converged to the same full-CI limit, for the strong spin-orbit coupling SOCI required higher levels of correlation compared to KRCI to account for the orbital relaxation effect. SOCC, in contrast, was able to recover both spin-orbit interaction and electron correlation in CC steps regardless of the spin-orbit strength, implying that SOCC could be the reliable and efficient relativistic ab initio method for moderate sized molecules containing heavy elements.

  1. Explicitly-correlated coupled cluster method for long-range dispersion coefficients

    NASA Astrophysics Data System (ADS)

    Bokhan, Denis; Trubnikov, Dmitrii N.; Perera, Ajith; Bartlett, Rodney J.

    2017-03-01

    A method of calculation of long-range dispersion C6 coefficients with wavefunctions, corresponding to linearly approximated explicitly correlated coupled-cluster singles and doubles [CCSD(F12)] model, has been developed. Designed approach uses CCSD(F12) wave functions for the calculation of dynamic polarizabilities at complex frequencies with further utilization of Casimir-Polder formula. As a part of the algorithm, the explicitly-correlated version of the coupled-perturbed CCSD equations for the case of complex frequencies has also been implemented. Numerical tests, conducted for the set of molecules show good agreement between dispersion coefficients, calculated with developed explicitly-correlated method and corresponding complete basis set results in regular CCSD already at triple- ζ level.

  2. Insights into the orbital invariance problem in state-specific multireference coupled cluster theory.

    PubMed

    Evangelista, Francesco A; Gauss, Jürgen

    2010-07-28

    In this communication we report the results of our studies on the orbital invariance properties of the state-specific multireference coupled cluster approach suggested by Mukherjee and co-workers (Mk-MRCC). In particular, we have gathered numerical evidence to show that even when the linear excitation manifold is modified in order to span the same space for each reference, the resulting method is not orbital invariant. In order to test this conjecture we have proposed a new truncation scheme (Mk-MRCCSDtq) which, in addition to full single and double excitations, contains partial triple and quadruple excitations. For a reference space generated by all possible combinations of two electrons in two orbitals, the linear excitation manifold of Mk-MRCCSDtq spans the same set for each reference determinant. Mk-MRCCSDtq is found to lack energy invariance for rotations among active molecular orbitals but it is less sensitive to orbital rotations than the conventional scheme which includes only singles and doubles (Mk-MRCCSD). Nevertheless, Mk-MRCCSDtq is a very accurate method, superior with respect to multireference configuration interaction approaches, and competitive with the active-space coupled cluster method and the MRexpT ansatz.

  3. Correlated natural transition orbitals for core excitation energies in multilevel coupled cluster models.

    PubMed

    Høyvik, Ida-Marie; Myhre, Rolf Heilemann; Koch, Henrik

    2017-04-14

    In this article, we present a black-box approach for the selection of orbital spaces when computing core excitation energies in the multilevel coupled cluster (MLCC) framework. Information available from the lower level of theory is used to generate correlated natural transition orbitals (CNTOs) for the high-level calculation by including both singles and doubles information in the construction of the transition orbitals. The inclusion of the doubles excitation information is essential to obtain a set of orbitals that all contain physical information, in contrast to the natural transition orbitals where only a small subset of the virtual orbitals contains physical information. The CNTOs may be included in an active space based on a cutoff threshold for the eigenvalues corresponding to the orbitals. We present MLCC results for core excitation energies calculated using coupled cluster singles and doubles (CCSD) in the inactive space and CCSD with perturbative triples (CC3) in the active space. The use of CNTOs results in small errors compared to full CC3.

  4. Correlated natural transition orbitals for core excitation energies in multilevel coupled cluster models

    NASA Astrophysics Data System (ADS)

    Høyvik, Ida-Marie; Myhre, Rolf Heilemann; Koch, Henrik

    2017-04-01

    In this article, we present a black-box approach for the selection of orbital spaces when computing core excitation energies in the multilevel coupled cluster (MLCC) framework. Information available from the lower level of theory is used to generate correlated natural transition orbitals (CNTOs) for the high-level calculation by including both singles and doubles information in the construction of the transition orbitals. The inclusion of the doubles excitation information is essential to obtain a set of orbitals that all contain physical information, in contrast to the natural transition orbitals where only a small subset of the virtual orbitals contains physical information. The CNTOs may be included in an active space based on a cutoff threshold for the eigenvalues corresponding to the orbitals. We present MLCC results for core excitation energies calculated using coupled cluster singles and doubles (CCSD) in the inactive space and CCSD with perturbative triples (CC3) in the active space. The use of CNTOs results in small errors compared to full CC3.

  5. Holograms for laser diode: Single mode optical fiber coupling

    NASA Technical Reports Server (NTRS)

    Fuhr, P. L.

    1982-01-01

    The low coupling efficiency of semiconductor laser emissions into a single mode optical fibers place a severe restriction on their use. Associated with these conventional optical coupling techniques are stringent alignment sensitivities. Using holographic elements, the coupling efficiency may be increased and the alignment sensitivity greatly reduced. Both conventional and computer methods used in the generation of the holographic couplers are described and diagrammed. The reconstruction geometries used are shown to be somewhat restrictive but substantially less rigid than their conventional optical counterparts. Single and double hologram techniques are examined concerning their respective ease of fabrication and relative merits.

  6. Explicitly correlated coupled cluster calculations for propadienylidene (H(2)CCC).

    PubMed

    Botschwina, Peter; Oswald, Rainer

    2010-09-16

    Propadienylidene (H(2)CCC), a reactive carbene of interest to combustion processes and astrochemistry, has been studied by explicitly correlated coupled cluster theory at the CCSD(T)-F12x (x = a, b) level. Vibrational configuration interaction (VCI) has been employed to calculate accurate wavenumbers for the fundamental vibrations of H(2)CCC, D(2)CCC, and HDCCC. The symmetric CH stretching vibration of H(2)CCC is predicted to occur at ν(1) = 2984 cm(-1). Absorptions observed by argon matrix infrared spectroscopy at 3049.5 and 3059.6 cm(-1) are reassigned to the combination tone ν(2) + ν(4), which interacts with ν(1) and is predicted to have a higher intensity than the latter. Furthermore, IR bands detected at 865.4 and 868.8 cm(-1) are assigned to ν(6)(HDCCC), and those observed at 904.0 and 909.8 cm(-1) are assigned to the out-of-plane bending vibration ν(8)(HDCCC). An accurate value of 79.8 +/- 0.2 kJ mol(-1) is recommended for the zero-point vibrational energy of H(2)CCC.

  7. Dissociation of homonuclear diatomic halogens via multireference coupled cluster calculations

    NASA Astrophysics Data System (ADS)

    Chattopadhyay, Sudip; Sinha Mahapatra, Uttam; Chaudhuri, Rajat K.

    2014-10-01

    We have computed the potential energy surfaces (PESs) of F2, Cl2, Br2, and I2 using the size-extensive state specific multireference coupled cluster (SS-MRCC) method. The MR character of the system considered here at large distances and the presence of low-lying intruder states are known to be the major causes of incorrect or inaccurate predictions of the PES. The SS-MRCC theory is tailored to treat degeneracies of varying extent while bypassing the intruder problem. The quality of the computed PES has been gauged by computing spectroscopic constants. The calculated properties show a good agreement with available experimental data and the errors in the calculated molecular properties compare favourably with the most elaborate current-generation calculations of the literature. The accuracy of the computed PES of F2 is such that it has been proved to calculate the vibrational spectrum of the 22 levels with a minimum and maximum absolute deviation of 2 and 57 cm-1, respectively, from the experimental values. The highly satisfactory performance of the SS-MRCC method, vis-a-vis the other sophisticated methods, in describing the vibrational levels is noticeable for one of the more difficult systems such as F2 clearly indicates that the present method is reliable in studying the vibrational energy levels.

  8. Coupled-cluster methods for core-hole dynamics

    NASA Astrophysics Data System (ADS)

    Picon, Antonio; Cheng, Lan; Hammond, Jeff R.; Stanton, John F.; Southworth, Stephen H.

    2014-05-01

    Coupled cluster (CC) is a powerful numerical method used in quantum chemistry in order to take into account electron correlation with high accuracy and size consistency. In the CC framework, excited, ionized, and electron-attached states can be described by the equation of motion (EOM) CC technique. However, bringing CC methods to describe molecular dynamics induced by x rays is challenging. X rays have the special feature of interacting with core-shell electrons that are close to the nucleus. Core-shell electrons can be ionized or excited to a valence shell, leaving a core-hole that will decay very fast (e.g. 2.4 fs for K-shell of Ne) by emitting photons (fluorescence process) or electrons (Auger process). Both processes are a clear manifestation of a many-body effect, involving electrons in the continuum in the case of Auger processes. We review our progress of developing EOM-CC methods for core-hole dynamics. Results of the calculations will be compared with measurements on core-hole decays in atomic Xe and molecular XeF2. This work is funded by the Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy, under Contract No. DE-AC02-06CH11357.

  9. Calculation of Dipole Transition Matrix Elements and Expectation Values by Vibrational Coupled Cluster Method.

    PubMed

    Banik, Subrata; Pal, Sourav; Prasad, M Durga

    2010-10-12

    An effective operator approach based on the coupled cluster method is described and applied to calculate vibrational expectation values and absolute transition matrix elements. Coupled cluster linear response theory (CCLRT) is used to calculate excited states. The convergence pattern of these properties with the rank of the excitation operator is studied. The method is applied to a water molecule. Arponen-type double similarity transformation in extended coupled cluster (ECCM) framework is also used to generate an effective operator, and the convergence pattern of these properties is compared to the normal coupled cluster (NCCM) approach. It is found that the coupled cluster method provides an accurate description of these quantities for low lying vibrational excited states. The ECCM provides a significant improvement for the calculation of the transition matrix elements.

  10. Single to quadruple quantum dots with tunable tunnel couplings

    SciTech Connect

    Takakura, T.; Noiri, A.; Obata, T.; Yoneda, J.; Yoshida, K.; Otsuka, T.; Tarucha, S.

    2014-03-17

    We prepare a gate-defined quadruple quantum dot to study the gate-tunability of single to quadruple quantum dots with finite inter-dot tunnel couplings. The measured charging energies of various double dots suggest that the dot size is governed by the gate geometry. For the triple and quadruple dots, we study the gate-tunable inter-dot tunnel couplings. For the triple dot, we find that the effective tunnel coupling between side dots significantly depends on the alignment of the center dot potential. These results imply that the present quadruple dot has a gate performance relevant for implementing spin-based four-qubits with controllable exchange couplings.

  11. The externally corrected coupled cluster approach with four- and five-body clusters from the CASSCF wave function

    NASA Astrophysics Data System (ADS)

    Xu, Enhua; Li, Shuhua

    2015-03-01

    An externally corrected CCSDt (coupled cluster with singles, doubles, and active triples) approach employing four- and five-body clusters from the complete active space self-consistent field (CASSCF) wave function (denoted as ecCCSDt-CASSCF) is presented. The quadruple and quintuple excitation amplitudes within the active space are extracted from the CASSCF wave function and then fed into the CCSDt-like equations, which can be solved in an iterative way as the standard CCSDt equations. With a size-extensive CASSCF reference function, the ecCCSDt-CASSCF method is size-extensive. When the CASSCF wave function is readily available, the computational cost of the ecCCSDt-CASSCF method scales as the popular CCSD method (if the number of active orbitals is small compared to the total number of orbitals). The ecCCSDt-CASSCF approach has been applied to investigate the potential energy surface for the simultaneous dissociation of two O-H bonds in H2O, the equilibrium distances and spectroscopic constants of 4 diatomic molecules (F2+, O2+, Be2, and NiC), and the reaction barriers for the automerization reaction of cyclobutadiene and the Cl + O3 → ClO + O2 reaction. In most cases, the ecCCSDt-CASSCF approach can provide better results than the CASPT2 (second order perturbation theory with a CASSCF reference function) and CCSDT methods.

  12. Toward enabling large-scale open-shell equation-of-motion coupled cluster calculations: triplet states of β-carotene.

    PubMed

    Hu, Han-Shi; Bhaskaran-Nair, Kiran; Aprà, Edoardo; Govind, Niranjan; Kowalski, Karol

    2014-10-02

    In this paper we discuss the application of novel parallel implementation of the coupled cluster (CC) and equation-of-motion coupled cluster methods (EOMCC) in calculations of excitation energies of triplet states in β-carotene. Calculated excitation energies are compared with experimental data, where available. We also provide a detailed description of the new parallel algorithms for iterative CC and EOMCC models involving singles and doubles excitations.

  13. Toward enabling large-scale open-shell equation-of-motion coupled cluster calculations: triplet states of β-carotene

    SciTech Connect

    Hu, Hanshi; Bhaskaran-Nair, Kiran; Apra, Edoardo; Govind, Niranjan; Kowalski, Karol

    2014-10-02

    In this paper we discuss the application of novel parallel implementation of the coupled cluster (CC) and equation-of-motion coupled cluster methods (EOMCC) in calculations of excitation energies of triplet states in beta-carotene. Calculated excitation energies are compared with experimental data, where available. We also provide a detailed description of the new parallel algorithms for iterative CC and EOMCC models involving single and doubles excitations.

  14. Description of spin–orbit coupling in excited states with two-component methods based on approximate coupled-cluster theory

    SciTech Connect

    Krause, Katharina; Klopper, Wim

    2015-03-14

    A generalization of the approximated coupled-cluster singles and doubles method and the algebraic diagrammatic construction scheme up to second order to two-component spinors obtained from a relativistic Hartree–Fock calculation is reported. Computational results for zero-field splittings of atoms and monoatomic cations, triplet lifetimes of two organic molecules, and the spin-forbidden part of the UV/Vis absorption spectrum of tris(ethylenediamine)cobalt(III) are presented.

  15. Noniterative Multireference Coupled Cluster Methods on Heterogeneous CPU-GPU Systems

    SciTech Connect

    Bhaskaran-Nair, Kiran; Ma, Wenjing; Krishnamoorthy, Sriram; Villa, Oreste; van Dam, Hubertus JJ; Apra, Edoardo; Kowalski, Karol

    2013-04-09

    A novel parallel algorithm for non-iterative multireference coupled cluster (MRCC) theories, which merges recently introduced reference-level parallelism (RLP) [K. Bhaskaran-Nair, J.Brabec, E. Aprà, H.J.J. van Dam, J. Pittner, K. Kowalski, J. Chem. Phys. 137, 094112 (2012)] with the possibility of accelerating numerical calculations using graphics processing unit (GPU) is presented. We discuss the performance of this algorithm on the example of the MRCCSD(T) method (iterative singles and doubles and perturbative triples), where the corrections due to triples are added to the diagonal elements of the MRCCSD (iterative singles and doubles) effective Hamiltonian matrix. The performance of the combined RLP/GPU algorithm is illustrated on the example of the Brillouin-Wigner (BW) and Mukherjee (Mk) state-specific MRCCSD(T) formulations.

  16. Auger decay rates of core hole states using equation of motion coupled cluster method

    NASA Astrophysics Data System (ADS)

    Ghosh, Aryya; Vaval, Nayana; Pal, Sourav

    2017-01-01

    The recent development of Linac coherent light source high intense X-ray laser makes it possible to create double core ionization in the molecule. The generation of double core hole state and its decay is identified by Auger spectroscopy. The decay of this double core hole (DCH) states can be used as a powerful spectroscopic tool in chemical analysis. In the present work, we have implemented a promising approach, known as CAP-EOMCC method, which is a combination of complex absorbing potential (CAP) and equation-of-motion coupled cluster (EOMCC) approach to calculate the lifetime of single and double core hole states. We have applied this method to calculate the lifetime of the single core hole (K-LL) and double core hole (KK-KLL) states of CH4, NH3 and HF molecules. The predicted lifetime is found to be extremely short.

  17. Dynamic Polarizabilities of Polyaromatic Hydrocarbons Using Coupled-Cluster Linear Response Theory

    SciTech Connect

    Hammond, Jeffrey R.; Kowalski, Karol; De Jong, Wibe A.

    2007-10-14

    Coupled-cluster theory with single and double excitations (CCSD) is applied to the calculation of optical properties of large polyaromatic hydrocarbons. Dipole polarizabilities are reported for benzene, pyrene, and the oligoacenes sequence n=2-6. Dynamic polarizabilities were calculated on polyacences as large asa pentacene for a single frequency and for benzene and pyrene at many frequencies. The basis set effect was studied for benzene using a variety of basis sets in the Pople and Dunning families up to aug-cc-pVQZ and the Sadlej p VTZ basis, which was used exclusively for the largest molecules. Optimized geometries were evaluated for some of the compounds using HF, B3LYP, PBE0, MP2 and CCSD to understand the role of bond-length-alteration (BLA). Finally, the polarizability results ere compared to four common density-functionals (B3LYP, BLYP, PBE0, PBE).

  18. Stability of two cluster solutions in pulse coupled networks of neural oscillators.

    PubMed

    Chandrasekaran, Lakshmi; Achuthan, Srisairam; Canavier, Carmen C

    2011-04-01

    Phase response curves (PRCs) have been widely used to study synchronization in neural circuits comprised of pacemaking neurons. They describe how the timing of the next spike in a given spontaneously firing neuron is affected by the phase at which an input from another neuron is received. Here we study two reciprocally coupled clusters of pulse coupled oscillatory neurons. The neurons within each cluster are presumed to be identical and identically pulse coupled, but not necessarily identical to those in the other cluster. We investigate a two cluster solution in which all oscillators are synchronized within each cluster, but in which the two clusters are phase locked at nonzero phase with each other. Intuitively, one might expect this solution to be stable only when synchrony within each isolated cluster is stable, but this is not the case. We prove rigorously the stability of the two cluster solution and show how reciprocal coupling can stabilize synchrony within clusters that cannot synchronize in isolation. These stability results for the two cluster solution suggest a mechanism by which reciprocal coupling between brain regions can induce local synchronization via the network feedback loop.

  19. Search for anomalous Wtb couplings in single top quark production.

    PubMed

    Abazov, V M; Abbott, B; Abolins, M; Acharya, B S; Adams, M; Adams, T; Aguilo, E; Ahsan, M; Alexeev, G D; Alkhazov, G; Alton, A; Alverson, G; Alves, G A; Anastasoaie, M; Ancu, L S; Andeen, T; Andrieu, B; Anzelc, M S; Aoki, M; Arnoud, Y; Arov, M; Arthaud, M; Askew, A; Asman, B; Assis Jesus, A C S; Atramentov, O; Avila, C; Badaud, F; Bagby, L; Baldin, B; Bandurin, D V; Banerjee, P; Banerjee, S; Barberis, E; Barfuss, A-F; Bargassa, P; Baringer, P; Barreto, J; Bartlett, J F; Bassler, U; Bauer, D; Beale, S; Bean, A; Begalli, M; Begel, M; Belanger-Champagne, C; Bellantoni, L; Bellavance, A; Benitez, J A; Beri, S B; Bernardi, G; Bernhard, R; Bertram, I; Besançon, M; Beuselinck, R; Bezzubov, V A; Bhat, P C; Bhatnagar, V; Biscarat, C; Blazey, G; Blekman, F; Blessing, S; Bloch, D; Bloom, K; Boehnlein, A; Boline, D; Bolton, T A; Boos, E E; Borissov, G; Bose, T; Brandt, A; Brock, R; Brooijmans, G; Bross, A; Brown, D; Bu, X B; Buchanan, N J; Buchholz, D; Buehler, M; Buescher, V; Bunichev, V; Burdin, S; Burnett, T H; Buszello, C P; Butler, J M; Calfayan, P; Calvet, S; Cammin, J; Carrera, E; Carvalho, W; Casey, B C K; Castilla-Valdez, H; Chakrabarti, S; Chakraborty, D; Chan, K M; Chandra, A; Cheu, E; Chevallier, F; Cho, D K; Choi, S; Choudhary, B; Christofek, L; Christoudias, T; Cihangir, S; Claes, D; Clutter, J; Cooke, M; Cooper, W E; Corcoran, M; Couderc, F; Cousinou, M-C; Crépé-Renaudin, S; Cuplov, V; Cutts, D; Cwiok, M; da Motta, H; Das, A; Davies, G; De, K; de Jong, S J; De La Cruz-Burelo, E; De Oliveira Martins, C; Degenhardt, J D; Déliot, F; Demarteau, M; Demina, R; Denisov, D; Denisov, S P; Desai, S; Diehl, H T; Diesburg, M; Dominguez, A; Dong, H; Dorland, T; Dubey, A; Dudko, L V; Duflot, L; Dugad, S R; Duggan, D; Duperrin, A; Dyer, J; Dyshkant, A; Eads, M; Edmunds, D; Ellison, J; Elvira, V D; Enari, Y; Eno, S; Ermolov, P; Evans, H; Evdokimov, A; Evdokimov, V N; Ferapontov, A V; Ferbel, T; Fiedler, F; Filthaut, F; Fisher, W; Fisk, H E; Fortner, M; Fox, H; Fu, S; Fuess, S; Gadfort, T; Galea, C F; Garcia, C; Garcia-Bellido, A; Gavrilov, V; Gay, P; Geist, W; Gelé, D; Geng, W; Gerber, C E; Gershtein, Y; Gillberg, D; Ginther, G; Gollub, N; Gómez, B; Goussiou, A; Grannis, P D; Greenlee, H; Greenwood, Z D; Gregores, E M; Grenier, G; Gris, Ph; Grivaz, J-F; Grohsjean, A; Grünendahl, S; Grünewald, M W; Guo, F; Guo, J; Gutierrez, G; Gutierrez, P; Haas, A; Hadley, N J; Haefner, P; Hagopian, S; Haley, J; Hall, I; Hall, R E; Han, L; Harder, K; Harel, A; Hauptman, J M; Hauser, R; Hays, J; Hebbeker, T; Hedin, D; Hegeman, J G; Heinson, A P; Heintz, U; Hensel, C; Herner, K; Hesketh, G; Hildreth, M D; Hirosky, R; Hobbs, J D; Hoeneisen, B; Hoeth, H; Hohlfeld, M; Hossain, S; Houben, P; Hu, Y; Hubacek, Z; Hynek, V; Iashvili, I; Illingworth, R; Ito, A S; Jabeen, S; Jaffré, M; Jain, S; Jakobs, K; Jarvis, C; Jesik, R; Johns, K; Johnson, C; Johnson, M; Jonckheere, A; Jonsson, P; Juste, A; Kajfasz, E; Kalk, J M; Karmanov, D; Kasper, P A; Katsanos, I; Kau, D; Kaushik, V; Kehoe, R; Kermiche, S; Khalatyan, N; Khanov, A; Kharchilava, A; Kharzheev, Y M; Khatidze, D; Kim, T J; Kirby, M H; Kirsch, M; Klima, B; Kohli, J M; Konrath, J-P; Kozelov, A V; Kraus, J; Kuhl, T; Kumar, A; Kupco, A; Kurca, T; Kuzmin, V A; Kvita, J; Lacroix, F; Lam, D; Lammers, S; Landsberg, G; Lebrun, P; Lee, W M; Leflat, A; Lellouch, J; Li, J; Li, L; Li, Q Z; Lietti, S M; Lim, J K; Lima, J G R; Lincoln, D; Linnemann, J; Lipaev, V V; Lipton, R; Liu, Y; Liu, Z; Lobodenko, A; Lokajicek, M; Love, P; Lubatti, H J; Luna, R; Lyon, A L; Maciel, A K A; Mackin, D; Madaras, R J; Mättig, P; Magass, C; Magerkurth, A; Mal, P K; Malbouisson, H B; Malik, S; Malyshev, V L; Mao, H S; Maravin, Y; Martin, B; McCarthy, R; Melnitchouk, A; Mendoza, L; Mercadante, P G; Merkin, M; Merritt, K W; Meyer, A; Meyer, J; Millet, T; Mitrevski, J; Mommsen, R K; Mondal, N K; Moore, R W; Moulik, T; Muanza, G S; Mulhearn, M; Mundal, O; Mundim, L; Nagy, E; Naimuddin, M; Narain, M; Naumann, N A; Neal, H A; Negret, J P; Neustroev, P; Nilsen, H; Nogima, H; Novaes, S F; Nunnemann, T; O'Dell, V; O'Neil, D C; Obrant, G; Ochando, C; Onoprienko, D; Oshima, N; Osman, N; Osta, J; Otec, R; Otero y Garzón, G J; Owen, M; Padley, P; Pangilinan, M; Parashar, N; Park, S-J; Park, S K; Parsons, J; Partridge, R; Parua, N; Patwa, A; Pawloski, G; Penning, B; Perfilov, M; Peters, K; Peters, Y; Pétroff, P; Petteni, M; Piegaia, R; Piper, J; Pleier, M-A; Podesta-Lerma, P L M; Podstavkov, V M; Pogorelov, Y; Pol, M-E; Polozov, P; Pope, B G; Popov, A V; Potter, C; Prado da Silva, W L; Prosper, H B; Protopopescu, S; Qian, J; Quadt, A; Quinn, B; Rakitine, A; Rangel, M S; Ranjan, K; Ratoff, P N; Renkel, P; Reucroft, S; Rich, P; Rieger, J; Rijssenbeek, M; Ripp-Baudot, I; Rizatdinova, F; Robinson, S; Rodrigues, R F; Rominsky, M; Royon, C; Rubinov, P; Ruchti, R; Safronov, G; Sajot, G; Sánchez-Hernández, A; Sanders, M P; Sanghi, B; Savage, G; Sawyer, L; Scanlon, T; Schaile, D; Schamberger, R D; Scheglov, Y; Schellman, H; Schliephake, T; Schlobohm, S; Schwanenberger, C; Schwartzman, A; Schwienhorst, R; Sekaric, J; Severini, H; Shabalina, E; Shamim, M; Shary, V; Shchukin, A A; Shivpuri, R K; Siccardi, V; Simak, V; Sirotenko, V; Skubic, P; Slattery, P; Smirnov, D; Snow, G R; Snow, J; Snyder, S; Söldner-Rembold, S; Sonnenschein, L; Sopczak, A; Sosebee, M; Soustruznik, K; Spurlock, B; Stark, J; Steele, J; Stolin, V; Stoyanova, D A; Strandberg, J; Strandberg, S; Strang, M A; Strauss, E; Strauss, M; Ströhmer, R; Strom, D; Stutte, L; Sumowidagdo, S; Svoisky, P; Sznajder, A; Tamburello, P; Tanasijczuk, A; Taylor, W; Tiller, B; Tissandier, F; Titov, M; Tokmenin, V V; Torchiani, I; Tsybychev, D; Tuchming, B; Tully, C; Tuts, P M; Unalan, R; Uvarov, L; Uvarov, S; Uzunyan, S; Vachon, B; van den Berg, P J; Van Kooten, R; van Leeuwen, W M; Varelas, N; Varnes, E W; Vasilyev, I A; Vaupel, M; Verdier, P; Vertogradov, L S; Verzocchi, M; Vilanova, D; Villeneuve-Seguier, F; Vint, P; Vokac, P; Von Toerne, E; Voutilainen, M; Wagner, R; Wahl, H D; Wang, L; Wang, M H L S; Warchol, J; Watts, G; Wayne, M; Weber, G; Weber, M; Welty-Rieger, L; Wenger, A; Wermes, N; Wetstein, M; White, A; Wicke, D; Wilson, G W; Wimpenny, S J; Wobisch, M; Wood, D R; Wyatt, T R; Xie, Y; Yacoob, S; Yamada, R; Yang, W-C; Yasuda, T; Yatsunenko, Y A; Yin, H; Yip, K; Yoo, H D; Youn, S W; Yu, J; Zeitnitz, C; Zelitch, S; Zhao, T; Zhou, B; Zhu, J; Zielinski, M; Zieminska, D; Zieminski, A; Zivkovic, L; Zutshi, V; Zverev, E G

    2008-11-28

    In 0.9 fb(-1) of pp[over] collisions, the D0 Collaboration presented evidence for single top quark production in events with an isolated lepton, missing transverse momentum, and two to four jets. We examine these data to study the Lorentz structure of the Wtb coupling. The standard model predicts a left-handed vector coupling at the Wtb vertex. The most general lowest dimension, CP-conserving Lagrangian admits right-handed vector and left- or right-handed tensor couplings as well. We find that the data prefer the left-handed vector coupling and set upper limits on the anomalous couplings. These are the first direct constraints on a general Wtb interaction and the first direct limits on left- and right-handed tensor couplings.

  20. Relativistic coupled cluster study of diatomic compounds of Hg, Cn, and Fl

    SciTech Connect

    Borschevsky, A.; Pershina, V.; Eliav, E.; Kaldor, U.

    2014-08-28

    The structure and energetics of eight diatomic heavy-atom molecules are presented. These include the species MAu, M{sub 2}, and MHg, with M standing for the Hg, Cn (element 112), and Fl (element 114) atoms. The infinite-order relativistic 2-component Hamiltonian, known to closely reproduce 4-component results at lower computational cost, is used as framework. High-accuracy treatment of correlation is achieved by using the coupled cluster scheme with single, double, and perturbative triple excitations in large converged basis sets. The calculated interatomic separation and bond energy of Hg{sub 2}, the only compound with known experimental data, are in good agreement with measurements. The binding of Fl to Au is stronger than that of Cn, predicting stronger adsorption on gold surfaces. The bond in the M{sub 2} species is strongest for Fl{sub 2}, being of chemical nature; weaker bonds appear in Cn{sub 2} and Hg{sub 2}, which are bound by van der Waals interactions, with the former bound more strongly due to the smaller van der Waals radius. The same set of calculations was also performed using the relativistic density functional theory approach, in order to test the performance of the latter for these weakly bound systems with respect to the more accurate coupled cluster calculations. It was found that for the MAu species the B3LYP functional provides better agreement with the coupled cluster results than the B88/P86 functional. However, for the M{sub 2} and the MHg molecules, B3LYP tends to underestimate the binding energies.

  1. Relativistic coupled cluster study of diatomic compounds of Hg, Cn, and Fl.

    PubMed

    Borschevsky, A; Pershina, V; Eliav, E; Kaldor, U

    2014-08-28

    The structure and energetics of eight diatomic heavy-atom molecules are presented. These include the species MAu, M2, and MHg, with M standing for the Hg, Cn (element 112), and Fl (element 114) atoms. The infinite-order relativistic 2-component Hamiltonian, known to closely reproduce 4-component results at lower computational cost, is used as framework. High-accuracy treatment of correlation is achieved by using the coupled cluster scheme with single, double, and perturbative triple excitations in large converged basis sets. The calculated interatomic separation and bond energy of Hg2, the only compound with known experimental data, are in good agreement with measurements. The binding of Fl to Au is stronger than that of Cn, predicting stronger adsorption on gold surfaces. The bond in the M2 species is strongest for Fl2, being of chemical nature; weaker bonds appear in Cn2 and Hg2, which are bound by van der Waals interactions, with the former bound more strongly due to the smaller van der Waals radius. The same set of calculations was also performed using the relativistic density functional theory approach, in order to test the performance of the latter for these weakly bound systems with respect to the more accurate coupled cluster calculations. It was found that for the MAu species the B3LYP functional provides better agreement with the coupled cluster results than the B88/P86 functional. However, for the M2 and the MHg molecules, B3LYP tends to underestimate the binding energies.

  2. Relativistic coupled cluster study of diatomic compounds of Hg, Cn, and Fl

    NASA Astrophysics Data System (ADS)

    Borschevsky, A.; Pershina, V.; Eliav, E.; Kaldor, U.

    2014-08-01

    The structure and energetics of eight diatomic heavy-atom molecules are presented. These include the species MAu, M2, and MHg, with M standing for the Hg, Cn (element 112), and Fl (element 114) atoms. The infinite-order relativistic 2-component Hamiltonian, known to closely reproduce 4-component results at lower computational cost, is used as framework. High-accuracy treatment of correlation is achieved by using the coupled cluster scheme with single, double, and perturbative triple excitations in large converged basis sets. The calculated interatomic separation and bond energy of Hg2, the only compound with known experimental data, are in good agreement with measurements. The binding of Fl to Au is stronger than that of Cn, predicting stronger adsorption on gold surfaces. The bond in the M2 species is strongest for Fl2, being of chemical nature; weaker bonds appear in Cn2 and Hg2, which are bound by van der Waals interactions, with the former bound more strongly due to the smaller van der Waals radius. The same set of calculations was also performed using the relativistic density functional theory approach, in order to test the performance of the latter for these weakly bound systems with respect to the more accurate coupled cluster calculations. It was found that for the MAu species the B3LYP functional provides better agreement with the coupled cluster results than the B88/P86 functional. However, for the M2 and the MHg molecules, B3LYP tends to underestimate the binding energies.

  3. Communication: Spin densities within a unitary group based spin-adapted open-shell coupled-cluster theory: Analytic evaluation of isotropic hyperfine-coupling constants for the combinatoric open-shell coupled-cluster scheme

    SciTech Connect

    Datta, Dipayan Gauss, Jürgen

    2015-07-07

    We report analytical calculations of isotropic hyperfine-coupling constants in radicals using a spin-adapted open-shell coupled-cluster theory, namely, the unitary group based combinatoric open-shell coupled-cluster (COSCC) approach within the singles and doubles approximation. A scheme for the evaluation of the one-particle spin-density matrix required in these calculations is outlined within the spin-free formulation of the COSCC approach. In this scheme, the one-particle spin-density matrix for an open-shell state with spin S and M{sub S} = + S is expressed in terms of the one- and two-particle spin-free (charge) density matrices obtained from the Lagrangian formulation that is used for calculating the analytic first derivatives of the energy. Benchmark calculations are presented for NO, NCO, CH{sub 2}CN, and two conjugated π-radicals, viz., allyl and 1-pyrrolyl in order to demonstrate the performance of the proposed scheme.

  4. Ab initio Bogoliubov coupled cluster theory for open-shell nuclei

    SciTech Connect

    Signoracci, Angelo J.; Duguet, Thomas; Hagen, Gaute; Jansen, G. R.

    2015-06-29

    Background: Ab initio many-body methods have been developed over the past 10 yr to address closed-shell nuclei up to mass A≈130 on the basis of realistic two- and three-nucleon interactions. A current frontier relates to the extension of those many-body methods to the description of open-shell nuclei. Several routes to address open-shell nuclei are currently under investigation, including ideas that exploit spontaneous symmetry breaking. Purpose: Singly open-shell nuclei can be efficiently described via the sole breaking of U(1) gauge symmetry associated with particle-number conservation as a way to account for their superfluid character. While this route was recently followed within the framework of self-consistent Green's function theory, the goal of the present work is to formulate a similar extension within the framework of coupled cluster theory. Methods: We formulate and apply Bogoliubov coupled cluster (BCC) theory, which consists of representing the exact ground-state wave function of the system as the exponential of a quasiparticle excitation cluster operator acting on a Bogoliubov reference state. Equations for the ground-state energy and the cluster amplitudes are derived at the singles and doubles level (BCCSD) both algebraically and diagrammatically. The formalism includes three-nucleon forces at the normal-ordered two-body level. The first BCC code is implemented in m scheme, which will permit the treatment of doubly open-shell nuclei via the further breaking of SU(2) symmetry associated with angular momentum conservation. Results: Proof-of-principle calculations in an Nmax=6 spherical harmonic oscillator basis for 16,18O and 18Ne in the BCCD approximation are in good agreement with standard coupled cluster results with the same chiral two-nucleon interaction, while 20O and 20Mg display underbinding relative to experiment. The breaking of U(1) symmetry, monitored by computing the variance

  5. Ab initio Bogoliubov coupled cluster theory for open-shell nuclei

    NASA Astrophysics Data System (ADS)

    Signoracci, A.; Duguet, T.; Hagen, G.; Jansen, G. R.

    2015-06-01

    Background: Ab initio many-body methods have been developed over the past 10 yr to address closed-shell nuclei up to mass A ≈130 on the basis of realistic two- and three-nucleon interactions. A current frontier relates to the extension of those many-body methods to the description of open-shell nuclei. Several routes to address open-shell nuclei are currently under investigation, including ideas that exploit spontaneous symmetry breaking. Purpose: Singly open-shell nuclei can be efficiently described via the sole breaking of U(1) gauge symmetry associated with particle-number conservation as a way to account for their superfluid character. While this route was recently followed within the framework of self-consistent Green's function theory, the goal of the present work is to formulate a similar extension within the framework of coupled cluster theory. Methods: We formulate and apply Bogoliubov coupled cluster (BCC) theory, which consists of representing the exact ground-state wave function of the system as the exponential of a quasiparticle excitation cluster operator acting on a Bogoliubov reference state. Equations for the ground-state energy and the cluster amplitudes are derived at the singles and doubles level (BCCSD) both algebraically and diagrammatically. The formalism includes three-nucleon forces at the normal-ordered two-body level. The first BCC code is implemented in m scheme, which will permit the treatment of doubly open-shell nuclei via the further breaking of SU(2) symmetry associated with angular momentum conservation. Results: Proof-of-principle calculations in an Nmax=6 spherical harmonic oscillator basis for O,1816 and 18Ne in the BCCD approximation are in good agreement with standard coupled cluster results with the same chiral two-nucleon interaction, while 20O and 20Mg display underbinding relative to experiment. The breaking of U(1) symmetry, monitored by computing the variance associated with the particle-number operator, is relatively

  6. Ab initio Bogoliubov coupled cluster theory for open-shell nuclei

    DOE PAGES

    Signoracci, Angelo J.; Duguet, Thomas; Hagen, Gaute; ...

    2015-06-29

    Background: Ab initio many-body methods have been developed over the past 10 yr to address closed-shell nuclei up to mass A≈130 on the basis of realistic two- and three-nucleon interactions. A current frontier relates to the extension of those many-body methods to the description of open-shell nuclei. Several routes to address open-shell nuclei are currently under investigation, including ideas that exploit spontaneous symmetry breaking. Purpose: Singly open-shell nuclei can be efficiently described via the sole breaking of U(1) gauge symmetry associated with particle-number conservation as a way to account for their superfluid character. While this route was recently followed withinmore » the framework of self-consistent Green's function theory, the goal of the present work is to formulate a similar extension within the framework of coupled cluster theory. Methods: We formulate and apply Bogoliubov coupled cluster (BCC) theory, which consists of representing the exact ground-state wave function of the system as the exponential of a quasiparticle excitation cluster operator acting on a Bogoliubov reference state. Equations for the ground-state energy and the cluster amplitudes are derived at the singles and doubles level (BCCSD) both algebraically and diagrammatically. The formalism includes three-nucleon forces at the normal-ordered two-body level. The first BCC code is implemented in m scheme, which will permit the treatment of doubly open-shell nuclei via the further breaking of SU(2) symmetry associated with angular momentum conservation. Results: Proof-of-principle calculations in an Nmax=6 spherical harmonic oscillator basis for 16,18O and 18Ne in the BCCD approximation are in good agreement with standard coupled cluster results with the same chiral two-nucleon interaction, while 20O and 20Mg display underbinding relative to experiment. The breaking of U(1) symmetry, monitored by computing the variance associated with the particle-number operator, is

  7. Electrochemical Single-Molecule Transistors with Optimized Gate Coupling.

    PubMed

    Osorio, Henrry M; Catarelli, Samantha; Cea, Pilar; Gluyas, Josef B G; Hartl, František; Higgins, Simon J; Leary, Edmund; Low, Paul J; Martín, Santiago; Nichols, Richard J; Tory, Joanne; Ulstrup, Jens; Vezzoli, Andrea; Milan, David C; Zeng, Qiang

    2015-11-18

    Electrochemical gating at the single molecule level of viologen molecular bridges in ionic liquids is examined. Contrary to previous data recorded in aqueous electrolytes, a clear and sharp peak in the single molecule conductance versus electrochemical potential data is obtained in ionic liquids. These data are rationalized in terms of a two-step electrochemical model for charge transport across the redox bridge. In this model the gate coupling in the ionic liquid is found to be fully effective with a modeled gate coupling parameter, ξ, of unity. This compares to a much lower gate coupling parameter of 0.2 for the equivalent aqueous gating system. This study shows that ionic liquids are far more effective media for gating the conductance of single molecules than either solid-state three-terminal platforms created using nanolithography, or aqueous media.

  8. Equation-of-motion coupled-cluster method for doubly ionized states with spin-orbit coupling

    SciTech Connect

    Wang, Zhifan; Hu, Shu; Guo, Jingwei; Wang, Fan

    2015-04-14

    In this work, we report implementation of the equation-of-motion coupled-cluster method for doubly ionized states (EOM-DIP-CC) with spin-orbit coupling (SOC) using a closed-shell reference. Double ionization potentials (DIPs) are calculated in the space spanned by 2h and 3h1p determinants with the EOM-DIP-CC approach at the CC singles and doubles level (CCSD). Time-reversal symmetry together with spatial symmetry is exploited to reduce computational effort. To circumvent the problem of unstable dianion references when diffuse basis functions are included, nuclear charges are scaled. Effect of this stabilization potential on DIPs is estimated based on results from calculations using a small basis set without diffuse basis functions. DIPs and excitation energies of some low-lying states for a series of open-shell atoms and molecules containing heavy elements with two unpaired electrons have been calculated with the EOM-DIP-CCSD approach. Results show that this approach is able to afford a reliable description on SOC splitting. Furthermore, the EOM-DIP-CCSD approach is shown to provide reasonable excitation energies for systems with a dianion reference when diffuse basis functions are not employed.

  9. Analytical Energy Gradients for Excited-State Coupled-Cluster Methods

    NASA Astrophysics Data System (ADS)

    Wladyslawski, Mark; Nooijen, Marcel

    The equation-of-motion coupled-cluster (EOM-CC) and similarity transformed equation-of-motion coupled-cluster (STEOM-CC) methods have been firmly established as accurate and routinely applicable extensions of single-reference coupled-cluster theory to describe electronically excited states. An overview of these methods is provided, with emphasis on the many-body similarity transform concept that is the key to a rationalization of their accuracy. The main topic of the paper is the derivation of analytical energy gradients for such non-variational electronic structure approaches, with an ultimate focus on obtaining their detailed algebraic working equations. A general theoretical framework using Lagrange's method of undetermined multipliers is presented, and the method is applied to formulate the EOM-CC and STEOM-CC gradients in abstract operator terms, following the previous work in [P.G. Szalay, Int. J. Quantum Chem. 55 (1995) 151] and [S.R. Gwaltney, R.J. Bartlett, M. Nooijen, J. Chem. Phys. 111 (1999) 58]. Moreover, the systematics of the Lagrange multiplier approach is suitable for automation by computer, enabling the derivation of the detailed derivative equations through a standardized and direct procedure. To this end, we have developed the SMART (Symbolic Manipulation and Regrouping of Tensors) package of automated symbolic algebra routines, written in the Mathematica programming language. The SMART toolkit provides the means to expand, differentiate, and simplify equations by manipulation of the detailed algebraic tensor expressions directly. The Lagrangian multiplier formulation establishes a uniform strategy to perform the automated derivation in a standardized manner: A Lagrange multiplier functional is constructed from the explicit algebraic equations that define the energy in the electronic method; the energy functional is then made fully variational with respect to all of its parameters, and the symbolic differentiations directly yield the explicit

  10. Communication: Multireference equation of motion coupled cluster: A transform and diagonalize approach to electronic structure

    SciTech Connect

    Nooijen, Marcel; Huntington, Lee M.; Demel, Ondřej; Datta, Dipayan; Kong, Liguo; Shamasundar, K. R.; Lotrich, V.; Neese, Frank

    2014-02-28

    The novel multireference equation-of-motion coupled-cluster (MREOM-CC) approaches provide versatile and accurate access to a large number of electronic states. The methods proceed by a sequence of many-body similarity transformations and a subsequent diagonalization of the transformed Hamiltonian over a compact subspace. The transformed Hamiltonian is a connected entity and preserves spin- and spatial symmetry properties of the original Hamiltonian, but is no longer Hermitean. The final diagonalization spaces are defined in terms of a complete active space (CAS) and limited excitations (1h, 1p, 2h, …) out of the CAS. The methods are invariant to rotations of orbitals within their respective subspaces (inactive, active, external). Applications to first row transition metal atoms (Cr, Mn, and Fe) are presented yielding results for up to 524 electronic states (for Cr) with an rms error compared to experiment of about 0.05 eV. The accuracy of the MREOM family of methods is closely related to its favorable extensivity properties as illustrated by calculations on the O{sub 2}–O{sub 2} dimer. The computational costs of the transformation steps in MREOM are comparable to those of closed-shell Coupled Cluster Singles and Doubles (CCSD) approach.

  11. Single atoms coupled to a near-concentric cavity

    NASA Astrophysics Data System (ADS)

    Nguyen, Chi Huan; Utama, Adrian Nugraha; Lewty, Nick; Durak, Kadir; Maslennikov, Gleb; Straupe, Stanislav; Steiner, Matthias; Kurtsiefer, Christian

    2017-09-01

    Concentric cavities can lead to strong photon-atom coupling without a need for high finesse or small physical-cavity volume. In this proof-of-principle experiment we demonstrate coupling of single Rb atoms to an 11-mm-long near-concentric cavity with a finesse F =138 (2 ) . Operating the cavity 1.7 (1 )μ m shorter than the critical length, we observe an atom-cavity coupling constant g0=2 π ×5.0 (2 ) MHz which exceeds the natural dipole decay rate γ by a factor of g0/γ =1.7 (1 ) .

  12. Alternative definition of excitation amplitudes in multi-reference state-specific coupled cluster

    NASA Astrophysics Data System (ADS)

    Garniron, Yann; Giner, Emmanuel; Malrieu, Jean-Paul; Scemama, Anthony

    2017-04-01

    A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) in the multi-exponential Jeziorski-Monkhorst formalism concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operators. If the reference space is a complete active space (CAS), the number of these amplitudes is larger than the number of singly and doubly excited determinants on which one may project the eigenequation, and one must impose additional conditions. The present work first defines a state-specific reference-independent operator T˜ ^ m which acting on the CAS component of the wave function |Ψ0m⟩ maximizes the overlap between (1 +T˜ ^ m ) |Ψ0m⟩ and the eigenvector of the CAS-SD (Singles and Doubles) Configuration Interaction (CI) matrix |ΨCAS-SDm⟩ . This operator may be used to generate approximate coefficients of the triples and quadruples, and a dressing of the CAS-SD CI matrix, according to the intermediate Hamiltonian formalism. The process may be iterated to convergence. As a refinement towards a strict coupled cluster formalism, one may exploit reference-independent amplitudes provided by (1 +T˜ ^ m ) |Ψ0m⟩ to define a reference-dependent operator T^ m by fitting the eigenvector of the (dressed) CAS-SD CI matrix. The two variants, which are internally uncontracted, give rather similar results. The new MR-CC version has been tested on the ground state potential energy curves of 6 molecules (up to triple-bond breaking) and two excited states. The non-parallelism error with respect to the full-CI curves is of the order of 1 mEh.

  13. Alternative definition of excitation amplitudes in multi-reference state-specific coupled cluster.

    PubMed

    Garniron, Yann; Giner, Emmanuel; Malrieu, Jean-Paul; Scemama, Anthony

    2017-04-21

    A central difficulty of state-specific Multi-Reference Coupled Cluster (MR-CC) in the multi-exponential Jeziorski-Monkhorst formalism concerns the definition of the amplitudes of the single and double excitation operators appearing in the exponential wave operators. If the reference space is a complete active space (CAS), the number of these amplitudes is larger than the number of singly and doubly excited determinants on which one may project the eigenequation, and one must impose additional conditions. The present work first defines a state-specific reference-independent operator T∼^(m) which acting on the CAS component of the wave function |Ψ0(m)⟩ maximizes the overlap between (1+T∼^(m))|Ψ0(m)⟩ and the eigenvector of the CAS-SD (Singles and Doubles) Configuration Interaction (CI) matrix |ΨCAS-SD(m)⟩. This operator may be used to generate approximate coefficients of the triples and quadruples, and a dressing of the CAS-SD CI matrix, according to the intermediate Hamiltonian formalism. The process may be iterated to convergence. As a refinement towards a strict coupled cluster formalism, one may exploit reference-independent amplitudes provided by (1+T∼^(m))|Ψ0(m)⟩ to define a reference-dependent operator T^(m) by fitting the eigenvector of the (dressed) CAS-SD CI matrix. The two variants, which are internally uncontracted, give rather similar results. The new MR-CC version has been tested on the ground state potential energy curves of 6 molecules (up to triple-bond breaking) and two excited states. The non-parallelism error with respect to the full-CI curves is of the order of 1 mEh.

  14. Development of New Open-Shell Perturbation and Coupled-Cluster Theories Based on Symmetric Spin Orbitals

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Arnold, James O. (Technical Monitor)

    1994-01-01

    A new spin orbital basis is employed in the development of efficient open-shell coupled-cluster and perturbation theories that are based on a restricted Hartree-Fock (RHF) reference function. The spin orbital basis differs from the standard one in the spin functions that are associated with the singly occupied spatial orbital. The occupied orbital (in the spin orbital basis) is assigned the delta(+) = 1/square root of 2(alpha+Beta) spin function while the unoccupied orbital is assigned the delta(-) = 1/square root of 2(alpha-Beta) spin function. The doubly occupied and unoccupied orbitals (in the reference function) are assigned the standard alpha and Beta spin functions. The coupled-cluster and perturbation theory wave functions based on this set of "symmetric spin orbitals" exhibit much more symmetry than those based on the standard spin orbital basis. This, together with interacting space arguments, leads to a dramatic reduction in the computational cost for both coupled-cluster and perturbation theory. Additionally, perturbation theory based on "symmetric spin orbitals" obeys Brillouin's theorem provided that spin and spatial excitations are both considered. Other properties of the coupled-cluster and perturbation theory wave functions and models will be discussed.

  15. Development of New Open-Shell Perturbation and Coupled-Cluster Theories Based on Symmetric Spin Orbitals

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Arnold, James O. (Technical Monitor)

    1994-01-01

    A new spin orbital basis is employed in the development of efficient open-shell coupled-cluster and perturbation theories that are based on a restricted Hartree-Fock (RHF) reference function. The spin orbital basis differs from the standard one in the spin functions that are associated with the singly occupied spatial orbital. The occupied orbital (in the spin orbital basis) is assigned the delta(+) = 1/square root of 2(alpha+Beta) spin function while the unoccupied orbital is assigned the delta(-) = 1/square root of 2(alpha-Beta) spin function. The doubly occupied and unoccupied orbitals (in the reference function) are assigned the standard alpha and Beta spin functions. The coupled-cluster and perturbation theory wave functions based on this set of "symmetric spin orbitals" exhibit much more symmetry than those based on the standard spin orbital basis. This, together with interacting space arguments, leads to a dramatic reduction in the computational cost for both coupled-cluster and perturbation theory. Additionally, perturbation theory based on "symmetric spin orbitals" obeys Brillouin's theorem provided that spin and spatial excitations are both considered. Other properties of the coupled-cluster and perturbation theory wave functions and models will be discussed.

  16. Single molecule detection using charge-coupled device array technology

    SciTech Connect

    Denton, M.B.

    1992-07-29

    A technique for the detection of single fluorescent chromophores in a flowing stream is under development. This capability is an integral facet of a rapid DNA sequencing scheme currently being developed by Los Alamos National Laboratory. In previous investigations, the detection sensitivity was limited by the background Raman emission from the water solvent. A detection scheme based on a novel mode of operating a Charge-Coupled Device (CCD) is being developed which should greatly enhance the discrimination between fluorescence from a single molecule and the background Raman scattering from the solvent. Register shifts between rows in the CCD are synchronized with the sample flow velocity so that fluorescence from a single molecule is collected in a single moving charge packet occupying an area approaching that of a single pixel while the background is spread evenly among a large number of pixels. Feasibility calculations indicate that single molecule detection should be achieved with an excellent signal-to-noise ratio.

  17. Coulomb Blockade Oscillations in Coupled Single-Electron Transistors

    NASA Astrophysics Data System (ADS)

    Shin, Mincheol; Lee, Seongjae; Park, Kyoung Wan

    2000-03-01

    The system we consider in this work is parallel coupled single-electron transistors (SETs) at strong coupling. For weak coupling, the transport characteristics of our coupled SETs are the same as those of the single SET, with the stability diagram exhibiting usual Coulomb diamonds. When the coupling becomes sufficiently strong, however, electron-hole binding and transport become important. In contrast to the previous works carried out in the cotunneling-dominating Coulomb blockade regime [1,2], we study e-h binding in the sequential-tunneling-dominating conducting regime. The major findings in this work are that the Coulomb diamonds in the conducting regime break up into fine internal structures at strong coupling, and that, although the cotunneling processes are much less frequent, they nonetheless play a crucial role. [1] D. V. Averin, A. N. Korotkov, and Yu. V. Nazarov, Phys. Rev. Lett. 66, 2818 (1991). [2] M. Matters, J. J. Versluys, and J. E. Mooij, Phys. Rev. Lett. 78, 2469 (1997).

  18. Waveguide-Coupled Superconducting Nanowire Single-Photon Detectors

    NASA Technical Reports Server (NTRS)

    Beyer, Andrew D.; Briggs, Ryan M.; Marsili, Francesco; Cohen, Justin D.; Meenehan, Sean M.; Painter, Oskar J.; Shaw, Matthew D.

    2015-01-01

    We have demonstrated WSi-based superconducting nanowire single-photon detectors coupled to SiNx waveguides with integrated ring resonators. This photonics platform enables the implementation of robust and efficient photon-counting detectors with fine spectral resolution near 1550 nm.

  19. Waveguide-Coupled Superconducting Nanowire Single-Photon Detectors

    NASA Technical Reports Server (NTRS)

    Beyer, Andrew D.; Briggs, Ryan M.; Marsili, Francesco; Cohen, Justin D.; Meenehan, Sean M.; Painter, Oskar J.; Shaw, Matthew D.

    2015-01-01

    We have demonstrated WSi-based superconducting nanowire single-photon detectors coupled to SiNx waveguides with integrated ring resonators. This photonics platform enables the implementation of robust and efficient photon-counting detectors with fine spectral resolution near 1550 nm.

  20. Single ion coupled to an optical fiber cavity.

    PubMed

    Steiner, Matthias; Meyer, Hendrik M; Deutsch, Christian; Reichel, Jakob; Köhl, Michael

    2013-01-25

    We present the realization of a combined trapped-ion and optical cavity system, in which a single Yb(+) ion is confined by a micron-scale ion trap inside a 230 μm-long optical fiber cavity. We characterize the spatial ion-cavity coupling and measure the ion-cavity coupling strength using a cavity-stimulated Λ transition. Owing to the small mode volume of the fiber resonator, the coherent coupling strength between the ion and a single photon exceeds the natural decay rate of the dipole moment. This system can be integrated into ion-photon quantum networks and is a step towards cavity quantum electrodynamics based quantum information processing with trapped ions.

  1. Equation of motion coupled cluster methods for electron attachment and ionization potential in polyacenes

    SciTech Connect

    Bhaskaran-Nair, Kiran; Kowalski, Karol; Jarrell, Mark; Moreno, Juana; Shelton, William A.

    2015-11-05

    Polyacenes have attracted considerable attention due to their use in organic based optoelectronic materials. Polyacenes are polycyclic aromatic hydrocarbons composed of fused benzene rings. Key to understanding and design of new functional materials is an understanding of their excited state properties starting with their electron affinity (EA) and ionization potential (IP). We have developed a highly accurate and com- putationally e*fficient EA/IP equation of motion coupled cluster singles and doubles (EA/IP-EOMCCSD) method that is capable of treating large systems and large basis set. In this study we employ the EA/IP-EOMCCSD method to calculate the electron affinity and ionization potential of naphthalene, anthracene, tetracene, pentacene, hex- acene and heptacene. We have compared our results with other previous theoretical studies and experimental data. Our EA/IP results are in very good agreement with experiment and when compared with the other theoretical investigations our results represent the most accurate calculations as compared to experiment.

  2. Low rank factorization of the Coulomb integrals for periodic coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Hummel, Felix; Tsatsoulis, Theodoros; Grüneis, Andreas

    2017-03-01

    We study a tensor hypercontraction decomposition of the Coulomb integrals of periodic systems where the integrals are factorized into a contraction of six matrices of which only two are distinct. We find that the Coulomb integrals can be well approximated in this form already with small matrices compared to the number of real space grid points. The cost of computing the matrices scales as O (N4) using a regularized form of the alternating least squares algorithm. The studied factorization of the Coulomb integrals can be exploited to reduce the scaling of the computational cost of expensive tensor contractions appearing in the amplitude equations of coupled cluster methods with respect to system size. We apply the developed methodologies to calculate the adsorption energy of a single water molecule on a hexagonal boron nitride monolayer in a plane wave basis set and periodic boundary conditions.

  3. Communication: Analytic gradients for the complex absorbing potential equation-of-motion coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Benda, Zsuzsanna; Jagau, Thomas-C.

    2017-01-01

    The general theory of analytic energy gradients is presented for the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) method together with an implementation within the singles and doubles approximation. Expressions for the CAP-EOM-CC energy gradient are derived based on a Lagrangian formalism with a special focus on the extra terms arising from the presence of the CAP. Our implementation allows for locating minima on high-dimensional complex-valued potential energy surfaces and thus enables geometry optimizations of resonance states of polyatomic molecules. The applicability of our CAP-EOM-CC gradients is illustrated by computations of the equilibrium structures and adiabatic electron affinities of the temporary anions of formaldehyde, formic acid, and ethylene. The results are compared to those obtained from standard EOM-CC calculations and the advantages of CAP methods are emphasized.

  4. Connected triple excitations in coupled-cluster calculations of hyperpolarizabilities: Neon

    NASA Technical Reports Server (NTRS)

    Rice, Julia E.; Scuseria, Gustavo E.; Lee, Timothy J.; Taylor, Peter R.; Almloef, Jan

    1992-01-01

    We have calculated the second hyperpolarizability gamma of neon using the CCSD(T) method. The accuracy of the CCSD(T) approach has been established by explicit comparison with the single, double and triple excitation coupled-cluster (CCSDT) method using extended basis sets that are known to be adequate for the description of gamma. Our best estimate for gamma(sub 0) of 110 +/- 3 a.u. is in good agreement with other recent theoretical values and with Shelton's recent experimental estimate of 108 +/- 2 a.u. Comparison of the MP2 and CCSD(T) hyperpolarizability values indicates that MP2 gives a very good description of the electron correlation contribution to gamma(sub 0). We have combined MP2 frequency-dependent corrections with the CCSD(T) gamma(sub 0) to yield values of gamma(-2 omega;omega,omega,0) and gamma(exp K)(-omega;omega,0,0).

  5. Relativistic extended-coupled-cluster method for the magnetic hyperfine structure constant

    NASA Astrophysics Data System (ADS)

    Sasmal, Sudip; Pathak, Himadri; Nayak, Malaya K.; Vaval, Nayana; Pal, Sourav

    2015-02-01

    The article deals with the general implementation of the four-component spinor relativistic extended-coupled-cluster (ECC) method to calculate first-order property of atoms and molecules in their open-shell ground-state configuration. The implemented relativistic ECC is employed to calculate hyperfine structure constants of alkali metals (Li, Na, K, Rb, and Cs), singly charged alkaline-earth-metal atoms (Be+ ,Mg+,Ca+, and Sr+), and molecules (BeH, MgF, and CaH). We have compared our ECC results with the calculations based on the restricted active space configuration interaction (RAS-CI) method. Our results are in better agreement with the available experimental values than those of the RAS-CI values.

  6. Coupled cluster calculations for static and dynamic polarizabilities of C60

    NASA Astrophysics Data System (ADS)

    Kowalski, Karol; Hammond, Jeff R.; de Jong, Wibe A.; Sadlej, Andrzej J.

    2008-12-01

    New theoretical predictions for the static and frequency dependent polarizabilities of C60 are reported. Using the linear response coupled cluster approach with singles and doubles and a basis set especially designed to treat the molecular properties in external electric field, we obtained 82.20 and 83.62 Å3 for static and dynamic (λ =1064 nm) polarizabilities. These numbers are in a good agreement with experimentally inferred data of 76.5±8 and 79±4 Å3 [R. Antoine et al., J. Chem. Phys.110, 9771 (1999); A. Ballard et al., J. Chem. Phys.113, 5732 (2000)]. The reported results were obtained with the highest wave function-based level of theory ever applied to the C60 system.

  7. State-selective multireference coupled-cluster theory: In pursuit of property calculation

    SciTech Connect

    Ghose, K.B.; Piecuch, P.; Pal, S.; Adamowicz, L. |

    1996-05-01

    In this work, we examine the efficiency of the recently developed [P. Piecuch {ital et} {ital al}., J. Chem. Phys. {bold 99}, 6732 (1993)] state-selective (SS) multi-reference (MR) coupled-cluster (CC) method for calculation of molecular properties. In our earlier papers, we demonstrated that the SSMRCC method with inclusion of single, double, and internal and semi-internal triple excitations [SSCCSD(T) approach] is capable of providing an accurate description of the ground-state potential energy surfaces. In this paper, we present the dipole moment and polarizability values of the HF molecule at equilibrium and stretched geometries calculated using finite field technique and SSCCSD(T) ansatz. The calculations use double zeta quality basis sets with and without polarization functions. Molecular orbital basis sets include both relaxed and nonrelaxed orbitals. {copyright} {ital 1996 American Institute of Physics.}

  8. Different equation-of-motion coupled cluster methods with different reference functions: The formyl radical

    NASA Astrophysics Data System (ADS)

    Kuś, Tomasz; Bartlett, Rodney J.

    2008-09-01

    The doublet and quartet excited states of the formyl radical have been studied by the equation-of-motion (EOM) coupled cluster (CC) method. The Sz spin-conserving singles and doubles (EOM-EE-CCSD) and singles, doubles, and triples (EOM-EE-CCSDT) approaches, as well as the spin-flipped singles and doubles (EOM-SF-CCSD) method have been applied, subject to unrestricted Hartree-Fock (HF), restricted open-shell HF, and quasirestricted HF references. The structural parameters, vertical and adiabatic excitation energies, and harmonic vibrational frequencies have been calculated. The issue of the reference function choice for the spin-flipped (SF) method and its impact on the results has been discussed using the experimental data and theoretical results available. The results show that if the appropriate reference function is chosen so that target states differ from the reference by only single excitations, then EOM-EE-CCSD and EOM-SF-CCSD methods give a very good description of the excited states. For the states that have a non-negligible contribution of the doubly excited configurations one is able to use the SF method with such a reference function, that in most cases the performance of the EOM-SF-CCSD method is better than that of the EOM-EE-CCSD approach.

  9. Different equation-of-motion coupled cluster methods with different reference functions: the formyl radical.

    PubMed

    Kuś, Tomasz; Bartlett, Rodney J

    2008-09-14

    The doublet and quartet excited states of the formyl radical have been studied by the equation-of-motion (EOM) coupled cluster (CC) method. The S(z) spin-conserving singles and doubles (EOM-EE-CCSD) and singles, doubles, and triples (EOM-EE-CCSDT) approaches, as well as the spin-flipped singles and doubles (EOM-SF-CCSD) method have been applied, subject to unrestricted Hartree-Fock (HF), restricted open-shell HF, and quasirestricted HF references. The structural parameters, vertical and adiabatic excitation energies, and harmonic vibrational frequencies have been calculated. The issue of the reference function choice for the spin-flipped (SF) method and its impact on the results has been discussed using the experimental data and theoretical results available. The results show that if the appropriate reference function is chosen so that target states differ from the reference by only single excitations, then EOM-EE-CCSD and EOM-SF-CCSD methods give a very good description of the excited states. For the states that have a non-negligible contribution of the doubly excited configurations one is able to use the SF method with such a reference function, that in most cases the performance of the EOM-SF-CCSD method is better than that of the EOM-EE-CCSD approach.

  10. Structurally coupled inversion of ERT and refraction seismic data combined with cluster-based model integration

    NASA Astrophysics Data System (ADS)

    Hellman, Kristofer; Ronczka, Mathias; Günther, Thomas; Wennermark, Marcus; Rücker, Carsten; Dahlin, Torleif

    2017-08-01

    Electrical resistivity tomography (ERT) and refraction seismics are among the most frequently used geophysical methods for site-investigations and the combined results can be very helpful to fill in the gaps between the point measurements made by traditional geotechnical methods such as Cone Penetration Test (CPT), core-drilling and geophysical borehole logging. The interpretation of the results from a geophysical investigation constituting a single method often yields ambiguous results. Hence, an approach utilizing multiple techniques is often necessary. To facilitate interpretation of such a combined dataset, we propose a more controlled and objective approach and present a method for a structurally coupled inversion of 2D electrical resistivity and refraction seismic data using unstructured meshes. Mean shift clustering is used to combine the two images and to compare the separate and coupled inversion methodologies. Two synthetic examples are used to demonstrate the method, and a field-data example is included as a proof of concept. In all cases a significant improvement by the coupling is visible. The methodology can be used as a tool for improved data interpretation and for obtaining a more comprehensive and complete picture of the subsurface by combining geophysical methods.

  11. A partial coupling power of single mode fiber fusion

    NASA Astrophysics Data System (ADS)

    Saktioto, Toto; Ali, Jalil; Rahman, Rosly Abdul; Fadhali, Mohammed; Zainal, Jasman

    2008-01-01

    Coupled fibers are successfully fabricated by injecting hydrogen flow at 1bar and fused slightly by unstable torch flame in the range of 800-1350°C. Optical parameters may vary significantly over wide range physical properties. Coupling coefficient and refractive index are estimated from the experimental result of the coupling ratio distribution from 1% to 75%. The change of structural and geometrical fiber affects the normalized frequency (V) even for single mode fibers. Coupling ratio as a function of coupling coefficient and separation of fiber axis changes with respect to V at coupling region. V is derived from radius, wavelength and refractive index parameters. Parametric variations are performed on the left and right hand side of the coupling region. At the center of the coupling region V is assumed constant. A partial power is modeled and derived using V, normalized lateral phase constant (u), and normalized lateral attenuation constant, (w) through the second kind of modified Bessel function of the l order, which obeys the normal mode, LP 01 and normalized propagation constant (b). Total power is maintained constant in order to comply with the energy conservation law. The power is integrated through V, u and w over the pulling length range of 7500-9500 μm for 1-D where radial and angle directions are ignored. The core radius of fiber significantly affects V and power partially at coupling region rather than wavelength and refractive index of core and cladding. This model has power phenomena in transmission and reflection for industrial application of coupled fibers.

  12. Relativistic coupled-cluster and density-functional studies of argon at high pressure

    NASA Astrophysics Data System (ADS)

    Schwerdtfeger, Peter; Steenbergen, Krista G.; Pahl, Elke

    2017-06-01

    The equation of state P (V ,T ) for solid argon is determined by the calculation of accurate static and vibrational terms in the free energy. The static component comes from a quantum theoretical many-body expansion summing over all energetic contributions from two-, three-, and four-body fragments treated with relativistic coupled cluster theory, while the lattice vibrations are described at an anharmonic level including two- and three-body forces as well as temperature effects. The dynamic part is calculated within the Debye and Einstein approximation, as well as by a more accurate phonon treatment where the vibrational motions in the lattice are coupled. Our results are in good agreement with room-temperature high-pressure experimental data up to ˜20 GPa. In the 20-100 GPa pressure range, however, we see considerable deviations between experiment and theory, perhaps indicating missing four-body contributions (beyond the quadruple dipole terms included here), missing five and higher-body effects, and the need to go beyond the coupled cluster singles-doubles with perturbative triples treatment in such higher-body forces. This contrasts with the results for solid neon, where excellent agreement has been achieved taking only two- and three-body forces into account [P. Schwerdtfeger and A. Hermann, Phys. Rev. B 80, 064106 (2009), 10.1103/PhysRevB.80.064106]. We demonstrate that the phase transition from fcc to hcp cannot account for the large discrepancies observed. Density functional calculations give very mixed results in the high-pressure region, but some functionals such as optB88-vdW (proposed by Lundqvist and co-workers) describe the many-body forces in argon reasonably well over the range of pressures investigated. Theoretical investigations of the heavier rare gas solids reaching experimental accuracy in the high-pressure regime therefore remain a significant challenge.

  13. Cluster Consensus of Nonlinearly Coupled Multi-Agent Systems in Directed Graphs

    NASA Astrophysics Data System (ADS)

    Lu, Xiao-Qing; Francis, Austin; Chen, Shi-Hua

    2010-05-01

    We investigate the cluster consensus problem in directed networks of nonlinearly coupled multi-agent systems by using pinning control. Depending on the community structure generated by the group partition of the underlying digraph, various clusters can be made coherently independent by applying feedback injections to a fraction of the agents. Sufficient conditions for cluster consensus are obtained using algebraic graph theory and matrix theory and some simulations results are included to illustrate the method.

  14. Similarity transformed coupled cluster response (ST-CCR) theory--a time-dependent similarity transformed equation-of-motion coupled cluster (STEOM-CC) approach.

    PubMed

    Landau, Arie

    2013-07-07

    This paper presents a new method for calculating spectroscopic properties in the framework of response theory utilizing a sequence of similarity transformations (STs). The STs are preformed using the coupled cluster (CC) and Fock-space coupled cluster operators. The linear and quadratic response functions of the new similarity transformed CC response (ST-CCR) method are derived. The poles of the linear response yield excitation-energy (EE) expressions identical to the ones in the similarity transformed equation-of-motion coupled cluster (STEOM-CC) approach. ST-CCR and STEOM-CC complement each other, in analogy to the complementarity of CC response (CCR) and equation-of-motion coupled cluster (EOM-CC). ST-CCR/STEOM-CC and CCR/EOM-CC yield size-extensive and size-intensive EEs, respectively. Other electronic-properties, e.g., transition dipole strengths, are also size-extensive within ST-CCR, in contrast to STEOM-CC. Moreover, analysis suggests that in comparison with CCR, the ST-CCR expressions may be confined to a smaller subspace, however, the precise scope of the truncation can only be determined numerically. In addition, reformulation of the time-independent STEOM-CC using the same parameterization as in ST-CCR, as well as an efficient truncation scheme, is presented. The shown convergence of the time-dependent and time-independent expressions displays the completeness of the presented formalism.

  15. Clustering and phase synchronization in populations of coupled phase oscillators

    NASA Astrophysics Data System (ADS)

    Cascallares, Guadalupe; Gleiser, Pablo M.

    2015-10-01

    In many species daily rhythms are endogenously generated by groups of coupled neurons that play the role of a circadian pacemaker. The adaptation of the circadian clock to environmental and seasonal changes has been proposed to be regulated by a dual oscillator system. In order to gain insight into this model, we analyzed the synchronization properties of two fully coupled groups of Kuramoto oscillators. Each group has an internal coupling parameter and the interaction between the two groups can be controlled by two parameters allowing for symmetric or non-symmetric coupling. We show that even for such a simple model counterintuitive behaviours take place, such as a global decrease in synchrony when the coupling between the groups is increased. Through a detailed analysis of the local synchronization processes we explain this behaviour.

  16. Coupling a single electron to a Bose-Einstein condensate.

    PubMed

    Balewski, Jonathan B; Krupp, Alexander T; Gaj, Anita; Peter, David; Büchler, Hans Peter; Löw, Robert; Hofferberth, Sebastian; Pfau, Tilman

    2013-10-31

    The coupling of electrons to matter lies at the heart of our understanding of material properties such as electrical conductivity. Electron-phonon coupling can lead to the formation of a Cooper pair out of two repelling electrons, which forms the basis for Bardeen-Cooper-Schrieffer superconductivity. Here we study the interaction of a single localized electron with a Bose-Einstein condensate and show that the electron can excite phonons and eventually trigger a collective oscillation of the whole condensate. We find that the coupling is surprisingly strong compared to that of ionic impurities, owing to the more favourable mass ratio. The electron is held in place by a single charged ionic core, forming a Rydberg bound state. This Rydberg electron is described by a wavefunction extending to a size of up to eight micrometres, comparable to the dimensions of the condensate. In such a state, corresponding to a principal quantum number of n = 202, the Rydberg electron is interacting with several tens of thousands of condensed atoms contained within its orbit. We observe surprisingly long lifetimes and finite size effects caused by the electron exploring the outer regions of the condensate. We anticipate future experiments on electron orbital imaging, the investigation of phonon-mediated coupling of single electrons, and applications in quantum optics.

  17. Coupling a single electron spin to a microwave resonator: controlling transverse and longitudinal couplings

    NASA Astrophysics Data System (ADS)

    Beaudoin, Félix; Lachance-Quirion, Dany; Coish, W. A.; Pioro-Ladrière, Michel

    2016-11-01

    Microwave-frequency superconducting resonators are ideally suited to perform dispersive qubit readout, to mediate two-qubit gates, and to shuttle states between distant quantum systems. A prerequisite for these applications is a strong qubit-resonator coupling. Strong coupling between an electron-spin qubit and a microwave resonator can be achieved by correlating spin- and orbital degrees of freedom. This correlation can be achieved through the Zeeman coupling of a single electron in a double quantum dot to a spatially inhomogeneous magnetic field generated by a nearby nanomagnet. In this paper, we consider such a device and estimate spin-resonator couplings of order ˜1 MHz with realistic parameters. Further, through realistic simulations, we show that precise placement of the double-dot relative to the nanomagnet allows to select between a purely longitudinal coupling (commuting with the bare spin Hamiltonian) and a purely transverse (spin non-conserving) coupling. Additionally, we suggest methods to mitigate dephasing and relaxation channels that are introduced in this coupling scheme. This analysis gives a clear route toward the realization of coherent state transfer between a microwave resonator and a single electron spin in a GaAs double quantum dot with a fidelity above 90%. Improved dynamical decoupling sequences, low-noise environments, and longer-lived microwave cavity modes may lead to substantially higher fidelities in the near future.

  18. Monte Carlo simulations of single and coupled synthetic molecular motors.

    PubMed

    Chen, C-M; Zuckermann, M

    2012-11-01

    We use a minimal model to study the processive motion of coupled synthetic molecular motors along a DNA track and we present data from Monte Carlo (MC) computer simulations based on this model. The model was originally proposed by Bromley et al. [HFSP J. 3, 204 (2009)] for studying the properties of a synthetic protein motor, the "Tumbleweed" (TW), and involves rigid Y-shaped motors diffusively rotating along the track while controlled by a series of periodically injected ligand pulses into the solution. The advantage of the model is that it mimics the mechanical properties of the TW motor in detail. Both the average first passage time which measures the diffusive motion of the motors, and the average dwell time on the track which measures their processivity are investigated by varying the parameters of the model. The latter includes ligand concentration and the range and strength of the binding interaction between motors and the track. In particular, it is of experimental interest to study the dependence of these dynamic time scales of the motors on the ligand concentration. Single rigid TW motors were first studied since no previous MC simulations of these motors have been performed. We first studied single motors for which we found a logarithmic decrease of the average first passage time and a logarithmic increase of the average dwell time with increasing ligand concentration. For two coupled motors, the dependence on ligand concentration is still logarithmic for the average first passage time but becomes linear for the average dwell time. This suggests a much greater stability in the processive motion of coupled motors as compared to single motors in the limit of large ligand concentration. By increasing the number of coupled motors, m, it was found that the average first passage time of the coupled motors only increases slowly with m while the average dwell time increases exponentially with m. Thus the stability of coupled motors on the track can be

  19. Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations

    NASA Astrophysics Data System (ADS)

    Lutnæs, Ola B.; Teale, Andrew M.; Helgaker, Trygve; Tozer, David J.; Ruud, Kenneth; Gauss, Jürgen

    2009-10-01

    An accurate set of benchmark rotational g tensors and magnetizabilities are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster single-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the results obtained is established for the rotational g tensors by careful comparison with experimental data, taking into account zero-point vibrational corrections. After an analysis of the basis sets employed, extrapolation techniques are used to provide estimates of the basis-set-limit quantities, thereby establishing an accurate benchmark data set. The utility of the data set is demonstrated by examining a wide variety of density functionals for the calculation of these properties. None of the density-functional methods are competitive with the CCSD or CCSD(T) methods. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of density-functional calculations constrained to give the same electronic density. The importance of current dependence in exchange-correlation functionals is discussed in light of this comparison.

  20. Ruprecht 106: The first single population globular cluster?

    SciTech Connect

    Villanova, S.; Geisler, D.; Muñoz, C.; Carraro, G.; Moni Bidin, C.

    2013-12-01

    All old Galactic globular clusters (GCs) studied in detail to date host at least two generations of stars, where the second is formed from gas polluted by processed material produced by massive stars of the first. This process can happen if the initial mass of the cluster exceeds a threshold above which ejecta are retained and a second generation is formed. A determination of this mass threshold is mandatory in order to understand how GCs form. We analyzed nine red giant branch stars belonging to the cluster Ruprecht 106. Targets were observed with the UVES@VLT2 spectrograph. Spectra cover a wide range and allowed us to measure abundances for light (O, Na, Mg, Al), α (Si, Ca, Ti), iron-peak (Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), and neutron-capture (Y, Zr, Ba, La, Ce, Pr, Nd, Sm, Eu, Dy, Pb) elements. Based on these abundances, we show that Ruprecht 106 is the first convincing example of a single-population GC (i.e., a true simple stellar population), although the sample is relatively small. This result is supported also by an independent photometric test and by the horizontal branch morphology and the dynamical state. It is old (∼12 Gyr) and, at odds with other GCs, has no α-enhancement. The material it formed from was contaminated by both s- and r-process elements. The abundance pattern points toward an extragalactic origin. Its present-day mass (M = 10{sup 4.83} M {sub ☉}) can be assumed as a strong lower limit for the initial mass threshold below which no second generation is formed. Clearly, its initial mass must have been significantly greater, but we have no current constraints on the amount of mass loss during its evolution.

  1. Ruprecht 106: The First Single Population Globular Cluster?

    NASA Astrophysics Data System (ADS)

    Villanova, S.; Geisler, D.; Carraro, G.; Moni Bidin, C.; Muñoz, C.

    2013-12-01

    All old Galactic globular clusters (GCs) studied in detail to date host at least two generations of stars, where the second is formed from gas polluted by processed material produced by massive stars of the first. This process can happen if the initial mass of the cluster exceeds a threshold above which ejecta are retained and a second generation is formed. A determination of this mass threshold is mandatory in order to understand how GCs form. We analyzed nine red giant branch stars belonging to the cluster Ruprecht 106. Targets were observed with the UVES@VLT2 spectrograph. Spectra cover a wide range and allowed us to measure abundances for light (O, Na, Mg, Al), α (Si, Ca, Ti), iron-peak (Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn), and neutron-capture (Y, Zr, Ba, La, Ce, Pr, Nd, Sm, Eu, Dy, Pb) elements. Based on these abundances, we show that Ruprecht 106 is the first convincing example of a single-population GC (i.e., a true simple stellar population), although the sample is relatively small. This result is supported also by an independent photometric test and by the horizontal branch morphology and the dynamical state. It is old (~12 Gyr) and, at odds with other GCs, has no α-enhancement. The material it formed from was contaminated by both s- and r-process elements. The abundance pattern points toward an extragalactic origin. Its present-day mass (M = 104.83 M ⊙) can be assumed as a strong lower limit for the initial mass threshold below which no second generation is formed. Clearly, its initial mass must have been significantly greater, but we have no current constraints on the amount of mass loss during its evolution.

  2. Cluster synchronization of starlike networks with normalized Laplacian coupling: master stability function approach

    NASA Astrophysics Data System (ADS)

    Kuptsov, Pavel V.; Kuptsova, Anna V.

    2016-04-01

    A generalized model of star-like network is suggested that takes into account non-additive coupling and nonlinear transformation of coupling variables. For this model a method of analysis of synchronized cluster stability is developed. Using this method three star-like networks based on Ikeda, predator-prey and Hénon maps are studied.

  3. Transitions from spatiotemporal chaos to cluster and complete synchronization states in a shift-invariant set of coupled nonlinear oscillators.

    PubMed

    Chembo Kouomou, Y; Woafo, P

    2003-04-01

    We study the spatiotemporal dynamics of a ring of diffusely coupled single-well Duffing oscillators. The transitions from spatiotemporal chaos to cluster and complete synchronization states are particularly investigated, as well as the Hopf bifurcations to instability. It is found that the underlying mechanism of these transitions relies on the motion of the representative points corresponding to the system's nondegenerated spatial transverse Fourier modes in the parametric Strutt diagram. A scaling law is used to demonstrate that the compact interval of the scalar coupling parameter values leading to cluster synchronization broadens in a square-power-like fashion as the number of oscillators is increased. The analytical approach is confirmed by numerical simulations.

  4. Pinning cluster synchronization in an array of coupled neural networks under event-based mechanism.

    PubMed

    Li, Lulu; Ho, Daniel W C; Cao, Jinde; Lu, Jianquan

    2016-04-01

    Cluster synchronization is a typical collective behavior in coupled dynamical systems, where the synchronization occurs within one group, while there is no synchronization among different groups. In this paper, under event-based mechanism, pinning cluster synchronization in an array of coupled neural networks is studied. A new event-triggered sampled-data transmission strategy, where only local and event-triggering states are utilized to update the broadcasting state of each agent, is proposed to realize cluster synchronization of the coupled neural networks. Furthermore, a self-triggered pinning cluster synchronization algorithm is proposed, and a set of iterative procedures is given to compute the event-triggered time instants. Hence, this will reduce the computational load significantly. Finally, an example is given to demonstrate the effectiveness of the theoretical results. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

  5. Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations.

    PubMed

    Epifanovsky, Evgeny; Klein, Kerstin; Stopkowicz, Stella; Gauss, Jürgen; Krylov, Anna I

    2015-08-14

    We present a formalism and an implementation for calculating spin-orbit couplings (SOCs) within the EOM-CCSD (equation-of-motion coupled-cluster with single and double substitutions) approach. The following variants of EOM-CCSD are considered: EOM-CCSD for excitation energies (EOM-EE-CCSD), EOM-CCSD with spin-flip (EOM-SF-CCSD), EOM-CCSD for ionization potentials (EOM-IP-CCSD) and electron attachment (EOM-EA-CCSD). We employ a perturbative approach in which the SOCs are computed as matrix elements of the respective part of the Breit-Pauli Hamiltonian using zeroth-order non-relativistic wave functions. We follow the expectation-value approach rather than the response-theory formulation for property calculations. Both the full two-electron treatment and the mean-field approximation (a partial account of the two-electron contributions) have been implemented and benchmarked using several small molecules containing elements up to the fourth row of the periodic table. The benchmark results show the excellent performance of the perturbative treatment and the mean-field approximation. When used with an appropriate basis set, the errors with respect to experiment are below 5% for the considered examples. The findings regarding basis-set requirements are in agreement with previous studies. The impact of different correlation treatment in zeroth-order wave functions is analyzed. Overall, the EOM-IP-CCSD, EOM-EA-CCSD, EOM-EE-CCSD, and EOM-SF-CCSD wave functions yield SOCs that agree well with each other (and with the experimental values when available). Using an EOM-CCSD approach that provides a more balanced description of the target states yields more accurate results.

  6. Coupled-cluster method for open-shell heavy-element systems with spin-orbit coupling.

    PubMed

    Cao, Zhanli; Wang, Fan; Yang, Mingli

    2017-04-07

    The coupled-cluster approach with spin-orbit coupling (SOC) included in post-self-consistent field treatment (SOC-CC) using relativistic effective core potentials is extended to spatially non-degenerate open-shell systems in this work. The unrestricted Hartree-Fock determinant corresponding to the scalar relativistic Hamiltonian is employed as the reference and the open-shell SOC-CC approach is implemented at the CC singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations (CCSD(T)). Due to the breaking of time-reversal symmetry and spatial symmetry, this open-shell SOC-CC approach is rather expensive compared with the closed-shell SOC-CC approach. The open-shell SOC-CC approach is applied to some open-shell atoms and diatomic molecules with s(1), p(3), σ(1), or π(2) configuration. Our results indicate that rather accurate results can be achieved with the open-shell SOC-CCSD(T) approach for these systems. Dissociation energies for some closed-shell molecules containing heavy IIIA or VIIA atoms are also calculated using the closed-shell SOC-CC approach, where energies of the IIIA or VIIA atoms are obtained from those of the closed-shell ions and experimental ionization potentials or electron affinities. SOC-CCSD(T) approach affords reliable dissociation energies for these molecules. Furthermore, scalar-relativistic CCSD(T) approach with the same strategy can also provide reasonable dissociation energies for the 5th row IIIA or VIIA molecules, while the error becomes pronounced for the 6th row elements.

  7. Spin-orbit couplings within the equation-of-motion coupled-cluster framework: Theory, implementation, and benchmark calculations

    SciTech Connect

    Epifanovsky, Evgeny; Klein, Kerstin; Gauss, Jürgen; Stopkowicz, Stella; Krylov, Anna I.

    2015-08-14

    We present a formalism and an implementation for calculating spin-orbit couplings (SOCs) within the EOM-CCSD (equation-of-motion coupled-cluster with single and double substitutions) approach. The following variants of EOM-CCSD are considered: EOM-CCSD for excitation energies (EOM-EE-CCSD), EOM-CCSD with spin-flip (EOM-SF-CCSD), EOM-CCSD for ionization potentials (EOM-IP-CCSD) and electron attachment (EOM-EA-CCSD). We employ a perturbative approach in which the SOCs are computed as matrix elements of the respective part of the Breit-Pauli Hamiltonian using zeroth-order non-relativistic wave functions. We follow the expectation-value approach rather than the response-theory formulation for property calculations. Both the full two-electron treatment and the mean-field approximation (a partial account of the two-electron contributions) have been implemented and benchmarked using several small molecules containing elements up to the fourth row of the periodic table. The benchmark results show the excellent performance of the perturbative treatment and the mean-field approximation. When used with an appropriate basis set, the errors with respect to experiment are below 5% for the considered examples. The findings regarding basis-set requirements are in agreement with previous studies. The impact of different correlation treatment in zeroth-order wave functions is analyzed. Overall, the EOM-IP-CCSD, EOM-EA-CCSD, EOM-EE-CCSD, and EOM-SF-CCSD wave functions yield SOCs that agree well with each other (and with the experimental values when available). Using an EOM-CCSD approach that provides a more balanced description of the target states yields more accurate results.

  8. Coupled-cluster method for open-shell heavy-element systems with spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Cao, Zhanli; Wang, Fan; Yang, Mingli

    2017-04-01

    The coupled-cluster approach with spin-orbit coupling (SOC) included in post-self-consistent field treatment (SOC-CC) using relativistic effective core potentials is extended to spatially non-degenerate open-shell systems in this work. The unrestricted Hartree-Fock determinant corresponding to the scalar relativistic Hamiltonian is employed as the reference and the open-shell SOC-CC approach is implemented at the CC singles and doubles (CCSD) level as well as at the CCSD level augmented by a perturbative treatment of triple excitations (CCSD(T)). Due to the breaking of time-reversal symmetry and spatial symmetry, this open-shell SOC-CC approach is rather expensive compared with the closed-shell SOC-CC approach. The open-shell SOC-CC approach is applied to some open-shell atoms and diatomic molecules with s1, p3, σ1, or π2 configuration. Our results indicate that rather accurate results can be achieved with the open-shell SOC-CCSD(T) approach for these systems. Dissociation energies for some closed-shell molecules containing heavy IIIA or VIIA atoms are also calculated using the closed-shell SOC-CC approach, where energies of the IIIA or VIIA atoms are obtained from those of the closed-shell ions and experimental ionization potentials or electron affinities. SOC-CCSD(T) approach affords reliable dissociation energies for these molecules. Furthermore, scalar-relativistic CCSD(T) approach with the same strategy can also provide reasonable dissociation energies for the 5th row IIIA or VIIA molecules, while the error becomes pronounced for the 6th row elements.

  9. The ACS survey of Galactic globular clusters - XIV. Bayesian single-population analysis of 69 globular clusters

    NASA Astrophysics Data System (ADS)

    Wagner-Kaiser, R.; Sarajedini, A.; von Hippel, T.; Stenning, D. C.; van Dyk, D. A.; Jeffery, E.; Robinson, E.; Stein, N.; Anderson, J.; Jefferys, W. H.

    2017-06-01

    We use Hubble Space Telescope (HST) imaging from the ACS Treasury Survey to determine fits for single population isochrones of 69 Galactic globular clusters. Using robust Bayesian analysis techniques, we simultaneously determine ages, distances, absorptions and helium values for each cluster under the scenario of a 'single' stellar population on model grids with solar ratio heavy element abundances. The set of cluster parameters is determined in a consistent and reproducible manner for all clusters using the Bayesian analysis suite BASE-9. Our results are used to re-visit the age-metallicity relation. We find correlations with helium and several other parameters such as metallicity, binary fraction and proxies for cluster mass. The helium abundances of the clusters are also considered in the context of carbon, nitrogen, and oxygen abundances and the multiple population scenario.

  10. A coupled cluster theory with iterative inclusion of triple excitations and associated equation of motion formulation for excitation energy and ionization potential

    NASA Astrophysics Data System (ADS)

    Maitra, Rahul; Akinaga, Yoshinobu; Nakajima, Takahito

    2017-08-01

    A single reference coupled cluster theory that is capable of including the effect of connected triple excitations has been developed and implemented. This is achieved by regrouping the terms appearing in perturbation theory and parametrizing through two different sets of exponential operators: while one of the exponentials, involving general substitution operators, annihilates the ground state but has a non-vanishing effect when it acts on the excited determinant, the other is the regular single and double excitation operator in the sense of conventional coupled cluster theory, which acts on the Hartree-Fock ground state. The two sets of operators are solved as coupled non-linear equations in an iterative manner without significant increase in computational cost than the conventional coupled cluster theory with singles and doubles excitations. A number of physically motivated and computationally advantageous sufficiency conditions are invoked to arrive at the working equations and have been applied to determine the ground state energies of a number of small prototypical systems having weak multi-reference character. With the knowledge of the correlated ground state, we have reconstructed the triple excitation operator and have performed equation of motion with coupled cluster singles, doubles, and triples to obtain the ionization potential and excitation energies of these molecules as well. Our results suggest that this is quite a reasonable scheme to capture the effect of connected triple excitations as long as the ground state remains weakly multi-reference.

  11. S-P coupling induced unusual open-shell metal clusters.

    PubMed

    Cheng, Shi-Bo; Berkdemir, Cuneyt; Melko, Joshua J; Castleman, A W

    2014-04-02

    Metal clusters featuring closed supershells or aromatic character usually exhibit remarkably enhanced stability in their cluster series. However, not all stable clusters are subject to these fundamental constraints. Here, by employing photoelectron imaging spectroscopy and ab initio calculations, we present experimental and theoretical evidence on the existence of unexpectedly stable open-shell clusters, which are more stable than their closed-shell and aromatic counterparts. The stabilization of these open-shell Al-Mg clusters is proposed to originate from the S-P molecular orbital coupling, leading to highly stable species with increased HOMO-LUMO gaps, akin to s-p hybridization in an organic carbon atom that is beneficial to form stable species. Introduction of the coupling effect highlighted here not only shows the limitations of the conventional closed-shell model and aromaticity but also provides the possibility to design valuable building blocks.

  12. Coupling a single trapped atom to a nanoscale optical cavity.

    PubMed

    Thompson, J D; Tiecke, T G; de Leon, N P; Feist, J; Akimov, A V; Gullans, M; Zibrov, A S; Vuletić, V; Lukin, M D

    2013-06-07

    Hybrid quantum devices, in which dissimilar quantum systems are combined in order to attain qualities not available with either system alone, may enable far-reaching control in quantum measurement, sensing, and information processing. A paradigmatic example is trapped ultracold atoms, which offer excellent quantum coherent properties, coupled to nanoscale solid-state systems, which allow for strong interactions. We demonstrate a deterministic interface between a single trapped rubidium atom and a nanoscale photonic crystal cavity. Precise control over the atom's position allows us to probe the cavity near-field with a resolution below the diffraction limit and to observe large atom-photon coupling. This approach may enable the realization of integrated, strongly coupled quantum nano-optical circuits.

  13. Modal Coupling of Single Photon Emitters Within Nanofiber Waveguides

    PubMed Central

    2016-01-01

    Nanoscale generation of individual photons in confined geometries is an exciting research field aiming at exploiting localized electromagnetic fields for light manipulation. One of the outstanding challenges of photonic systems combining emitters with nanostructured media is the selective channelling of photons emitted by embedded sources into specific optical modes and their transport at distant locations in integrated systems. Here, we show that soft-matter nanofibers, electrospun with embedded emitters, combine subwavelength field localization and large broadband near-field coupling with low propagation losses. By momentum spectroscopy, we quantify the modal coupling efficiency identifying the regime of single-mode coupling. These nanofibers do not rely on resonant interactions, making them ideal for room-temperature operation, and offer a scalable platform for future quantum information technology. PMID:27203403

  14. Excited states with internally contracted multireference coupled-cluster linear response theory

    NASA Astrophysics Data System (ADS)

    Samanta, Pradipta Kumar; Mukherjee, Debashis; Hanauer, Matthias; Köhn, Andreas

    2014-04-01

    In this paper, the linear response (LR) theory for the variant of internally contracted multireference coupled cluster (ic-MRCC) theory described by Hanauer and Köhn [J. Chem. Phys. 134, 204211 (2011)] has been formulated and implemented for the computation of the excitation energies relative to a ground state of pronounced multireference character. We find that straightforward application of the linear-response formalism to the time-averaged ic-MRCC Lagrangian leads to unphysical second-order poles. However, the coupling matrix elements that cause this behavior are shown to be negligible whenever the internally contracted approximation as such is justified. Hence, for the numerical implementation of the method, we adopt a Tamm-Dancoff-type approximation and neglect these couplings. This approximation is also consistent with an equation-of-motion based derivation, which neglects these couplings right from the start. We have implemented the linear-response approach in the ic-MRCC singles-and-doubles framework and applied our method to calculate excitation energies for a number of molecules ranging from CH2 to p-benzyne and conjugated polyenes (up to octatetraene). The computed excitation energies are found to be very accurate, even for the notoriously difficult case of doubly excited states. The ic-MRCC-LR theory is also applicable to systems with open-shell ground-state wavefunctions and is by construction not biased towards a particular reference determinant. We have also compared the linear-response approach to the computation of energy differences by direct state-specific ic-MRCC calculations. We finally compare to Mk-MRCC-LR theory for which spurious roots have been reported [T.-C. Jagau and J. Gauss, J. Chem. Phys. 137, 044116 (2012)], being due to the use of sufficiency conditions to solve the Mk-MRCC equations. No such problem is present in ic-MRCC-LR theory.

  15. Excited states with internally contracted multireference coupled-cluster linear response theory.

    PubMed

    Samanta, Pradipta Kumar; Mukherjee, Debashis; Hanauer, Matthias; Köhn, Andreas

    2014-04-07

    In this paper, the linear response (LR) theory for the variant of internally contracted multireference coupled cluster (ic-MRCC) theory described by Hanauer and Köhn [J. Chem. Phys. 134, 204211 (2011)] has been formulated and implemented for the computation of the excitation energies relative to a ground state of pronounced multireference character. We find that straightforward application of the linear-response formalism to the time-averaged ic-MRCC Lagrangian leads to unphysical second-order poles. However, the coupling matrix elements that cause this behavior are shown to be negligible whenever the internally contracted approximation as such is justified. Hence, for the numerical implementation of the method, we adopt a Tamm-Dancoff-type approximation and neglect these couplings. This approximation is also consistent with an equation-of-motion based derivation, which neglects these couplings right from the start. We have implemented the linear-response approach in the ic-MRCC singles-and-doubles framework and applied our method to calculate excitation energies for a number of molecules ranging from CH2 to p-benzyne and conjugated polyenes (up to octatetraene). The computed excitation energies are found to be very accurate, even for the notoriously difficult case of doubly excited states. The ic-MRCC-LR theory is also applicable to systems with open-shell ground-state wavefunctions and is by construction not biased towards a particular reference determinant. We have also compared the linear-response approach to the computation of energy differences by direct state-specific ic-MRCC calculations. We finally compare to Mk-MRCC-LR theory for which spurious roots have been reported [T.-C. Jagau and J. Gauss, J. Chem. Phys. 137, 044116 (2012)], being due to the use of sufficiency conditions to solve the Mk-MRCC equations. No such problem is present in ic-MRCC-LR theory.

  16. Implementation of the multireference Brillouin-Wigner and Mukherjee’s coupled cluster methods with non-iterative triple excitations utilizing reference-level parallelism

    SciTech Connect

    Bhaskaran-Nair, Kiran; Brabec, Jiri; Apra, Edoardo; van Dam, Hubertus JJ; Pittner, Jiri; Kowalski, Karol

    2012-09-07

    In this paper we discuss the performance of the non-iterative State-Specific Mul- tireference Coupled Cluster (SS-MRCC) methods accounting for the effect of triply excited cluster amplitudes. The corrections to the Brillouin-Wigner and Mukherjee MRCC models based on the manifold of singly and doubly excited cluster amplitudes (BW-MRCCSD and Mk-MRCCSD, respectively) are tested and compared with the exact full configuration interaction results (FCI) for small systems (H2O, N2, and Be3). For larger systems (naphthyne isomers and -carotene), the non-iterative BW-MRCCSD(T) and Mk-MRCCSD(T) methods are compared against the results obtained with the single reference coupled cluster methods. We also report on the parallel performance of the non-iterative implementations based on the use of pro- cessor groups.

  17. Quantum tunneling of two coupled single-molecular magnets

    NASA Astrophysics Data System (ADS)

    Hu, Jianming; Chen, Zhide; Shen, Shunqing

    2003-03-01

    Jian-Ming Hu, Zhi-De Chen and Shun-Qing Shen Department of Physics, The University of Hong Kong Pokfulam Road, Hong Kong December 02, 2002 Very recently a supramolecular dimer of two single-molecule magnets (SMM) was reported to be synthesized successfully. Two single-molecule magnets are coupled antiferromagnetically to form a supramolecule dimer. We study the coupling effect and tunneling process by the numerical exact diagonalization method. The sweeping rate effect in the derivatives of hysteresis loops has been quantitatively investigated using the modified Landau-Zener model. In addiction we find that exchange coupling between the two SMMs provides a biased field to expel the tunneling between SMMs to two new resonant points via an intermediate state, and direct tunneling is prohibited. The model parameters are calculated for the dimer based on the tunneling process. The outcome indicates that the coupling effect will not change the parameters of each SMM too much at all. This work is supported by a CRCG grant of The University of Hong Kong.

  18. High electronic couplings of single mesitylene molecular junctions.

    PubMed

    Komoto, Yuki; Fujii, Shintaro; Nishino, Tomoaki; Kiguchi, Manabu

    2015-01-01

    We report on an experimental analysis of the charge transport properties of single mesitylene (1,3,5-trimethylbenzene) molecular junctions. The electronic conductance and the current-voltage characteristics of mesitylene molecules wired into Au electrodes were measured by a scanning tunnelling microscopy-based break-junction method at room temperature in a liquid environment. We found the molecular junctions exhibited two distinct conductance states with high conductance values of ca. 10(-1) G 0 and of more than 10(-3) G 0 (G 0 = 2e (2)/h) in the electronic conductance measurements. We further performed a statistical analysis of the current-voltage characteristics of the molecular junctions in the two states. Within a single channel resonant tunnelling model, we obtained electronic couplings in the molecular junctions by fitting the current-voltage characteristics to the single channel model. The origin of the high conductance was attributed to experimentally obtained large electronic couplings of the direct π-bonded molecular junctions (ca. 0.15 eV). Based on analysis of the stretch length of the molecular junctions and the large electronic couplings obtained from the I-V analysis, we proposed two structural models, in which (i) mesitylene binds to the Au electrode perpendicular to the charge transport direction and (ii) mesitylene has tilted from the perpendicular orientation.

  19. Optical Sizing of Immunolabel Clusters through Multispectral Plasmon Coupling Microscopy

    PubMed Central

    Wang, Hongyun; Rong, Guoxin; Yan, Bo; Yang, Linglu; Reinhard, Björn M.

    2011-01-01

    The wavelength dependent scattering cross-sections of self-assembled silver nanoparticle clusters of known size (n) were measured on five different wavelength channels between 427 and 510 nm through correlation of multispectral imaging and scanning electron microscopy. A multivariate statistical analysis of the spectral response of this training set provided a correlation between spectral response and cluster size and enabled a classification of new measurements into four distinct nanoparticle association levels (I1 – I4) whose compositions were dominated by monomers (I1), dimers (I2), trimers and tetramers (I3), and larger clusters (I4), respectively. One potential application of the optical sizing approach is to map association levels of silver immunolabels on cellular surfaces. We demonstrate the feasibility of this approach using silver immunolabels targeted at the epidermal growth factor receptor on A431 cells in a proof of principle experiment. The ability to measure immunolabel association levels on sub-cellular length scales in an optical microscope provides new opportunities for experimentally assessing receptor density distributions on living cells in solution. PMID:21247191

  20. Speeding up equation of motion coupled cluster theory with the chain of spheres approximation

    SciTech Connect

    Dutta, Achintya Kumar; Neese, Frank Izsák, Róbert

    2016-01-21

    In the present paper, the chain of spheres exchange (COSX) approximation is applied to the highest scaling terms in the equation of motion (EOM) coupled cluster equations with single and double excitations, in particular, the terms involving integrals with four virtual labels. It is found that even the acceleration of this single term yields significant computational gains without compromising the desired accuracy of the method. For an excitation energy calculation on a cluster of five water molecules using 585 basis functions, the four virtual term is 9.4 times faster using COSX with a loose grid than using the canonical implementation, which yields a 2.6 fold acceleration for the whole of the EOM calculation. For electron attachment calculations, the four virtual term is 15 times and the total EOM calculation is 10 times faster than the canonical calculation for the same system. The accuracy of the new method was tested using Thiel’s test set for excited states using the same settings and the maximum absolute deviation over the whole test set was found to be 12.945 cm{sup −1} (59 μHartree) for excitation energies and 6.799 cm{sup −1} (31 μHartree) for electron attachments. Using MP2 amplitudes for the ground state in combination with the parallel evaluation of the full EOM equations in the manner discussed in this paper enabled us to perform calculations for large systems. Electron affinity values for the two lowest states of a Zn protoporphyrine model compound (224 correlated electrons and 1120 basis functions) were obtained in 3 days 19 h using 4 cores of a Xeon E5-2670 processor allocating 10 GB memory per core. Calculating the lowest two excitation energies for trans-retinal (114 correlated electrons and 539 basis functions) took 1 day 21 h using eight cores of the same processor and identical memory allocation per core.

  1. Dimer and cluster approach for the evaluation of electronic couplings governing charge transport: Application to two pentacene polymorphs

    NASA Astrophysics Data System (ADS)

    Canola, Sofia; Pecoraro, Claudia; Negri, Fabrizia

    2016-10-01

    Hole transport properties are modeled for two polymorphs of pentacene: the single crystal polymorph and the thin film polymorph relevant for organic thin-film transistor applications. Electronic couplings are evaluated in the standard dimer approach but also considering a cluster approach in which the central molecule is surrounded by a large number of molecules quantum-chemically described. The effective electronic couplings suitable for the parametrization of a tight-binding model are derived either from the orthogonalization scheme limited to HOMO orbitals and from the orthogonalization of the full basis of molecular orbitals. The angular dependent mobilities estimated for the two polymorphs using the predicted pattern of couplings display different anisotropy characteristics as suggested from experimental investigations.

  2. Monte Carlo simulations of single and coupled synthetic molecular motors

    NASA Astrophysics Data System (ADS)

    Chen, C.-M.; Zuckermann, M.

    2012-11-01

    We use a minimal model to study the processive motion of coupled synthetic molecular motors along a DNA track and we present data from Monte Carlo (MC) computer simulations based on this model. The model was originally proposed by Bromley [HFSP J.10.2976/1.3111282 3, 204 (2009)] for studying the properties of a synthetic protein motor, the “Tumbleweed” (TW), and involves rigid Y-shaped motors diffusively rotating along the track while controlled by a series of periodically injected ligand pulses into the solution. The advantage of the model is that it mimics the mechanical properties of the TW motor in detail. Both the average first passage time which measures the diffusive motion of the motors, and the average dwell time on the track which measures their processivity are investigated by varying the parameters of the model. The latter includes ligand concentration and the range and strength of the binding interaction between motors and the track. In particular, it is of experimental interest to study the dependence of these dynamic time scales of the motors on the ligand concentration. Single rigid TW motors were first studied since no previous MC simulations of these motors have been performed. We first studied single motors for which we found a logarithmic decrease of the average first passage time and a logarithmic increase of the average dwell time with increasing ligand concentration. For two coupled motors, the dependence on ligand concentration is still logarithmic for the average first passage time but becomes linear for the average dwell time. This suggests a much greater stability in the processive motion of coupled motors as compared to single motors in the limit of large ligand concentration. By increasing the number of coupled motors, m, it was found that the average first passage time of the coupled motors only increases slowly with m while the average dwell time increases exponentially with m. Thus the stability of coupled motors on the track can

  3. Systematic Comparison of Second-Order Polarization Propagator Approximation (SOPPA) and Equation-of-Motion Coupled Cluster Singles and Doubles (EOM-CCSD) Spin-Spin Coupling Constants for Molecules with C, N, and O Double and Triple Bonds and Selected F-Substituted Derivatives.

    PubMed

    Del Bene, Janet E; Alkorta, Ibon; Elguero, José

    2009-01-13

    Ab initio EOM-CCSD and SOPPA calculations with the Ahlrichs (qzp,qz2p) basis set have been carried out to evaluate one-, two-, and three-bond spin-spin coupling constants for molecules HmXYHn and HmXYHn for X, Y = (13)C, (15)N, and (17)O, and selected (19)F-substituted derivatives. In the great majority of cases, EOM-CCSD one-bond C-C, C-N, C-O, C-F, N-N, N-O, and N-F coupling constants and three-bond F-F coupling constants are smaller in absolute value than the corresponding SOPPA coupling constants, with the EOM-CCSD values in better agreement with experimental data. SOPPA tends to significantly overestimate the absolute values of large one- and three-bond couplings involving fluorine. The majority of two-bond SOPPA coupling constants are in better agreement with experiment than EOM-CCSD, although differences between EOM-CCSD and experimental values are not dramatic. A statistical analysis of thirty EOM-CCSD and SOPPA coupling constants versus experimental coupling constants demonstrates that better agreement with experiment is found when EOM-CCSD is the computational method.

  4. Tapered fiber coupling of single photons emitted by a deterministically positioned single nitrogen vacancy center

    SciTech Connect

    Liebermeister, Lars Petersen, Fabian; Münchow, Asmus v.; Burchardt, Daniel; Hermelbracht, Juliane; Tashima, Toshiyuki; Schell, Andreas W.; Benson, Oliver; Meinhardt, Thomas; Krueger, Anke; Stiebeiner, Ariane; Rauschenbeutel, Arno; Weinfurter, Harald; Weber, Markus

    2014-01-20

    A diamond nano-crystal hosting a single nitrogen vacancy (NV) center is optically selected with a confocal scanning microscope and positioned deterministically onto the subwavelength-diameter waist of a tapered optical fiber (TOF) with the help of an atomic force microscope. Based on this nano-manipulation technique, we experimentally demonstrate the evanescent coupling of single fluorescence photons emitted by a single NV-center to the guided mode of the TOF. By comparing photon count rates of the fiber-guided and the free-space modes and with the help of numerical finite-difference time domain simulations, we determine a lower and upper bound for the coupling efficiency of (9.5 ± 0.6)% and (10.4 ± 0.7)%, respectively. Our results are a promising starting point for future integration of single photon sources into photonic quantum networks and applications in quantum information science.

  5. Tapered fiber coupling of single photons emitted by a deterministically positioned single nitrogen vacancy center

    NASA Astrophysics Data System (ADS)

    Liebermeister, Lars; Petersen, Fabian; Münchow, Asmus v.; Burchardt, Daniel; Hermelbracht, Juliane; Tashima, Toshiyuki; Schell, Andreas W.; Benson, Oliver; Meinhardt, Thomas; Krueger, Anke; Stiebeiner, Ariane; Rauschenbeutel, Arno; Weinfurter, Harald; Weber, Markus

    2014-01-01

    A diamond nano-crystal hosting a single nitrogen vacancy (NV) center is optically selected with a confocal scanning microscope and positioned deterministically onto the subwavelength-diameter waist of a tapered optical fiber (TOF) with the help of an atomic force microscope. Based on this nano-manipulation technique, we experimentally demonstrate the evanescent coupling of single fluorescence photons emitted by a single NV-center to the guided mode of the TOF. By comparing photon count rates of the fiber-guided and the free-space modes and with the help of numerical finite-difference time domain simulations, we determine a lower and upper bound for the coupling efficiency of (9.5 ± 0.6)% and (10.4 ± 0.7)%, respectively. Our results are a promising starting point for future integration of single photon sources into photonic quantum networks and applications in quantum information science.

  6. Spin coupling and orbital angular momentum quenching in free iron clusters.

    PubMed

    Niemeyer, M; Hirsch, K; Zamudio-Bayer, V; Langenberg, A; Vogel, M; Kossick, M; Ebrecht, C; Egashira, K; Terasaki, A; Möller, T; Issendorff, B V; Lau, J T

    2012-02-03

    Magnetic spin and orbital moments of size-selected free iron cluster ions Fe{n}{+} (n=3-20) have been determined via x-ray magnetic circular dichroism spectroscopy. Iron atoms within the clusters exhibit ferromagnetic coupling except for Fe{13}{+}, where the central atom is coupled antiferromagnetically to the atoms in the surrounding shell. Even in very small clusters, the orbital magnetic moment is strongly quenched and reduced to 5%-25% of its atomic value while the spin magnetic moment remains at 60%-90%. This demonstrates that the formation of bonds quenches orbital angular momenta in homonuclear iron clusters already for coordination numbers much smaller than those of the bulk.

  7. Coupling single quantum dots to plasmonic nanocones: optical properties.

    PubMed

    Meixner, Alfred J; Jäger, Regina; Jäger, Sebastian; Bräuer, Annika; Scherzinger, Kerstin; Fulmes, Julia; Krockhaus, Sven zur Oven; Gollmer, Dominik A; Kern, Dieter P; Fleischer, Monika

    2015-01-01

    Coupling a single quantum emitter, such as a fluorescent molecule or a quantum dot (QD), to a plasmonic nanostructure is an important issue in nano-optics and nano-spectroscopy, relevant for a wide range of applications, including tip-enhanced near-field optical microscopy, plasmon enhanced molecular sensing and spectroscopy, and nanophotonic amplifiers or nanolasers, to mention only a few. While the field enhancement of a sharp nanoantenna increasing the excitation rate of a very closely positioned single molecule or QD has been well investigated, the detailed physical mechanisms involved in the emission of a photon from such a system are, by far, less investigated. In one of our ongoing research projects, we try to address these issues by constructing and spectroscopically analysing geometrically simple hybrid heterostructures consisting of sharp gold cones with single quantum dots attached to the very tip apex. An important goal of this work is to tune the longitudinal plasmon resonance by adjusting the cones' geometry to the emission maximum of the core-shell CdSe/ZnS QDs at nominally 650 nm. Luminescence spectra of the bare cones, pure QDs and hybrid systems were distinguished successfully. In the next steps we will further investigate, experimentally and theoretically, the optical properties of the coupled systems in more detail, such as the fluorescence spectra, blinking statistics, and the current results on the fluorescence lifetimes, and compare them with uncoupled QDs to obtain a clearer picture of the radiative and non-radiative processes.

  8. Single and coupled quantum wells: SiGe

    NASA Astrophysics Data System (ADS)

    Usami, N.; Shiraki, Y.

    This document is part of subvolume C3 'Optical Properties' of volume 34 'Semiconductor quantum structures' of Landolt-Börnstein, Group III, Condensed Matter, on the optical properties of quantum structures based on group IV semiconductors. It discusses single and coupled quantum wells based on SiGe. Topics include the photoluminescence from SiGe/Si quantum wells (spectral features, dependence on excitation power and temperature), effects of quantum confinement, post-growth annealing, electric fields and external stress, the Fermi-edge singularity, time-resolved photoluminescence, growth mode transition, type-II strained Si quantum wells, coupled quantum wells, electroluminescence, interband absorption and intraband absorption, second-harmonic generation, and phonon modes.

  9. Cluster analysis of Scedosporium boydii infections in a single hospital.

    PubMed

    Bernhardt, Anne; Seibold, Michael; Rickerts, Volker; Tintelnot, Kathrin

    2015-10-01

    Scedosporiosis is a rare, but often fatal mycotic infection occurring in immunosuppressed as well as in immunocompetent patients. Over a period of 14 months, Scedosporium boydii isolates were sent to our reference laboratory from six immunocompetent patients treated at a single hospital in Germany. In analogy to the EORTC/MSG criteria, four patients were classified as proven invasive scedosporiosis cases, and two patients as probable or possible cases. Of note, in five patients scedosporiosis was diagnosed between 1 and 14 months (median 5.0 months) after cardiac surgery. Despite antimycotic treatment two patients died, and three were lost for long-term follow-up. All clinical S. boydii isolates were characterized by molecular analysis using multilocus sequence typing (MLST). An identical MLST type was found in five patients who had been treated in the surgery unit, suggesting a link between these infections. The source of S. boydii has not been identified. Within an observation period of 2 years before and after this cluster of infections no further cases of scedosporiosis were reported from this hospital.

  10. Single Nucleotide Polymorphism Clustering in Systemic Autoimmune Diseases

    PubMed Central

    Charlon, Thomas; Bossini-Castillo, Lara; Carmona, F. David; Di Cara, Alessandro; Wojcik, Jérôme; Voloshynovskiy, Sviatoslav

    2016-01-01

    Systemic Autoimmune Diseases, a group of chronic inflammatory conditions, have variable symptoms and difficult diagnosis. In order to reclassify them based on genetic markers rather than clinical criteria, we performed clustering of Single Nucleotide Polymorphisms. However naive approaches tend to group patients primarily by their geographic origin. To reduce this “ancestry signal”, we developed SNPClust, a method to select large sources of ancestry-independent genetic variations from all variations detected by Principal Component Analysis. Applied to a Systemic Lupus Erythematosus case control dataset, SNPClust successfully reduced the ancestry signal. Results were compared with association studies between the cases and controls without or with reference population stratification correction methods. SNPClust amplified the disease discriminating signal and the ratio of significant associations outside the HLA locus was greater compared to population stratification correction methods. SNPClust will enable the use of ancestry-independent genetic information in the reclassification of Systemic Autoimmune Diseases. SNPClust is available as an R package and demonstrated on the public Human Genome Diversity Project dataset at https://github.com/ThomasChln/snpclust. PMID:27490238

  11. Parallelization of the Wolff single-cluster algorithm

    NASA Astrophysics Data System (ADS)

    Kaupužs, J.; Rimšāns, J.; Melnik, R. V. N.

    2010-02-01

    A parallel [open multiprocessing (OpenMP)] implementation of the Wolff single-cluster algorithm has been developed and tested for the three-dimensional (3D) Ising model. The developed procedure is generalizable to other lattice spin models and its effectiveness depends on the specific application at hand. The applicability of the developed methodology is discussed in the context of the applications, where a sophisticated shuffling scheme is used to generate pseudorandom numbers of high quality, and an iterative method is applied to find the critical temperature of the 3D Ising model with a great accuracy. For the lattice with linear size L=1024 , we have reached the speedup about 1.79 times on two processors and about 2.67 times on four processors, as compared to the serial code. According to our estimation, the speedup about three times on four processors is reachable for the O(n) models with n≥2 . Furthermore, the application of the developed OpenMP code allows us to simulate larger lattices due to greater operative (shared) memory available.

  12. Parallelization of the Wolff single-cluster algorithm.

    PubMed

    Kaupuzs, J; Rimsāns, J; Melnik, R V N

    2010-02-01

    A parallel [open multiprocessing (OpenMP)] implementation of the Wolff single-cluster algorithm has been developed and tested for the three-dimensional (3D) Ising model. The developed procedure is generalizable to other lattice spin models and its effectiveness depends on the specific application at hand. The applicability of the developed methodology is discussed in the context of the applications, where a sophisticated shuffling scheme is used to generate pseudorandom numbers of high quality, and an iterative method is applied to find the critical temperature of the 3D Ising model with a great accuracy. For the lattice with linear size L=1024, we have reached the speedup about 1.79 times on two processors and about 2.67 times on four processors, as compared to the serial code. According to our estimation, the speedup about three times on four processors is reachable for the O(n) models with n> or =2. Furthermore, the application of the developed OpenMP code allows us to simulate larger lattices due to greater operative (shared) memory available.

  13. Persistent Memory in Single Node Delay-Coupled Reservoir Computing

    PubMed Central

    Pipa, Gordon; Toutounji, Hazem

    2016-01-01

    Delays are ubiquitous in biological systems, ranging from genetic regulatory networks and synaptic conductances, to predator/pray population interactions. The evidence is mounting, not only to the presence of delays as physical constraints in signal propagation speed, but also to their functional role in providing dynamical diversity to the systems that comprise them. The latter observation in biological systems inspired the recent development of a computational architecture that harnesses this dynamical diversity, by delay-coupling a single nonlinear element to itself. This architecture is a particular realization of Reservoir Computing, where stimuli are injected into the system in time rather than in space as is the case with classical recurrent neural network realizations. This architecture also exhibits an internal memory which fades in time, an important prerequisite to the functioning of any reservoir computing device. However, fading memory is also a limitation to any computation that requires persistent storage. In order to overcome this limitation, the current work introduces an extended version to the single node Delay-Coupled Reservoir, that is based on trained linear feedback. We show by numerical simulations that adding task-specific linear feedback to the single node Delay-Coupled Reservoir extends the class of solvable tasks to those that require nonfading memory. We demonstrate, through several case studies, the ability of the extended system to carry out complex nonlinear computations that depend on past information, whereas the computational power of the system with fading memory alone quickly deteriorates. Our findings provide the theoretical basis for future physical realizations of a biologically-inspired ultrafast computing device with extended functionality. PMID:27783690

  14. Persistent Memory in Single Node Delay-Coupled Reservoir Computing.

    PubMed

    Kovac, André David; Koall, Maximilian; Pipa, Gordon; Toutounji, Hazem

    2016-01-01

    Delays are ubiquitous in biological systems, ranging from genetic regulatory networks and synaptic conductances, to predator/pray population interactions. The evidence is mounting, not only to the presence of delays as physical constraints in signal propagation speed, but also to their functional role in providing dynamical diversity to the systems that comprise them. The latter observation in biological systems inspired the recent development of a computational architecture that harnesses this dynamical diversity, by delay-coupling a single nonlinear element to itself. This architecture is a particular realization of Reservoir Computing, where stimuli are injected into the system in time rather than in space as is the case with classical recurrent neural network realizations. This architecture also exhibits an internal memory which fades in time, an important prerequisite to the functioning of any reservoir computing device. However, fading memory is also a limitation to any computation that requires persistent storage. In order to overcome this limitation, the current work introduces an extended version to the single node Delay-Coupled Reservoir, that is based on trained linear feedback. We show by numerical simulations that adding task-specific linear feedback to the single node Delay-Coupled Reservoir extends the class of solvable tasks to those that require nonfading memory. We demonstrate, through several case studies, the ability of the extended system to carry out complex nonlinear computations that depend on past information, whereas the computational power of the system with fading memory alone quickly deteriorates. Our findings provide the theoretical basis for future physical realizations of a biologically-inspired ultrafast computing device with extended functionality.

  15. In search of massive single-population globular clusters

    NASA Astrophysics Data System (ADS)

    Caloi, Vittoria; D'Antona, Francesca

    2011-10-01

    The vast majority of globular clusters so far examined shows the chemical signatures of hosting (at least) two stellar populations. According to recent ideas, this feature requires a two-step process, in which the nuclearly processed matter from a 'first generation' (FG) of stars gives birth to a 'second generation' (SG), bearing the fingerprint of a fully carbon-nitrogen-oxygen (CNO) cycled matter. Since, as observed, the present population of most globular clusters is made up largely of SG stars, a substantial fraction of the FG (≳90 per cent) must be lost. Nevertheless, two types of clusters dominated by a simple stellar population (FG clusters) should exist: clusters initially too small to be able to retain a cooling flow and form a second generation (FG-only clusters) and massive clusters that could retain the CNO-processed ejecta and form an SG, but were unable to lose a significant fraction of their FG (mainly-FG clusters). Identification of mainly-FG clusters may provide an estimate of the fraction of the initial mass involved in the formation of the SG. We attempt a first classification of FG clusters, based on the morphology of their horizontal branches (HBs), as displayed in the published catalogues of photometric data for 106 clusters. We select, as FG candidates, the clusters in which the HB can be reproduced by the evolution of an almost unique mass. We find that less than 20 per cent of clusters with [Fe/H] < -0.8 appear to be FG, but only ˜10 per cent probably had a mass sufficient to form at all an SG. This small percentage confirms on a wider data base the spectroscopic result that the SG is a dominant constituent of today's clusters, suggesting that its formation is an ingredient necessary for the survival of globular clusters during their dynamical evolution in the Galactic tidal field. In more detail we show that Pal 3 turns out to be a good example of FG-only cluster. Instead, HB simulations and space distribution of its components indicate

  16. Near-Edge X-ray Absorption Fine Structure within Multilevel Coupled Cluster Theory.

    PubMed

    Myhre, Rolf H; Coriani, Sonia; Koch, Henrik

    2016-06-14

    Core excited states are challenging to calculate, mainly because they are embedded in a manifold of high-energy valence-excited states. However, their locality makes their determination ideal for local correlation methods. In this paper, we demonstrate the performance of multilevel coupled cluster theory in computing core spectra both within the core-valence separated and the asymmetric Lanczos implementations of coupled cluster linear response theory. We also propose a visualization tool to analyze the excitations using the difference between the ground-state and excited-state electron densities.

  17. Carrier doping and interlayer coupling in HTSC single crystals

    SciTech Connect

    Kishio, K.; Shimoyama, J.; Kimura, T.; Kotaka, Y.; Kitazawa, K.; Yamafuji, K.; Li, Q.; Suenaga, M.

    1994-09-01

    Experimental results of the effect of carrier doping on the irreversibility lines in (La,Sr){sub 2}CuO{sub 4{minus}{delta}} and Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8 + {delta}} single crystals are summarized. As a function of Sr or oxygen contents, systematic and dramatic widening of the irreversible regions in the B {minus} T phase diagram was observed in both systems. The present study suggests the critical importance of carrier concentration which directly affects the interlayer coupling strength and dimensionality of the flux line lattice in all the layered HTSC compounds as a universal feature.

  18. Laser to single-mode-fiber coupling: A laboratory guide

    NASA Technical Reports Server (NTRS)

    Ladany, I.

    1992-01-01

    All the information necessary to achieve reasonably efficient coupling of semiconductor lasers to single mode fibers is collected from the literature, reworked when necessary, and presented in a mostly tabular form. Formulas for determining the laser waist radius and the fiber mode radius are given. Imaging relations connecting these values with the object and image distances are given for three types of lenses: ball, hemisphere, and Gradient Index (GRIN). Sources for these lenses are indicated, and a brief discussion is given about ways of reducing feedback effects.

  19. Laser to single-mode-fiber coupling: A laboratory guide

    NASA Astrophysics Data System (ADS)

    Ladany, I.

    1992-07-01

    All the information necessary to achieve reasonably efficient coupling of semiconductor lasers to single mode fibers is collected from the literature, reworked when necessary, and presented in a mostly tabular form. Formulas for determining the laser waist radius and the fiber mode radius are given. Imaging relations connecting these values with the object and image distances are given for three types of lenses: ball, hemisphere, and Gradient Index (GRIN). Sources for these lenses are indicated, and a brief discussion is given about ways of reducing feedback effects.

  20. Application of the coupled-cluster approach to the electric dipole moment of atoms and molecules due to parity and time-reversal violation

    NASA Astrophysics Data System (ADS)

    Shukla, Alok; Das, B. P.; Mukherjee, D.

    1994-09-01

    In this paper we present a variant of Monkhorst's coupled-cluster-based linear-response approach designed for direct calculations of static properties of closed-shell many-fermion systems [Int. J. Quantum Chem Symp. 11, 421 (1977)]. All the required equations are derived in the framework of the coupled-cluster singles and doubles model. Although the approach has been developed with the calculation of electric-dipole moment of atoms and molecules due to parity- and time-reversal-violating interactions in mind, it is general enough to be applicable to other problems which require the presence of two one-electron perturbations.

  1. Strong coupling between single-electron tunneling and nanomechanical motion.

    PubMed

    Steele, G A; Hüttel, A K; Witkamp, B; Poot, M; Meerwaldt, H B; Kouwenhoven, L P; van der Zant, H S J

    2009-08-28

    Nanoscale resonators that oscillate at high frequencies are useful in many measurement applications. We studied a high-quality mechanical resonator made from a suspended carbon nanotube driven into motion by applying a periodic radio frequency potential using a nearby antenna. Single-electron charge fluctuations created periodic modulations of the mechanical resonance frequency. A quality factor exceeding 10(5) allows the detection of a shift in resonance frequency caused by the addition of a single-electron charge on the nanotube. Additional evidence for the strong coupling of mechanical motion and electron tunneling is provided by an energy transfer to the electrons causing mechanical damping and unusual nonlinear behavior. We also discovered that a direct current through the nanotube spontaneously drives the mechanical resonator, exerting a force that is coherent with the high-frequency resonant mechanical motion.

  2. Strong Coupling Between Single-Electron Tunneling and Nanomechanical Motion

    NASA Astrophysics Data System (ADS)

    Steele, G. A.; Hüttel, A. K.; Witkamp, B.; Poot, M.; Meerwaldt, H. B.; Kouwenhoven, L. P.; van der Zant, H. S. J.

    2009-08-01

    Nanoscale resonators that oscillate at high frequencies are useful in many measurement applications. We studied a high-quality mechanical resonator made from a suspended carbon nanotube driven into motion by applying a periodic radio frequency potential using a nearby antenna. Single-electron charge fluctuations created periodic modulations of the mechanical resonance frequency. A quality factor exceeding 105 allows the detection of a shift in resonance frequency caused by the addition of a single-electron charge on the nanotube. Additional evidence for the strong coupling of mechanical motion and electron tunneling is provided by an energy transfer to the electrons causing mechanical damping and unusual nonlinear behavior. We also discovered that a direct current through the nanotube spontaneously drives the mechanical resonator, exerting a force that is coherent with the high-frequency resonant mechanical motion.

  3. Geminal-spanning orbitals make explicitly correlated reduced-scaling coupled-cluster methods robust, yet simple

    NASA Astrophysics Data System (ADS)

    Pavošević, Fabijan; Neese, Frank; Valeev, Edward F.

    2014-08-01

    We present a production implementation of reduced-scaling explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) method based on pair-natural orbitals (PNOs). A key feature is the reformulation of the explicitly correlated terms using geminal-spanning orbitals that greatly reduce the truncation errors of the F12 contribution. For the standard S66 benchmark of weak intermolecular interactions, the cc-pVDZ-F12 PNO CCSD F12 interaction energies reproduce the complete basis set CCSD limit with mean absolute error <0.1 kcal/mol, and at a greatly reduced cost compared to the conventional CCSD F12.

  4. Current rectification in a single molecule diode: the role of electrode coupling

    NASA Astrophysics Data System (ADS)

    Sherif, Siya; Rubio-Bollinger, Gabino; Pinilla-Cienfuegos, Elena; Coronado, Eugenio; Cuevas, Juan Carlos; Agraït, Nicolás

    2015-07-01

    We demonstrate large rectification ratios (\\gt 100) in single-molecule junctions based on a metal-oxide cluster (polyoxometalate), using a scanning tunneling microscope (STM) both at ambient conditions and at low temperature. These rectification ratios are the largest ever observed in a single-molecule junction, and in addition these junctions sustain current densities larger than 105 A cm-2. By following the variation of the I-V characteristics with tip-molecule separation we demonstrate unambiguously that rectification is due to asymmetric coupling to the electrodes of a molecule with an asymmetric level structure. This mechanism can be implemented in other type of molecular junctions using both organic and inorganic molecules and provides a simple strategy for the rational design of molecular diodes.

  5. Ab-initio coupled-cluster effective interactions for the shell model: Application to neutron-rich oxygen and carbon isotopes

    SciTech Connect

    Jansen, G. R.; Engel, Jonathan; Hagen, Gaute; Navratil, Petr; Signoracci, Angelo J.

    2014-10-03

    We derive and compute effective valence-space shell-model interactions from ab initio coupled-cluster theory and apply them to open-shell and neutron-rich oxygen and carbon isotopes. Our shell-model interactions are based on nucleon-nucleon and three-nucleon forces from chiral effective-field theory. We compute the energies of ground and low-lying states, and find good agreement with experiment. In particular, our computed 2+ states are consistent with N=14,16 shell closures in 22,24O, and a weaker N=14 shell closure in 20C. We find good agreement between our coupled-cluster effective-interaction results with those obtained from standard single-reference coupled-cluster calculations for up to eight valence neutrons.

  6. SC3: consensus clustering of single-cell RNA-seq data.

    PubMed

    Kiselev, Vladimir Yu; Kirschner, Kristina; Schaub, Michael T; Andrews, Tallulah; Yiu, Andrew; Chandra, Tamir; Natarajan, Kedar N; Reik, Wolf; Barahona, Mauricio; Green, Anthony R; Hemberg, Martin

    2017-03-27

    Single-cell RNA-seq enables the quantitative characterization of cell types based on global transcriptome profiles. We present single-cell consensus clustering (SC3), a user-friendly tool for unsupervised clustering, which achieves high accuracy and robustness by combining multiple clustering solutions through a consensus approach (http://bioconductor.org/packages/SC3). We demonstrate that SC3 is capable of identifying subclones from the transcriptomes of neoplastic cells collected from patients.

  7. Coupling graphene nanomechanical motion to a single-electron transistor.

    PubMed

    Luo, Gang; Zhang, Zhuo-Zhi; Deng, Guang-Wei; Li, Hai-Ou; Cao, Gang; Xiao, Ming; Guo, Guang-Can; Guo, Guo-Ping

    2017-05-04

    Graphene-based electromechanical resonators have attracted great interest recently because of the outstanding mechanical and electrical properties of graphene and their various applications. However, the coupling between mechanical motion and charge transport has not been explored in graphene. Herein, we studied the mechanical properties of a suspended 50 nm wide graphene nanoribbon, which also acts as a single-electron transistor (SET) at low temperatures. Using the SET as a sensitive detector, we found that the resonance frequency could be tuned from 82 MHz to 100 MHz and the quality factor exceeded 30 000. The strong charge-mechanical coupling was demonstrated by observing the SET induced ∼140 kHz resonance frequency shifts and mechanical damping. We also found that the SET can enhance the nonlinearity of the resonator. Our SET-coupled graphene mechanical resonator could approach an ultra-sensitive mass resolution of ∼0.55 × 10(-21) g and a force sensitivity of ∼1.9 × 10(-19) N (Hz)(-1/2), and can be further improved. These properties indicate that our device is a good platform for both fundamental physical studies and potential applications.

  8. Homeostatic plasticity for single node delay-coupled reservoir computing.

    PubMed

    Toutounji, Hazem; Schumacher, Johannes; Pipa, Gordon

    2015-06-01

    Supplementing a differential equation with delays results in an infinite-dimensional dynamical system. This property provides the basis for a reservoir computing architecture, where the recurrent neural network is replaced by a single nonlinear node, delay-coupled to itself. Instead of the spatial topology of a network, subunits in the delay-coupled reservoir are multiplexed in time along one delay span of the system. The computational power of the reservoir is contingent on this temporal multiplexing. Here, we learn optimal temporal multiplexing by means of a biologically inspired homeostatic plasticity mechanism. Plasticity acts locally and changes the distances between the subunits along the delay, depending on how responsive these subunits are to the input. After analytically deriving the learning mechanism, we illustrate its role in improving the reservoir's computational power. To this end, we investigate, first, the increase of the reservoir's memory capacity. Second, we predict a NARMA-10 time series, showing that plasticity reduces the normalized root-mean-square error by more than 20%. Third, we discuss plasticity's influence on the reservoir's input-information capacity, the coupling strength between subunits, and the distribution of the readout coefficients.

  9. Hydrodynamic chromatography coupled with single particle-inductively coupled plasma mass spectrometry for investigating nanoparticles agglomerates.

    PubMed

    Rakcheev, Denis; Philippe, Allan; Schaumann, Gabriele E

    2013-11-19

    Studying the environmental fate of engineered or natural colloids requires efficient methods for measuring their size and quantifying them in the environment. For example, an ideal method should maintain its correctness, accuracy, reproducibility, and robustness when applied to samples contained in complex matrixes and distinguish the target particles from the natural colloidal background signals. Since it is expected that a large portion of nanoparticles will form homo- or heteroagglomerates when released into environmental media, it is necessary to differentiate agglomerates from primary particles. At present, most sizing techniques do not fulfill these requirements. In this study, we used online coupling of two promising complementary sizing techniques: hydrodynamic chromatography (HDC) and single-particle ICPMS analysis to analyze gold nanoparticles agglomerated under controlled conditions. We used the single-particle mode of the ICPMS detector to detect single particles eluted from an HDC-column and determine a mass and an effective diameter for each particle using a double calibration approach. The average agglomerate relative density and fractal dimension were calculated using these data and used to follow the morphological evolution of agglomerates over time during the agglomeration process. The results demonstrate the ability of HDC coupled to single-particle analysis to identify and characterize nanoparticle homoagglomerates and is a very promising technique for the analysis of colloids in complex media.

  10. Monolithically integrated single quantum dots coupled to bowtie nanoantennas

    NASA Astrophysics Data System (ADS)

    Lyamkina, A. A.; Schraml, K.; Regler, A.; Schalk, M.; Bakarov, A. K.; Toropov, A. I.; Moshchenko, S. P.; Kaniber, Michael

    2016-12-01

    Deterministically integrating semiconductor quantum emitters with plasmonic nano-devices paves the way towards chip-scale integrable, true nanoscale quantum photonics technologies. For this purpose, stable and bright semiconductor emitters are needed, which moreover allow for CMOS-compatibility and optical activity in the telecommunication band. Here, we demonstrate strongly enhanced light-matter coupling of single near-surface ($<10\\,nm$) InAs quantum dots monolithically integrated into electromagnetic hot-spots of sub-wavelength sized metal nanoantennas. The antenna strongly enhances the emission intensity of single quantum dots by up to $\\sim16\\times$, an effect accompanied by an up to $3.4\\times$ Purcell-enhanced spontaneous emission rate. Moreover, the emission is strongly polarised along the antenna axis with degrees of linear polarisation up to $\\sim85\\,\\%$. The results unambiguously demonstrate the efficient coupling of individual quantum dots to state-of-the-art nanoantennas. Our work provides new perspectives for the realisation of quantum plasmonic sensors, step-changing photovoltaic devices, bright and ultrafast quantum light sources and efficent nano-lasers.

  11. Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations

    SciTech Connect

    Wykes, M. Parambil, R.; Gierschner, J.; Beljonne, D.

    2015-09-21

    Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

  12. Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations.

    PubMed

    Wykes, M; Parambil, R; Beljonne, D; Gierschner, J

    2015-09-21

    Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

  13. Vibronic coupling in molecular crystals: A Franck-Condon Herzberg-Teller model of H-aggregate fluorescence based on quantum chemical cluster calculations

    NASA Astrophysics Data System (ADS)

    Wykes, M.; Parambil, R.; Beljonne, D.; Gierschner, J.

    2015-09-01

    Here, we present a general approach to treating vibronic coupling in molecular crystals based on atomistic simulations of large clusters. Such clusters comprise model aggregates treated at the quantum chemical level embedded within a realistic environment treated at the molecular mechanics level. As we calculate ground and excited state equilibrium geometries and vibrational modes of model aggregates, our approach is able to capture effects arising from coupling to intermolecular degrees of freedom, absent from existing models relying on geometries and normal modes of single molecules. Using the geometries and vibrational modes of clusters, we are able to simulate the fluorescence spectra of aggregates for which the lowest excited state bears negligible oscillator strength (as is the case, e.g., ideal H-aggregates) by including both Franck-Condon (FC) and Herzberg-Teller (HT) vibronic transitions. The latter terms allow the adiabatic excited state of the cluster to couple with vibrations in a perturbative fashion via derivatives of the transition dipole moment along nuclear coordinates. While vibronic coupling simulations employing FC and HT terms are well established for single-molecules, to our knowledge this is the first time they are applied to molecular aggregates. Here, we apply this approach to the simulation of the low-temperature fluorescence spectrum of para-distyrylbenzene single-crystal H-aggregates and draw comparisons with coarse-grained Frenkel-Holstein approaches previously extensively applied to such systems.

  14. Is It Possible To Obtain Coupled Cluster Quality Energies at near Density Functional Theory Cost? Domain-Based Local Pair Natural Orbital Coupled Cluster vs Modern Density Functional Theory.

    PubMed

    Liakos, Dimitrios G; Neese, Frank

    2015-09-08

    The recently developed domain-based local pair natural orbital coupled cluster theory with single, double, and perturbative triple excitations (DLPNO-CCSD(T)) delivers results that are closely approaching those of the parent canonical coupled cluster method at a small fraction of the computational cost. A recent extended benchmark study established that, depending on the three main truncation thresholds, it is possible to approach the canonical CCSD(T) results within 1 kJ (default setting, TightPNO), 1 kcal/mol (default setting, NormalPNO), and 2-3 kcal (default setting, LoosePNO). Although thresholds for calculations with TightPNO are 2-4 times slower than those based on NormalPNO thresholds, they are still many orders of magnitude faster than canonical CCSD(T) calculations, even for small and medium sized molecules where there is little locality. The computational effort for the coupled cluster step scales nearly linearly with system size. Since, in many instances, the coupled cluster step in DLPNO-CCSD(T) is cheaper or at least not much more expensive than the preceding Hartree-Fock calculation, it is useful to compare the method against modern density functional theory (DFT), which requires an effort comparable to that of Hartree-Fock theory (at least if Hartree-Fock exchange is part of the functional definition). Double hybrid density functionals (DHDF's) even require a MP2-like step. The purpose of this article is to evaluate the cost vs accuracy ratio of DLPNO-CCSD(T) against modern DFT (including the PBE, B3LYP, M06-2X, B2PLYP, and B2GP-PLYP functionals and, where applicable, their van der Waals corrected counterparts). To eliminate any possible bias in favor of DLPNO-CCSD(T), we have chosen established benchmark sets that were specifically proposed for evaluating DFT functionals. It is demonstrated that DLPNO-CCSD(T) with any of the three default thresholds is more accurate than any of the DFT functionals. Furthermore, using the aug-cc-pVTZ basis set and

  15. Chemical physics without the Born-Oppenheimer approximation: The molecular coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Monkhorst, Hendrik J.

    1987-08-01

    The Born-Oppenheimer (BO) and Born-Huang (BH) treatments of molecular eigenstates are reexamined. It is argued that in application of the BO approximation to nonrigid molecules and chemical dynamics involving single potential-energy surfaces (PES's), errors on the order of tens of percents can easily occur in many computed properties. Introduction of a BH expansion (in BO states) will always lead to poor convergence when the BO approximation fails; its diagonal (or adiabatic) approximation will not change this situation. The main problem in the above applications is the absence of well-developed, well-separated minima in the PES (or no minima at all). Inspired by a non-BO view of a molecule by Essén [Int. J. Quantum Chem. 12, 721 (1977)], a molecular coupled-cluster (MCC) method is formulated. An Essén molecule consists of neutral subunits (``atoms''), weakly interacting (``bonds'') in some spatial arrangement (``structure''). The quasiseparation in collective and individual motions within the molecule comes about by virtue of the virial theorem, not the smallness of the electron-to-nuclear mass ratio. The MCC method not only should converge well in the cluster sizes, but it also is capable of describing electronic shell and molecular geometric structures. It can be viewed as the workable formalism for Essén's physical picture of a molecule. The time-independent and time-dependent versions are described. The latter one is useful for scattering, chemical dynamics, laser chemistry, half-collisions, and any other phenomena that can be described as the time evolution of many-particle wave packets. Close relationship to time-dependent Hartree-Fock theory exists. A few implementational aspects are discussed, such as symmetry, conservation laws, approximations, numerical techniques, as well as a possible relation with a non-BO PES. Appendixes contain mathematical details.

  16. The coupled cluster approach with a hybrid treatment of connected triple excitations based on the restricted Hartree-Fock reference.

    PubMed

    Shen, Jun; Kou, Zhuangfei; Xu, Enhua; Li, Shuhua

    2011-01-28

    A generalization of the coupled cluster (CC) singles, doubles, and a hybrid treatment of connected triples [denoted as CCSD(T)-h] [Shen et al., J. Chem. Phys. 132, 114115 (2010)] to the restricted Hartree-Fock (RHF) reference is presented. In this approach, active (or pseudoactive) RHF orbitals are constructed automatically by performing unitary transformations of canonical RHF orbitals so that they spatially mimic the natural orbitals of the unrestricted Hartree-Fock reference. The present RHF-based CCSD(T)-h approach has been applied to study the potential energy surfaces in several typical bond breaking processes and the singlet-triplet gaps in a diradical (HFH)(-1). For all systems under study, the overall performance of CCSD(T)-h is very close to that of the corresponding CCSD(T) (CC singles, doubles, and triples), and much better than that of CCSD(T) (CC singles, doubles, and perturbative triples).

  17. Entangled states decoherence in coupled molecular spin clusters

    NASA Astrophysics Data System (ADS)

    Troiani, Filippo; Szallas, Attila; Bellini, Valerio; Affronte, Marco

    2010-03-01

    Localized electron spins in solid-state systems are widely investigated as potential building blocks of quantum devices and computers. While most efforts in the field have been focused on semiconductor low-dimensional structures, molecular antiferromagnets were recently recognized as alternative implementations of effective few-level spin systems. Heterometallic, Cr-based spin rings behave as effective spin-1/2 systems at low temperature and show long decoherence times [1]; besides, they can be chemically linked and magnetically coupled in a controllable fascion [2]. Here, we theoretically investigate the decoherence of the Bell states in such ring dimers, resulting from hyperfine interactions with nuclear spins. Based on a microscopic description of the molecules [3], we simulate the effect of inhomogeneous broadening, spectral diffusion and electron-nuclear entanglement on the electron-spin coherence, estimating the role of the different nuclei (and of possible chemical substitutions), as well as the effect of simple spin-echo sequences. References: [1] F. Troiani, et al., Phys. Rev. Lett. 94, 207208 (2005). [2] G. A. Timco, S: Carretta, F. Troiani et al., Nature Nanotech. 4, 173 (2009). [3] F. Troiani, V. Bellini, and M. Affronte, Phys. Rev. B 77, 054428 (2008).

  18. An efficient and near linear scaling pair natural orbital based local coupled cluster method

    NASA Astrophysics Data System (ADS)

    Riplinger, Christoph; Neese, Frank

    2013-01-01

    In previous publications, it was shown that an efficient local coupled cluster method with single- and double excitations can be based on the concept of pair natural orbitals (PNOs) [F. Neese, A. Hansen, and D. G. Liakos, J. Chem. Phys. 131, 064103 (2009), 10.1063/1.3173827]. The resulting local pair natural orbital-coupled-cluster single double (LPNO-CCSD) method has since been proven to be highly reliable and efficient. For large molecules, the number of amplitudes to be determined is reduced by a factor of 105-106 relative to a canonical CCSD calculation on the same system with the same basis set. In the original method, the PNOs were expanded in the set of canonical virtual orbitals and single excitations were not truncated. This led to a number of fifth order scaling steps that eventually rendered the method computationally expensive for large molecules (e.g., >100 atoms). In the present work, these limitations are overcome by a complete redesign of the LPNO-CCSD method. The new method is based on the combination of the concepts of PNOs and projected atomic orbitals (PAOs). Thus, each PNO is expanded in a set of PAOs that in turn belong to a given electron pair specific domain. In this way, it is possible to fully exploit locality while maintaining the extremely high compactness of the original LPNO-CCSD wavefunction. No terms are dropped from the CCSD equations and domains are chosen conservatively. The correlation energy loss due to the domains remains below <0.05%, which implies typically 15-20 but occasionally up to 30 atoms per domain on average. The new method has been given the acronym DLPNO-CCSD ("domain based LPNO-CCSD"). The method is nearly linear scaling with respect to system size. The original LPNO-CCSD method had three adjustable truncation thresholds that were chosen conservatively and do not need to be changed for actual applications. In the present treatment, no additional truncation parameters have been introduced. Any additional truncation

  19. Recent Advances in Open-Shell Perturbation Theory and Coupled-Cluster Theory

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Comparisons of various recently developed open-shell RHF perturbation theories will be presented. Among the aspects considered are spin-contamination, computational cost, and quality of numerical results. In addition, a new approach to avoid the disk storage and I/O bottlenecks in large scale coupled-cluster calculations will be discussed.

  20. Recent Advances in Open-Shell Perturbation Theory and Coupled-Cluster Theory

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    Comparisons of various recently developed open-shell RHF perturbation theories will be presented. Among the aspects considered are spin-contamination, computational cost, and quality of numerical results. In addition, a new approach to avoid the disk storage and I/O bottlenecks in large scale coupled-cluster calculations will be discussed.

  1. Multireference linearized coupled cluster theory for strongly correlated systems using matrix product states

    NASA Astrophysics Data System (ADS)

    Sharma, Sandeep; Alavi, Ali

    2015-09-01

    We propose a multireference linearized coupled cluster theory using matrix product states (MPSs-LCC) which provides remarkably accurate ground-state energies, at a computational cost that has the same scaling as multireference configuration interaction singles and doubles, for a wide variety of electronic Hamiltonians. These range from first-row dimers at equilibrium and stretched geometries to highly multireference systems such as the chromium dimer and lattice models such as periodic two-dimensional 1-band and 3-band Hubbard models. The MPS-LCC theory shows a speed up of several orders of magnitude over the usual Density Matrix Renormalization Group (DMRG) algorithm while delivering energies in excellent agreement with converged DMRG calculations. Also, in all the benchmark calculations presented here, MPS-LCC outperformed the commonly used multi-reference quantum chemistry methods in some cases giving energies in excess of an order of magnitude more accurate. As a size-extensive method that can treat large active spaces, MPS-LCC opens up the use of multireference quantum chemical techniques in strongly correlated ab initio Hamiltonians, including two- and three-dimensional solids.

  2. Parallel implementation of multireference coupled-cluster theories based on the reference-level parallelism

    SciTech Connect

    Brabec, Jiri; Pittner, Jiri; van Dam, Hubertus JJ; Apra, Edoardo; Kowalski, Karol

    2012-02-01

    A novel algorithm for implementing general type of multireference coupled-cluster (MRCC) theory based on the Jeziorski-Monkhorst exponential Ansatz [B. Jeziorski, H.J. Monkhorst, Phys. Rev. A 24, 1668 (1981)] is introduced. The proposed algorithm utilizes processor groups to calculate the equations for the MRCC amplitudes. In the basic formulation each processor group constructs the equations related to a specific subset of references. By flexible choice of processor groups and subset of reference-specific sufficiency conditions designated to a given group one can assure optimum utilization of available computing resources. The performance of this algorithm is illustrated on the examples of the Brillouin-Wigner and Mukherjee MRCC methods with singles and doubles (BW-MRCCSD and Mk-MRCCSD). A significant improvement in scalability and in reduction of time to solution is reported with respect to recently reported parallel implementation of the BW-MRCCSD formalism [J.Brabec, H.J.J. van Dam, K. Kowalski, J. Pittner, Chem. Phys. Lett. 514, 347 (2011)].

  3. Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

    NASA Technical Reports Server (NTRS)

    Barnes, Leslie A.; Lindh, Roland

    1994-01-01

    A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method.

  4. Perturbative approximation to hybrid equation of motion coupled cluster/effective fragment potential method

    SciTech Connect

    Ghosh, Debashree

    2014-03-07

    Hybrid quantum mechanics/molecular mechanics (QM/MM) methods provide an attractive way to closely retain the accuracy of the QM method with the favorable computational scaling of the MM method. Therefore, it is not surprising that QM/MM methods are being increasingly used for large chemical/biological systems. Hybrid equation of motion coupled cluster singles doubles/effective fragment potential (EOM-CCSD/EFP) methods have been developed over the last few years to understand the effect of solvents and other condensed phases on the electronic spectra of chromophores. However, the computational cost of this approach is still dominated by the steep scaling of the EOM-CCSD method. In this work, we propose and implement perturbative approximations to the EOM-CCSD method in this hybrid scheme to reduce the cost of EOM-CCSD/EFP. The timings and accuracy of this hybrid approach is tested for calculation of ionization energies, excitation energies, and electron affinities of microsolvated nucleic acid bases (thymine and cytosine), phenol, and phenolate.

  5. Natural triple excitations in local coupled cluster calculations with pair natural orbitals

    NASA Astrophysics Data System (ADS)

    Riplinger, Christoph; Sandhoefer, Barbara; Hansen, Andreas; Neese, Frank

    2013-10-01

    In this work, the extension of the previously developed domain based local pair-natural orbital (DLPNO) based singles- and doubles coupled cluster (DLPNO-CCSD) method to perturbatively include connected triple excitations is reported. The development is based on the concept of triples-natural orbitals that span the joint space of the three pair natural orbital (PNO) spaces of the three electron pairs that are involved in the calculation of a given triple-excitation contribution. The truncation error is very smooth and can be significantly reduced through extrapolation to the zero threshold. However, the extrapolation procedure does not improve relative energies. The overall computational effort of the method is asymptotically linear with the system size O(N). Actual linear scaling has been confirmed in test calculations on alkane chains. The accuracy of the DLPNO-CCSD(T) approximation relative to semicanonical CCSD(T0) is comparable to the previously developed DLPNO-CCSD method relative to canonical CCSD. Relative energies are predicted with an average error of approximately 0.5 kcal/mol for a challenging test set of medium sized organic molecules. The triples correction typically adds 30%-50% to the overall computation time. Thus, very large systems can be treated on the basis of the current implementation. In addition to the linear C150H302 (452 atoms, >8800 basis functions) we demonstrate the first CCSD(T) level calculation on an entire protein, Crambin with 644 atoms, and more than 6400 basis functions.

  6. Investigating tunnel and above-barrier ionization using complex-scaled coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Jagau, Thomas-C.

    2016-11-01

    The theory and implementation of the complex-scaled coupled-cluster method with singles and doubles excitations (cs-CCSD) for studying resonances induced by static electric fields are presented. Within this framework, Stark shifts and ionization rates are obtained directly from the real and imaginary parts of the complex energy. The method is applied to the ground states of hydrogen, helium, lithium, beryllium, neon, argon, and carbon at varying field strengths. Complex-scaled Hartree-Fock, second-order many-body perturbation theory, and CCSD results are reported and analyzed with a focus on the impact of electron correlation on the ionization process. cs-CCSD calculations with suitably augmented standard Gaussian basis sets are found to deliver accurate strong-field ionization rates over a range of six orders of magnitude. The field-induced resonances are characterized beyond energy and ionization rate through their dipole moments, second moments, as well as Dyson orbitals and comparisons are drawn to autoionizing and autodetaching resonances. Marked differences are found between the tunneling and above-barrier regimes allowing for a clear distinction of the two mechanisms.

  7. Simulation of the photodetachment spectrum of HHfO- using coupled-cluster calculations

    NASA Astrophysics Data System (ADS)

    Mok, Daniel K. W.; Dyke, John M.; Lee, Edmond P. F.

    2016-12-01

    The photodetachment spectrum of HHfO- was simulated using restricted-spin coupled-cluster single-double plus perturbative triple {RCCSD(T)} calculations performed on the ground electronic states of HHfO and HHfO-, employing basis sets of up to quintuple-zeta quality. The computed RCCSD(T) electron affinity of 1.67 ± 0.02 eV at the complete basis set limit, including Hf 5s25p6 core correlation and zero-point energy corrections, agrees well with the experimental value of 1.70 ± 0.05 eV from a recent photodetachment study [X. Li et al., J. Chem. Phys. 136, 154306 (2012)]. For the simulation, Franck-Condon factors were computed which included allowances for anharmonicity and Duschinsky rotation. Comparisons between simulated and experimental spectra confirm the assignments of the molecular carrier and electronic states involved but suggest that the experimental vibrational structure has suffered from poor signal-to-noise ratio. An alternative assignment of the vibrational structure to that suggested in the experimental work is presented.

  8. Multireference linearized coupled cluster theory for strongly correlated systems using matrix product states

    SciTech Connect

    Sharma, Sandeep; Alavi, Ali

    2015-09-14

    We propose a multireference linearized coupled cluster theory using matrix product states (MPSs-LCC) which provides remarkably accurate ground-state energies, at a computational cost that has the same scaling as multireference configuration interaction singles and doubles, for a wide variety of electronic Hamiltonians. These range from first-row dimers at equilibrium and stretched geometries to highly multireference systems such as the chromium dimer and lattice models such as periodic two-dimensional 1-band and 3-band Hubbard models. The MPS-LCC theory shows a speed up of several orders of magnitude over the usual Density Matrix Renormalization Group (DMRG) algorithm while delivering energies in excellent agreement with converged DMRG calculations. Also, in all the benchmark calculations presented here, MPS-LCC outperformed the commonly used multi-reference quantum chemistry methods in some cases giving energies in excess of an order of magnitude more accurate. As a size-extensive method that can treat large active spaces, MPS-LCC opens up the use of multireference quantum chemical techniques in strongly correlated ab initio Hamiltonians, including two- and three-dimensional solids.

  9. A new approach to approximate equation-of-motion coupled cluster with triple excitations

    NASA Astrophysics Data System (ADS)

    Matthews, Devin A.; Stanton, John F.

    2016-09-01

    Accurate methods for excited, ionized, and electron-attached states are critical to the study of many chemical species such as reactive intermediates, radicals, and ionized systems. The equation-of-motion coupled cluster singles, doubles, and triples (EOM-CCSDT) family of methods is very accurate (roughly similar in accuracy as for CCSDT calculations of the ground state), but the computational cost scales iteratively as the eighth power of the system size. Many approximations already exist, although most either correct only the excited state or require an iterative 𝒪(n7) procedure which can also be prohibitively expensive. In this paper, new methods, termed EOM-CCSD(T)(a) and EOM-CCSD(T)(a)*, are proposed which correct both the ground and excited states based on a shared effective Hamiltonian, and the latter of which includes only non-iterative corrections to both the CCSD and EOM-CCSD energies. These methods are found to significantly improve the description of excited and ionized potential energy surfaces, equilibrium geometries, and harmonic frequencies; the accuracy is very close to that of full EOM-CCSDT.

  10. Experimental observation of chimera and cluster states in a minimal globally coupled network

    SciTech Connect

    Hart, Joseph D.; Bansal, Kanika; Murphy, Thomas E.; Roy, Rajarshi

    2016-09-15

    A “chimera state” is a dynamical pattern that occurs in a network of coupled identical oscillators when the symmetry of the oscillator population is broken into synchronous and asynchronous parts. We report the experimental observation of chimera and cluster states in a network of four globally coupled chaotic opto-electronic oscillators. This is the minimal network that can support chimera states, and our study provides new insight into the fundamental mechanisms underlying their formation. We use a unified approach to determine the stability of all the observed partially synchronous patterns, highlighting the close relationship between chimera and cluster states as belonging to the broader phenomenon of partial synchronization. Our approach is general in terms of network size and connectivity. We also find that chimera states often appear in regions of multistability between global, cluster, and desynchronized states.

  11. Experimental observation of chimera and cluster states in a minimal globally coupled network

    NASA Astrophysics Data System (ADS)

    Hart, Joseph D.; Bansal, Kanika; Murphy, Thomas E.; Roy, Rajarshi

    2016-09-01

    A "chimera state" is a dynamical pattern that occurs in a network of coupled identical oscillators when the symmetry of the oscillator population is broken into synchronous and asynchronous parts. We report the experimental observation of chimera and cluster states in a network of four globally coupled chaotic opto-electronic oscillators. This is the minimal network that can support chimera states, and our study provides new insight into the fundamental mechanisms underlying their formation. We use a unified approach to determine the stability of all the observed partially synchronous patterns, highlighting the close relationship between chimera and cluster states as belonging to the broader phenomenon of partial synchronization. Our approach is general in terms of network size and connectivity. We also find that chimera states often appear in regions of multistability between global, cluster, and desynchronized states.

  12. Experimental observation of chimera and cluster states in a minimal globally coupled network.

    PubMed

    Hart, Joseph D; Bansal, Kanika; Murphy, Thomas E; Roy, Rajarshi

    2016-09-01

    A "chimera state" is a dynamical pattern that occurs in a network of coupled identical oscillators when the symmetry of the oscillator population is broken into synchronous and asynchronous parts. We report the experimental observation of chimera and cluster states in a network of four globally coupled chaotic opto-electronic oscillators. This is the minimal network that can support chimera states, and our study provides new insight into the fundamental mechanisms underlying their formation. We use a unified approach to determine the stability of all the observed partially synchronous patterns, highlighting the close relationship between chimera and cluster states as belonging to the broader phenomenon of partial synchronization. Our approach is general in terms of network size and connectivity. We also find that chimera states often appear in regions of multistability between global, cluster, and desynchronized states.

  13. Assessment of the accuracy of coupled cluster perturbation theory for open-shell systems. I. Triples expansions.

    PubMed

    Eriksen, Janus J; Matthews, Devin A; Jørgensen, Poul; Gauss, Jürgen

    2016-05-21

    The accuracy at which total energies of open-shell atoms and organic radicals may be calculated is assessed for selected coupled cluster perturbative triples expansions, all of which augment the coupled cluster singles and doubles (CCSD) energy by a non-iterative correction for the effect of triple excitations. Namely, the second- through sixth-order models of the recently proposed CCSD(T-n) triples series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)] are compared to the acclaimed CCSD(T) model for both unrestricted as well as restricted open-shell Hartree-Fock (UHF/ROHF) reference determinants. By comparing UHF- and ROHF-based statistical results for a test set of 18 modest-sized open-shell species with comparable RHF-based results, no behavioral differences are observed for the higher-order models of the CCSD(T-n) series in their correlated descriptions of closed- and open-shell species. In particular, we find that the convergence rate throughout the series towards the coupled cluster singles, doubles, and triples (CCSDT) solution is identical for the two cases. For the CCSD(T) model, on the other hand, not only its numerical consistency, but also its established, yet fortuitous cancellation of errors breaks down in the transition from closed- to open-shell systems. The higher-order CCSD(T-n) models (orders n > 3) thus offer a consistent and significant improvement in accuracy relative to CCSDT over the CCSD(T) model, equally for RHF, UHF, and ROHF reference determinants, albeit at an increased computational cost.

  14. Assessment of the accuracy of coupled cluster perturbation theory for open-shell systems. I. Triples expansions

    NASA Astrophysics Data System (ADS)

    Eriksen, Janus J.; Matthews, Devin A.; Jørgensen, Poul; Gauss, Jürgen

    2016-05-01

    The accuracy at which total energies of open-shell atoms and organic radicals may be calculated is assessed for selected coupled cluster perturbative triples expansions, all of which augment the coupled cluster singles and doubles (CCSD) energy by a non-iterative correction for the effect of triple excitations. Namely, the second- through sixth-order models of the recently proposed CCSD(T-n) triples series [J. J. Eriksen et al., J. Chem. Phys. 140, 064108 (2014)] are compared to the acclaimed CCSD(T) model for both unrestricted as well as restricted open-shell Hartree-Fock (UHF/ROHF) reference determinants. By comparing UHF- and ROHF-based statistical results for a test set of 18 modest-sized open-shell species with comparable RHF-based results, no behavioral differences are observed for the higher-order models of the CCSD(T-n) series in their correlated descriptions of closed- and open-shell species. In particular, we find that the convergence rate throughout the series towards the coupled cluster singles, doubles, and triples (CCSDT) solution is identical for the two cases. For the CCSD(T) model, on the other hand, not only its numerical consistency, but also its established, yet fortuitous cancellation of errors breaks down in the transition from closed- to open-shell systems. The higher-order CCSD(T-n) models (orders n > 3) thus offer a consistent and significant improvement in accuracy relative to CCSDT over the CCSD(T) model, equally for RHF, UHF, and ROHF reference determinants, albeit at an increased computational cost.

  15. Coupled Deep Autoencoder for Single Image Super-Resolution.

    PubMed

    Zeng, Kun; Yu, Jun; Wang, Ruxin; Li, Cuihua; Tao, Dacheng

    2017-01-01

    Sparse coding has been widely applied to learning-based single image super-resolution (SR) and has obtained promising performance by jointly learning effective representations for low-resolution (LR) and high-resolution (HR) image patch pairs. However, the resulting HR images often suffer from ringing, jaggy, and blurring artifacts due to the strong yet ad hoc assumptions that the LR image patch representation is equal to, is linear with, lies on a manifold similar to, or has the same support set as the corresponding HR image patch representation. Motivated by the success of deep learning, we develop a data-driven model coupled deep autoencoder (CDA) for single image SR. CDA is based on a new deep architecture and has high representational capability. CDA simultaneously learns the intrinsic representations of LR and HR image patches and a big-data-driven function that precisely maps these LR representations to their corresponding HR representations. Extensive experimentation demonstrates the superior effectiveness and efficiency of CDA for single image SR compared to other state-of-the-art methods on Set5 and Set14 datasets.

  16. Coupling of single NV center to adiabatically tapered optical single mode fiber

    NASA Astrophysics Data System (ADS)

    Vorobyov, Vadim V.; Soshenko, Vladimir V.; Bolshedvorskii, Stepan V.; Javadzade, Javid; Lebedev, Nikolay; Smolyaninov, Andrey N.; Sorokin, Vadim N.; Akimov, Alexey V.

    2016-12-01

    We demonstrated a simple and reliable technique of coupling diamond nanocrystal containing NV center to tapered optical fiber. The NV center emission was collected by the fiber via nearfield interaction between NV center and the tapered portion of the fiber. Single photon statistics was demonstrated at the fiber end as well as up to 3 times improvement in collection efficiency with respect to our confocal microscope. Also, we carefully studied fluorescence of the fiber itself and were able to suppress it to the level lower than single photon emission from the NV center.

  17. Performance of the coupled cluster and DFT methods for through-space magnetic interactions of nitroxide dimer

    NASA Astrophysics Data System (ADS)

    Saito, Toru; Ito, Akira; Watanabe, Tomohiro; Kawakami, Takashi; Okumura, Mitsutaka; Yamaguchi, Kizashi

    2012-07-01

    We have performed comparisons of several theoretical methods focusing on the through-space interactions of the F2 molecule and nitroxide (dihydronitrosyl) dimer based on the exchange coupling constant. The restricted Hartree-Fock (RHF) based coupled cluster full singles, doubles, and triples (RHF-CCSDT) and approximations to it do not show the exponential decay with increasing intermolecular distance for both antiferromagnetic and ferromagnetic interactions. On the other hand, Mukherjee's multireference CCSD (MkCCSD) method and the unrestricted HF (UHF) based CCSD (UHF-CCSD) with an approximate spin-projection (AP) method give reliable results. The present benchmark calculations are expected to contribute to the selection of an appropriate density functional theory (DFT) exchange-correlation functionals for larger systems.

  18. Renormalized coupled cluster approaches in the cluster-in-molecule framework: predicting vertical electron binding energies of the anionic water clusters (H2O)(n)(-).

    PubMed

    Xu, Peng; Gordon, Mark S

    2014-09-04

    Anionic water clusters are generally considered to be extremely challenging to model using fragmentation approaches due to the diffuse nature of the excess electron distribution. The local correlation coupled cluster (CC) framework cluster-in-molecule (CIM) approach combined with the completely renormalized CR-CC(2,3) method [abbreviated CIM/CR-CC(2,3)] is shown to be a viable alternative for computing the vertical electron binding energies (VEBE). CIM/CR-CC(2,3) with the threshold parameter ζ set to 0.001, as a trade-off between accuracy and computational cost, demonstrates the reliability of predicting the VEBE, with an average percentage error of ∼15% compared to the full ab initio calculation at the same level of theory. The errors are predominantly from the electron correlation energy. The CIM/CR-CC(2,3) approach provides the ease of a black-box type calculation with few threshold parameters to manipulate. The cluster sizes that can be studied by high-level ab initio methods are significantly increased in comparison with full CC calculations. Therefore, the VEBE computed by the CIM/CR-CC(2,3) method can be used as benchmarks for testing model potential approaches in small-to-intermediate-sized water clusters.

  19. Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies

    DOE PAGES

    Piecuch, Piotr; Hansen, Jared A.; Ajala, Adeayo O.

    2015-09-15

    When vertical energies are excited for a comprehensive test set of about 150 singlet excited states of 28 medium-sized organic molecules computed using two variants of the completely renormalised (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as δ-CR-EOMCCSD(T), and the analogous two variants of the newer, left-eigenstate δ-CR-EOMCC(2,3) approach are benchmarked against the previously published CASPT2, CC3, and EOMCCSDT-3 results, as well as the suggested theoretical best estimate (TBE) values. The δ-CR-EOMCC approaches are also used to identify and characterise about 50 additional excited states, including several states having substantial two-electron excitation components, whichmore » have not been found in the previous work and which can be used in future benchmark studies. We demonstrated that the non-iterative triples corrections to the EOMCCSD excitation energies defining the relatively inexpensive, single-reference, black-box δ-CR-EOMCC approaches provide significant improvements in the EOMCCSD data, while closely matching the results of the iterative and considerably more expensive CC3 and EOMCCSDT-3 calculations and their CASPT2 and TBE counterparts. It is also shown that the δ-CR-EOMCC methods, especially δ-CR-EOMCC(2,3), are capable of bringing the results of the CC3 and EOMCCSDT-3 calculations to a closer agreement with the CASPT2 and TBE data, demonstrating the utility of the cost-effective δ-CR-EOMCC methods in applications involving molecular electronic spectra. Finally, we show that there may exist a relationship between the magnitude of the triples corrections defining δ-CR-EOMCC approaches and the reduced excitation level diagnostic resulting from EOMCCSD.« less

  20. Benchmarking the completely renormalised equation-of-motion coupled-cluster approaches for vertical excitation energies

    SciTech Connect

    Piecuch, Piotr; Hansen, Jared A.; Ajala, Adeayo O.

    2015-09-15

    When vertical energies are excited for a comprehensive test set of about 150 singlet excited states of 28 medium-sized organic molecules computed using two variants of the completely renormalised (CR) equation-of-motion (EOM) coupled-cluster (CC) method with singles, doubles, and non-iterative triples, abbreviated as δ-CR-EOMCCSD(T), and the analogous two variants of the newer, left-eigenstate δ-CR-EOMCC(2,3) approach are benchmarked against the previously published CASPT2, CC3, and EOMCCSDT-3 results, as well as the suggested theoretical best estimate (TBE) values. The δ-CR-EOMCC approaches are also used to identify and characterise about 50 additional excited states, including several states having substantial two-electron excitation components, which have not been found in the previous work and which can be used in future benchmark studies. We demonstrated that the non-iterative triples corrections to the EOMCCSD excitation energies defining the relatively inexpensive, single-reference, black-box δ-CR-EOMCC approaches provide significant improvements in the EOMCCSD data, while closely matching the results of the iterative and considerably more expensive CC3 and EOMCCSDT-3 calculations and their CASPT2 and TBE counterparts. It is also shown that the δ-CR-EOMCC methods, especially δ-CR-EOMCC(2,3), are capable of bringing the results of the CC3 and EOMCCSDT-3 calculations to a closer agreement with the CASPT2 and TBE data, demonstrating the utility of the cost-effective δ-CR-EOMCC methods in applications involving molecular electronic spectra. Finally, we show that there may exist a relationship between the magnitude of the triples corrections defining δ-CR-EOMCC approaches and the reduced excitation level diagnostic resulting from EOMCCSD.

  1. A pair natural orbital implementation of the coupled cluster model CC2 for excitation energies

    NASA Astrophysics Data System (ADS)

    Helmich, Benjamin; Hättig, Christof

    2013-08-01

    We demonstrate how to extend the pair natural orbital (PNO) methodology for excited states, presented in a previous work for the perturbative doubles correction to configuration interaction singles (CIS(D)), to iterative coupled cluster methods such as the approximate singles and doubles model CC2. The original O(N^5) scaling of the PNO construction is reduced by using orbital-specific virtuals (OSVs) as an intermediate step without spoiling the initial accuracy of the PNO method. Furthermore, a slower error convergence for charge-transfer states is analyzed and resolved by a numerical Laplace transformation during the PNO construction, so that an equally accurate treatment of local and charge-transfer excitations is achieved. With state-specific truncated PNO expansions, the eigenvalue problem is solved by combining the Davidson algorithm with deflation to project out roots that have already been determined and an automated refresh with a generation of new PNOs to achieve self-consistency of the PNO space. For a large test set, we found that truncation errors for PNO-CC2 excitation energies are only slightly larger than for PNO-CIS(D). The computational efficiency of PNO-CC2 is demonstrated for a large organic dye, where a reduction of the doubles space by a factor of more than 1000 is obtained compared to the canonical calculation. A compression of the doubles space by a factor 30 is achieved by a unified OSV space only. Moreover, calculations with the still preliminary PNO-CC2 implementation on a series of glycine oligomers revealed an early break even point with a canonical RI-CC2 implementation between 100 and 300 basis functions.

  2. A pair natural orbital implementation of the coupled cluster model CC2 for excitation energies.

    PubMed

    Helmich, Benjamin; Hättig, Christof

    2013-08-28

    We demonstrate how to extend the pair natural orbital (PNO) methodology for excited states, presented in a previous work for the perturbative doubles correction to configuration interaction singles (CIS(D)), to iterative coupled cluster methods such as the approximate singles and doubles model CC2. The original O(N(5)) scaling of the PNO construction is reduced by using orbital-specific virtuals (OSVs) as an intermediate step without spoiling the initial accuracy of the PNO method. Furthermore, a slower error convergence for charge-transfer states is analyzed and resolved by a numerical Laplace transformation during the PNO construction, so that an equally accurate treatment of local and charge-transfer excitations is achieved. With state-specific truncated PNO expansions, the eigenvalue problem is solved by combining the Davidson algorithm with deflation to project out roots that have already been determined and an automated refresh with a generation of new PNOs to achieve self-consistency of the PNO space. For a large test set, we found that truncation errors for PNO-CC2 excitation energies are only slightly larger than for PNO-CIS(D). The computational efficiency of PNO-CC2 is demonstrated for a large organic dye, where a reduction of the doubles space by a factor of more than 1000 is obtained compared to the canonical calculation. A compression of the doubles space by a factor 30 is achieved by a unified OSV space only. Moreover, calculations with the still preliminary PNO-CC2 implementation on a series of glycine oligomers revealed an early break even point with a canonical RI-CC2 implementation between 100 and 300 basis functions.

  3. Bridging Single- and Multireference Domains for Electron Correlation: Spin-Extended Coupled Electron Pair Approximation.

    PubMed

    Tsuchimochi, Takashi; Ten-No, Seiichiro

    2017-04-11

    We propose a size-consistent generalization of the recently developed spin-extended configuration interaction with singles and doubles (ECISD), where a CI wave function is explicitly spin-projected. The size-consistent effect is effectively incorporated by treating quadruples within the formulation of coupled electron pair approximation. As in coupled-cluster theory, quadruple excitations are approximated by a disconnected product of double excitations. Despite its conceptual similarity to the standard single-reference and multireference analogues, such a generalization requires careful derivation, as the spin-projected CI space is nonorthogonal and overcomplete. Although our methods generally yield better results than ECISD, size-consistency is only approximately retained because the action of a symmetry-projection operator is size-inconsistent. In this work, we focus on simple models where exclusion-principle-violating terms, which eliminate undesired contributions to the correlation effects, are either completely neglected or averaged. These models possess an orbital-invariant energy functional that is to be minimized by diagonalizing an energy-shifted effective Hamiltonian within the singles and doubles manifold. This allows for a straightforward generalization of the ECISD analytical gradients needed to determine molecular properties and geometric optimization. Given the multireference nature of the spin-projected Hartree-Fock method, the proposed approaches are expected to handle static correlation, unlike single-reference analogues. We critically assess the performance of our methods using dissociation curves of molecules, singlet-triplet splitting gaps, hyperfine coupling constants, and the chromium dimer. The size-consistency and size-extensivity of the methods are also discussed.

  4. Signal transduction across cellular membranes can be mediated by coupling of the clustering of anchored proteins in both leaflets

    NASA Astrophysics Data System (ADS)

    Yue, Tongtao; Zhang, Xianren

    2012-01-01

    One key question in signal transduction is how the signal is relayed from the outer leaflet of a cellular membrane to the inner leaflet. Using a simulation model, a mechanism for the mediation of signal transduction is proposed here in which the coupling between membrane proteins in different leaflets can be achieved by the clustering of anchored proteins, without recruiting transmembrane proteins. Depending on the hydrophobic length of the anchored proteins, three coupling patterns, including face-to-face clustering, interdigitated clustering, and weak-coupled clustering, are observed in this work. This observation provides a possible explanation of how a particular downstream signaling pathway is selected.

  5. The Effect of Approximating Some Molecular Integrals in Coupled-Cluster Calculations: Fundamental Frequencies and Rovibrational Spectroscopic Constants of Cyclopropenylidene

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.

    2005-01-01

    The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), has been used, in conjunction with approximate integral techniques, to compute highly accurate rovibrational spectroscopic constants of cyclopropenylidene, C3H2. The approximate integral technique was proposed in 1994 by Rendell and Lee in order to avoid disk storage and input/output bottlenecks, and today it will also significantly aid in the development of algorithms for distributed memory, massively parallel computer architectures. It is shown in this study that use of approximate integrals does not impact the accuracy of CCSD(T) calculations. In addition, the most accurate spectroscopic data yet for C3H2 is presented based on a CCSD(T)/cc-pVQZ quartic force field that is modified to include the effects of core-valence electron correlation. Cyclopropenylidene is of great astronomical and astrobiological interest because it is the smallest aromatic ringed compound to be positively identified in the interstellar medium, and is thus involved in the prebiotic processing of carbon and hydrogen. The singles and doubles coupled-cluster method that includes a perturbational estimate of

  6. Critical comparison of various connected quadruple excitation approximations in the coupled-cluster treatment of bond breaking

    NASA Astrophysics Data System (ADS)

    Musiał, Monika; Bartlett, Rodney J.

    2005-06-01

    To assess the limits of single-reference coupled-cluster (CC) methods for potential-energy surfaces, several methods have been considered for the inclusion of connected quadruple excitations. Most are based upon the factorized inclusion of the connected quadruple contribution (Qf) [J. Chem. Phys. 108, 9221 (1998)]. We compare the methods for the treatment of potential-energy curves for small molecules. These include CCSD(TQf), where the initial contributions of triple (T) and factorized quadruple excitations are added to coupled-cluster singles (S) and doubles (D), its generalization to CCSD(Q˜f), where instead of measuring their first contribution from orders in H, it is measured from orders in H˜=e-(T1+T2)He(T1+T2); renormalized approximations of both, and CCSD(2) defined in [J. Chem. Phys. 115, 2014 (2001)]. We also consider CCSDT, CCSDT(Qf), CCSDTQ, and CCSDTQP for comparison, where T, Q, and P indicate full triple, quadruple, and pentuple excitations, respectively. Illustrations for F2, the double bond breaking in water, and N2 are shown, including effects of quadruples on equilibrium geometries and vibrational frequencies. Despite the fact that no perturbative approximation, as opposed to an iterative approximation, should be able to separate a molecule correctly for a restricted-Hartree-Fock reference function, some of these higher-order approximations have a role to play in developing new, more robust procedures.

  7. Critical comparison of various connected quadruple excitation approximations in the coupled-cluster treatment of bond breaking.

    PubMed

    Musiał, Monika; Bartlett, Rodney J

    2005-06-08

    To assess the limits of single-reference coupled-cluster (CC) methods for potential-energy surfaces, several methods have been considered for the inclusion of connected quadruple excitations. Most are based upon the factorized inclusion of the connected quadruple contribution (Qf) [J. Chem. Phys. 108, 9221 (1998)]. We compare the methods for the treatment of potential-energy curves for small molecules. These include CCSD(TQf), where the initial contributions of triple (T) and factorized quadruple excitations are added to coupled-cluster singles (S) and doubles (D), its generalization to CCSD(TQf), where instead of measuring their first contribution from orders in H, it is measured from orders in H=e(-(T1+T2))He(T1+T2); renormalized approximations of both, and CCSD2 defined in [J. Chem. Phys. 115, 2014 (2001)]. We also consider CCSDT, CCSDT(Qf), CCSDTQ, and CCSDTQP for comparison, where T, Q, and P indicate full triple, quadruple, and pentuple excitations, respectively. Illustrations for F2, the double bond breaking in water, and N2 are shown, including effects of quadruples on equilibrium geometries and vibrational frequencies. Despite the fact that no perturbative approximation, as opposed to an iterative approximation, should be able to separate a molecule correctly for a restricted-Hartree-Fock reference function, some of these higher-order approximations have a role to play in developing new, more robust procedures.

  8. The Effect of Approximating Some Molecular Integrals in Coupled-Cluster Calculations: Fundamental Frequencies and Rovibrational Spectroscopic Constants of Cyclopropenylidene

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Dateo, Christopher E.

    2005-01-01

    The singles and doubles coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), has been used, in conjunction with approximate integral techniques, to compute highly accurate rovibrational spectroscopic constants of cyclopropenylidene, C3H2. The approximate integral technique was proposed in 1994 by Rendell and Lee in order to avoid disk storage and input/output bottlenecks, and today it will also significantly aid in the development of algorithms for distributed memory, massively parallel computer architectures. It is shown in this study that use of approximate integrals does not impact the accuracy of CCSD(T) calculations. In addition, the most accurate spectroscopic data yet for C3H2 is presented based on a CCSD(T)/cc-pVQZ quartic force field that is modified to include the effects of core-valence electron correlation. Cyclopropenylidene is of great astronomical and astrobiological interest because it is the smallest aromatic ringed compound to be positively identified in the interstellar medium, and is thus involved in the prebiotic processing of carbon and hydrogen. The singles and doubles coupled-cluster method that includes a perturbational estimate of

  9. Calcium Domains around Single and Clustered IP3 Receptors and Their Modulation by Buffers

    PubMed Central

    Rüdiger, S.; Nagaiah, Ch.; Warnecke, G.; Shuai, J.W.

    2010-01-01

    Abstract We study Ca2+ release through single and clustered IP3 receptor channels on the ER membrane under presence of buffer proteins. Our computational scheme couples reaction-diffusion equations and a Markovian channel model and allows our investigating the effects of buffer proteins on local calcium concentrations and channel gating. We find transient and stationary elevations of calcium concentrations around active channels and show how they determine release amplitude. Transient calcium domains occur after closing of isolated channels and constitute an important part of the channel's feedback. They cause repeated openings (bursts) and mediate increased release due to Ca2+ buffering by immobile proteins. Stationary domains occur during prolonged activity of clustered channels, where the spatial proximity of IP3Rs produces a distinct [Ca2+] scale (0.5–10 μM), which is smaller than channel pore concentrations (>100 μM) but larger than transient levels. While immobile buffer affects transient levels only, mobile buffers in general reduce both transient and stationary domains, giving rise to Ca2+ evacuation and biphasic modulation of release amplitude. Our findings explain recent experiments in oocytes and provide a general framework for the understanding of calcium signals. PMID:20655827

  10. Carbon X-ray absorption spectra of fluoroethenes and acetone: a study at the coupled cluster, density functional, and static-exchange levels of theory.

    PubMed

    Fransson, Thomas; Coriani, Sonia; Christiansen, Ove; Norman, Patrick

    2013-03-28

    Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger π-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to π∗-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate π∗-peak separations due to spectral compressions, a characteristic which is inherent to this

  11. Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory

    SciTech Connect

    Fransson, Thomas; Norman, Patrick; Coriani, Sonia; Christiansen, Ove

    2013-03-28

    Near carbon K-edge X-ray absorption fine structure spectra of a series of fluorine-substituted ethenes and acetone have been studied using coupled cluster and density functional theory (DFT) polarization propagator methods, as well as the static-exchange (STEX) approach. With the complex polarization propagator (CPP) implemented in coupled cluster theory, relaxation effects following the excitation of core electrons are accounted for in terms of electron correlation, enabling a systematic convergence of these effects with respect to electron excitations in the cluster operator. Coupled cluster results have been used as benchmarks for the assessment of propagator methods in DFT as well as the state-specific static-exchange approach. Calculations on ethene and 1,1-difluoroethene illustrate the possibility of using nonrelativistic coupled cluster singles and doubles (CCSD) with additional effects of electron correlation and relativity added as scalar shifts in energetics. It has been demonstrated that CPP spectra obtained with coupled cluster singles and approximate doubles (CC2), CCSD, and DFT (with a Coulomb attenuated exchange-correlation functional) yield excellent predictions of chemical shifts for vinylfluoride, 1,1-difluoroethene, trifluoroethene, as well as good spectral features for acetone in the case of CCSD and DFT. Following this, CPP-DFT is considered to be a viable option for the calculation of X-ray absorption spectra of larger {pi}-conjugated systems, and CC2 is deemed applicable for chemical shifts but not for studies of fine structure features. The CCSD method as well as the more approximate CC2 method are shown to yield spectral features relating to {pi}*-resonances in good agreement with experiment, not only for the aforementioned molecules but also for ethene, cis-1,2-difluoroethene, and tetrafluoroethene. The STEX approach is shown to underestimate {pi}*-peak separations due to spectral compressions, a characteristic which is inherent to this

  12. SAIC: an iterative clustering approach for analysis of single cell RNA-seq data.

    PubMed

    Yang, Lu; Liu, Jiancheng; Lu, Qiang; Riggs, Arthur D; Wu, Xiwei

    2017-10-03

    Research interests toward single cell analysis have greatly increased in basic, translational and clinical research areas recently, as advances in whole-transcriptome amplification technique allow scientists to get accurate sequencing result at single cell level. An important step in the single-cell transcriptome analysis is to identify distinct cell groups that have different gene expression patterns. Currently there are limited bioinformatics approaches available for single-cell RNA-seq analysis. Many studies rely on principal component analysis (PCA) with arbitrary parameters to identify the genes that will be used to cluster the single cells. We have developed a novel algorithm, called SAIC (Single cell Analysis via Iterative Clustering), that identifies the optimal set of signature genes to separate single cells into distinct groups. Our method utilizes an iterative clustering approach to perform an exhaustive search for the best parameters within the search space, which is defined by a number of initial centers and P values. The end point is identification of a signature gene set that gives the best separation of the cell clusters. Using a simulated data set, we showed that SAIC can successfully identify the pre-defined signature gene sets that can correctly separated the cells into predefined clusters. We applied SAIC to two published single cell RNA-seq datasets. For both datasets, SAIC was able to identify a subset of signature genes that can cluster the single cells into groups that are consistent with the published results. The signature genes identified by SAIC resulted in better clusters of cells based on DB index score, and many genes also showed tissue specific expression. In summary, we have developed an efficient algorithm to identify the optimal subset of genes that separate single cells into distinct clusters based on their expression patterns. We have shown that it performs better than PCA method using published single cell RNA-seq datasets.

  13. Calculation of vibrational energy of molecule using coupled cluster linear response theory in bosonic representation: convergence studies.

    PubMed

    Banik, Subrata; Pal, Sourav; Prasad, M Durga

    2008-10-07

    Vibrational excited state energies have been calculated using vibrational coupled cluster linear response theory (CCLRT). The method has been implemented on formaldehyde and water molecule. Convergence studies have been shown with varying the cluster operator from S(4) to S(6) as well as the excitation operator from four bosons to six bosons. A good agreement with full configuration interaction results has been observed with S(6) truncation at coupled-cluster method level and six bosonic excitations at CCLRT level.

  14. A Ferromagnetic Salicylaldoximate/Azide Mn(II)2Mn(III)6 Cluster with an S = 17 Ground State and a Single-Molecule-Magnet Response.

    PubMed

    Vicente, R; El Fallah, M S; Casanovas, B; Font-Bardia, M; Escuer, A

    2016-06-20

    One new Mn(II)2Mn(III)6 cluster exhibiting an S = 17 spin ground state and single-molecule-magnet properties has been designed linking Mn(III)3-salicylaldoximate triangles and tetracoordinated Mn(II) cations by means of end-on azido bridges. The ferromagnetic coupling has been rationalized as a function of their structural parameters.

  15. Mobile clusters of single board computers: an option for providing resources to student projects and researchers.

    PubMed

    Baun, Christian

    2016-01-01

    Clusters usually consist of servers, workstations or personal computers as nodes. But especially for academic purposes like student projects or scientific projects, the cost for purchase and operation can be a challenge. Single board computers cannot compete with the performance or energy-efficiency of higher-value systems, but they are an option to build inexpensive cluster systems. Because of the compact design and modest energy consumption, it is possible to build clusters of single board computers in a way that they are mobile and can be easily transported by the users. This paper describes the construction of such a cluster, useful applications and the performance of the single nodes. Furthermore, the clusters' performance and energy-efficiency is analyzed by executing the High Performance Linpack benchmark with a different number of nodes and different proportion of the systems total main memory utilized.

  16. A Comparison of Single Sample and Bootstrap Methods to Assess Mediation in Cluster Randomized Trials

    ERIC Educational Resources Information Center

    Pituch, Keenan A.; Stapleton, Laura M.; Kang, Joo Youn

    2006-01-01

    A Monte Carlo study examined the statistical performance of single sample and bootstrap methods that can be used to test and form confidence interval estimates of indirect effects in two cluster randomized experimental designs. The designs were similar in that they featured random assignment of clusters to one of two treatment conditions and…

  17. Sizeable Kane-Mele-like spin orbit coupling in graphene decorated with iridium clusters

    NASA Astrophysics Data System (ADS)

    Qin, Yuyuan; Wang, Siqi; Wang, Rui; Bu, Haijun; Wang, Xuefeng; Wang, Xinran; Song, Fengqi; Wang, Baigeng; Wang, Guanghou

    2016-05-01

    The spin-orbit coupling strength of graphene can be enhanced by depositing iridium nanoclusters. Weak localization is intensely suppressed near zero fields after the cluster deposition, rather than changing to weak anti-localization. Fitting the magnetoresistance gives the spin relaxation time, which increases by two orders with the application of a back gate. The spin relaxation time is found to be proportional to the electronic elastic scattering time, demonstrating the Elliot-Yafet spin relaxation mechanism. A sizeable Kane-Mele-like coupling strength of over 5.5 meV is determined by extrapolating the temperature dependence to zero.

  18. Sizeable Kane–Mele-like spin orbit coupling in graphene decorated with iridium clusters

    SciTech Connect

    Qin, Yuyuan; Wang, Siqi; Wang, Rui; Bu, Haijun; Song, Fengqi E-mail: bgwang@nju.edu.cn; Wang, Baigeng E-mail: bgwang@nju.edu.cn; Wang, Guanghou; Wang, Xuefeng; Wang, Xinran

    2016-05-16

    The spin-orbit coupling strength of graphene can be enhanced by depositing iridium nanoclusters. Weak localization is intensely suppressed near zero fields after the cluster deposition, rather than changing to weak anti-localization. Fitting the magnetoresistance gives the spin relaxation time, which increases by two orders with the application of a back gate. The spin relaxation time is found to be proportional to the electronic elastic scattering time, demonstrating the Elliot–Yafet spin relaxation mechanism. A sizeable Kane–Mele-like coupling strength of over 5.5 meV is determined by extrapolating the temperature dependence to zero.

  19. Coupled-cluster theory for atoms and molecules in strong magnetic fields

    SciTech Connect

    Stopkowicz, Stella Lange, Kai K.; Tellgren, Erik I.; Helgaker, Trygve; Gauss, Jürgen

    2015-08-21

    An implementation of coupled-cluster (CC) theory to treat atoms and molecules in finite magnetic fields is presented. The main challenges for the implementation stem from the magnetic-field dependence in the Hamiltonian, or, more precisely, the appearance of the angular momentum operator, due to which the wave function becomes complex and which introduces a gauge-origin dependence. For this reason, an implementation of a complex CC code is required together with the use of gauge-including atomic orbitals to ensure gauge-origin independence. Results of coupled-cluster singles–doubles–perturbative-triples (CCSD(T)) calculations are presented for atoms and molecules with a focus on the dependence of correlation and binding energies on the magnetic field.

  20. Effects of spherical mode coupling on near-field focusing by clusters of dielectric microspheres.

    PubMed

    Pikulin, Alexander; Afanasiev, Andrei; Agareva, Nadezhda; Alexandrov, Alexander P; Bredikhin, Vladimir; Bityurin, Nikita

    2012-04-09

    Colloidal particle lens array (CPLA) proved to be an efficient near-field focusing device for laser nanoprocessing of materials. Within CPLA, spherical particles do not act as independent microlenses. Due to the coupling of the spherical modes, the field near the clusters of spherical microparticles cannot be calculated by means of the superposition of Mie solutions for individual spheres. In the paper, the electromagnetic field distributions near laser-irradiated clusters of dielectric microspheres with configurations that match the fragments of the close-packed CPLA are studied. It is shown that some practically important mode coupling effects can be understood in terms of an effective immersion medium formed for the spherical particle by its surrounding.

  1. Quantum implementation of the unitary coupled cluster for simulating molecular electronic structure

    NASA Astrophysics Data System (ADS)

    Shen, Yangchao; Zhang, Xiang; Zhang, Shuaining; Zhang, Jing-Ning; Yung, Man-Hong; Kim, Kihwan

    2017-02-01

    In classical computational chemistry, the coupled-cluster ansatz is one of the most commonly used ab initio methods, which is critically limited by its nonunitary nature. The unitary modification as an ideal solution to the problem is, however, extremely inefficient in classical conventional computation. Here, we provide experimental evidence that indeed the unitary version of the coupled-cluster ansatz can be reliably performed in a physical quantum system, a trapped-ion system. We perform a simulation on the electronic structure of a molecular ion (HeH+), where the ground-state energy surface curve is probed, the energies of the excited states are studied, and bond dissociation is simulated nonperturbatively. Our simulation takes advantages from quantum computation to overcome the intrinsic limitations in classical computation, and our experimental results indicate that the method is promising for preparing molecular ground states for quantum simulations.

  2. NOx Catalyzed Pathway of Stratospheric Ozone Depletion: A Coupled Cluster Investigation.

    PubMed

    Dutta, Achintya Kumar; Vaval, Nayana; Pal, Sourav

    2012-06-12

    We report a theoretical investigation on the NOx catalyzed pathways of stratospheric ozone depletion using highly accurate coupled cluster methods. These catalytic reactions represent a great challenge to state-of-the-art ab initio methods, while their mechanisms remain unclear to both experimentalists and theoreticians. In this work, we have used the so-called "gold standard of quantum chemistry," the CCSD(T) method, to identify the saddle points on NOx-based reaction pathways of ozone hole formation. Energies of the saddle points are calculated using the multireference variants of coupled cluster methods. The calculated activation energies and rate constants show good agreement with available experimental results. Tropospheric precursors to stratospheric NOx radicals have been identified, and their potential importance in stratospheric chemistry has been discussed. Our calculations resolve previous conflicts between ab initio and experimental results for a trans nitro peroxide intermediate, in the NOx catalyzed pathway of ozone depletion.

  3. Linear scaling coupled cluster and perturbation theories in the atomic orbital basis

    NASA Astrophysics Data System (ADS)

    Scuseria, Gustavo E.; Ayala, Philippe Y.

    1999-11-01

    We present a reformulation of the coupled cluster equations in the atomic orbital (AO) basis that leads to a linear scaling algorithm for large molecules. Neglecting excitation amplitudes in a screening process designed to achieve a target energy accuracy, we obtain an AO coupled cluster method which is competitive in terms of number of amplitudes with the traditional molecular orbital (MO) solution, even for small molecules. For large molecules, the decay properties of integrals and excitation amplitudes becomes evident and our AO method yields a linear scaling algorithm with respect to molecular size. We present benchmark calculations to demonstrate that our AO reformulation of the many-body electron correlation problem defeats the "exponential scaling wall" that has characterized high-level MO quantum chemistry calculations for many years.

  4. Symmetry broken and restored coupled-cluster theory: II. Global gauge symmetry and particle number

    NASA Astrophysics Data System (ADS)

    Duguet, T.; Signoracci, A.

    2017-01-01

    We have recently extended many-body perturbation theory (MBPT) and coupled-cluster theory performed on top of a Slater determinant breaking rotational symmetry to allow for the restoration of the angular momentum at any truncation order (Duguet 2015 J. Phys. G: Nucl. Part. Phys. 42 025107). Following a similar route, we presently extend Bogoliubov MBPT and Bogoliubov coupled cluster theory performed on top of a Bogoliubov reference state breaking global gauge symmetry to allow for the restoration of the particle number at any truncation order. Eventually, formalisms can be merged to handle SU(2) and U(1) symmetries at the same time. The long-term goal relates to the ab initio description of near-degenerate finite quantum systems with an open-shell character.

  5. Generation of strongly coupled Xe cluster nanoplasmas by low intensive soft x-ray laser irradiation

    SciTech Connect

    Namba, S.; Hasegawa, N.; Kishimoto, M.; Nishikino, M.; Kawachi, T.

    2012-07-11

    A seeding gas jet including Xe clusters was irradiated with a laser-driven plasma soft x-ray laser pulse ({lambda}=13.9 nm, {approx}7 ps, {<=}5 Multiplication-Sign 10{sup 9} W/cm{sup 2}), where the laser photon energy is high enough to ionize 4d core electrons. In order to clarify how the innershell ionization followed by the Auger electron emission is affected under the intense laser irradiation, the electron energy distribution was measured. Photoelectron spectra showed that the peak position attributed to 4d hole shifted to lower energy and the spectral width was broadened with increasing cluster size. Moreover, the energy distribution exhibited that a strongly coupled cluster nanoplasma with several eV was generated.

  6. A coupled-cluster analysis of the photoelectron spectrum of FeCl3

    SciTech Connect

    Watts, John D.; Dupuis, Michel

    2005-08-10

    Coupled-cluster calculations including effects of connected triple excitations have been performed on the ground state of and several electronic states of FeCl3. The vertical electron detachment energies closely correspond to the band energies of the photoelectron spectrum recently obtained by Yang et al. [Yang et al. J. chem. Phys., 119, 8311 (2003).], and thus provide a possible assignment of the spectrum.

  7. A Massively Parallel Tensor Contraction Framework for Coupled-Cluster Computations

    DTIC Science & Technology

    2014-08-02

    Processing (IPDPS), 2013. [14] ERIK DEUMENS, VICTOR F. LOTRICH, AJITH PERERA, MARK J. PONTON, BEVERLY A. SANDERS, AND RODNEY J. BARTLETT, Software... TOLEDO , AND ALEXANDER TISKIN, Communication lower bounds for distributed-memory matrix multiplication, Journal of Parallel and Distributed Computing...KUCHARSKI, AND RODNEY J. BARTLETT, A coupled cluster ap- proach with triple excitations, Journal of Chemical Physics, 81 (1984), p. 5906. [31] VICTOR

  8. Relativistic coupled-cluster calculations of transition properties in highly charged inert-gas ions

    NASA Astrophysics Data System (ADS)

    Nandy, D. K.

    2016-11-01

    We have carried out an extensive investigation of various spectroscopic properties of highly charged inert-gas ions using a relativistic coupled-cluster method through a one-electron detachment procedure. In particular, we have calculated the atomic states 2 s22 p53/2 2P, 2 s22 p51/2 2P, and 2 s 2 p61/2 2S in F-like inert-gas ions; 3 s23 p53/2 2P, 3 s23 p51/2 2P, and 3 s 3 p61/2 2S states in Cl-like Kr, Xe, and Rn; and 4 s24 p53/2 2P, 4 s24 p51/2 2P, and 4 s 4 p61/2 2S states in Br-like Xe and Rn. Starting from a single-reference Dirac-Hartree-Fock wave function, we construct our exact atomic states by including the dynamic correlation effects in an all-order perturbative fashion. Employing this method, we estimate the ionization potential energies of three low-lying orbitals present in their respective closed-shell configurations. Since the considered highly charged inert-gas ions exhibit huge relativistic effects, we have taken into account the corrections due to Breit interaction as well as from the dominant quantum electrodynamic correction such as vacuum polarization and self-energy effects in these systems. Using our calculated relativistic atomic wave functions and energies, we accurately determine various transition properties such as wavelengths, line strengths, oscillator strengths, transition probabilities, and lifetimes of the excited states.

  9. Method for exploratory cluster analysis and visualisation of single-trial ERP ensembles.

    PubMed

    Williams, N J; Nasuto, S J; Saddy, J D

    2015-07-30

    The validity of ensemble averaging on event-related potential (ERP) data has been questioned, due to its assumption that the ERP is identical across trials. Thus, there is a need for preliminary testing for cluster structure in the data. We propose a complete pipeline for the cluster analysis of ERP data. To increase the signal-to-noise (SNR) ratio of the raw single-trials, we used a denoising method based on Empirical Mode Decomposition (EMD). Next, we used a bootstrap-based method to determine the number of clusters, through a measure called the Stability Index (SI). We then used a clustering algorithm based on a Genetic Algorithm (GA) to define initial cluster centroids for subsequent k-means clustering. Finally, we visualised the clustering results through a scheme based on Principal Component Analysis (PCA). After validating the pipeline on simulated data, we tested it on data from two experiments - a P300 speller paradigm on a single subject and a language processing study on 25 subjects. Results revealed evidence for the existence of 6 clusters in one experimental condition from the language processing study. Further, a two-way chi-square test revealed an influence of subject on cluster membership. Our analysis operates on denoised single-trials, the number of clusters are determined in a principled manner and the results are presented through an intuitive visualisation. Given the cluster structure in some experimental conditions, we suggest application of cluster analysis as a preliminary step before ensemble averaging. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Benchmarking density-functional theory calculations of NMR shielding constants and spin-rotation constants using accurate coupled-cluster calculations.

    PubMed

    Teale, Andrew M; Lutnæs, Ola B; Helgaker, Trygve; Tozer, David J; Gauss, Jürgen

    2013-01-14

    Accurate sets of benchmark nuclear-magnetic-resonance shielding constants and spin-rotation constants are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the calculated coupled-cluster constants is established by a careful comparison with experimental data, taking into account zero-point vibrational corrections. Coupled-cluster basis-set convergence is analyzed and extrapolation techniques are employed to estimate basis-set-limit quantities, thereby establishing an accurate benchmark data set. Together with the set provided for rotational g-tensors and magnetizabilities in our previous work [O. B. Lutnæs, A. M. Teale, T. Helgaker, D. J. Tozer, K. Ruud, and J. Gauss, J. Chem. Phys. 131, 144104 (2009)], it provides a substantial source of consistently calculated high-accuracy data on second-order magnetic response properties. The utility of this benchmark data set is demonstrated by examining a wide variety of Kohn-Sham exchange-correlation functionals for the calculation of these properties. None of the existing approximate functionals provide an accuracy competitive with that provided by CCSD or CCSD(T) theory. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of Kohn-Sham calculations constrained to give the same electronic density. Routes to future improvements are discussed in light of this comparison.

  11. Particle-particle and quasiparticle random phase approximations: Connections to coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Scuseria, Gustavo E.; Henderson, Thomas M.; Bulik, Ireneusz W.

    2013-09-01

    We establish a formal connection between the particle-particle (pp) random phase approximation (RPA) and the ladder channel of the coupled cluster doubles (CCD) equations. The relationship between RPA and CCD is best understood within a Bogoliubov quasiparticle (qp) RPA formalism. This work is a follow-up to our previous formal proof on the connection between particle-hole (ph) RPA and ring-CCD. Whereas RPA is a quasibosonic approximation, CC theory is a "correct bosonization" in the sense that the wavefunction and Hilbert space are exactly fermionic, yet the amplitude equations can be interpreted as adding different quasibosonic RPA channels together. Coupled cluster theory achieves this goal by interacting the ph (ring) and pp (ladder) diagrams via a third channel that we here call "crossed-ring" whose presence allows for full fermionic antisymmetry. Additionally, coupled cluster incorporates what we call "mosaic" terms which can be absorbed into defining a new effective one-body Hamiltonian. The inclusion of these mosaic terms seems to be quite important. The pp-RPA and qp-RPA equations are textbook material in nuclear structure physics but are largely unknown in quantum chemistry, where particle number fluctuations and Bogoliubov determinants are rarely used. We believe that the ideas and connections discussed in this paper may help design improved ways of incorporating RPA correlation into density functionals based on a CC perspective.

  12. Particle-particle and quasiparticle random phase approximations: connections to coupled cluster theory.

    PubMed

    Scuseria, Gustavo E; Henderson, Thomas M; Bulik, Ireneusz W

    2013-09-14

    We establish a formal connection between the particle-particle (pp) random phase approximation (RPA) and the ladder channel of the coupled cluster doubles (CCD) equations. The relationship between RPA and CCD is best understood within a Bogoliubov quasiparticle (qp) RPA formalism. This work is a follow-up to our previous formal proof on the connection between particle-hole (ph) RPA and ring-CCD. Whereas RPA is a quasibosonic approximation, CC theory is a "correct bosonization" in the sense that the wavefunction and Hilbert space are exactly fermionic, yet the amplitude equations can be interpreted as adding different quasibosonic RPA channels together. Coupled cluster theory achieves this goal by interacting the ph (ring) and pp (ladder) diagrams via a third channel that we here call "crossed-ring" whose presence allows for full fermionic antisymmetry. Additionally, coupled cluster incorporates what we call "mosaic" terms which can be absorbed into defining a new effective one-body Hamiltonian. The inclusion of these mosaic terms seems to be quite important. The pp-RPA and qp-RPA equations are textbook material in nuclear structure physics but are largely unknown in quantum chemistry, where particle number fluctuations and Bogoliubov determinants are rarely used. We believe that the ideas and connections discussed in this paper may help design improved ways of incorporating RPA correlation into density functionals based on a CC perspective.

  13. Direct Photonic-Plasmonic Coupling and Routing in Single Nanowires

    SciTech Connect

    Yan, Rouxue; Pausauskie, Peter; Huang, Jiaxing; Yang, Piedong

    2009-10-20

    Metallic nanoscale structures are capable of supporting surface plasmon polaritons (SPPs), propagating collective electron oscillations with tight spatial confinement at the metal surface. SPPs represent one of the most promising structures to beat the diffraction limit imposed by conventional dielectric optics. Ag nano wires have drawn increasing research attention due to 2D sub-100 nm mode confinement and lower losses as compared with fabricated metal structures. However, rational and versatile integration of Ag nanowires with other active and passive optical components, as well as Ag nanowire based optical routing networks, has yet to be achieved. Here, we demonstrate that SPPs can be excited simply by contacting a silver nanowire with a SnO2 nanoribbon that serves both as an unpolarized light source and a dielectric waveguide. The efficient coupling makes it possible to measure the propagation-distance-dependent waveguide spectra and frequency-dependent propagation length on a single Ag nanowire. Furthermore, we have demonstrated prototypical photonic-plasmonic routing devices, which are essential for incorporating low-loss Ag nanowire waveguides as practical components into high-capacity photonic circuits.

  14. Calculation of the magnetic hyperfine structure constant of alkali metals and alkaline-earth-metal ions using the relativistic coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Sasmal, Sudip

    2017-07-01

    The Z -vector method in the relativistic coupled-cluster framework is used to calculate the magnetic hyperfine structure constant (AJ) of alkali metals and singly charged alkaline earth metals in their ground state electronic configuration. The Z -vector results are in very good agreement with the experiment. The AJ values of Li, Na, K, Rb, Cs, Be+, Mg+, Ca+, and Sr+ obtained in the Z -vector method are compared with the extended coupled-cluster results taken from Phys. Rev. A 91, 022512 (2015), 10.1103/PhysRevA.91.022512. The same basis and cutoff are used for the comparison purpose. The comparison shows that the Z -vector method with the single and double approximation can produce a more precise wave function in the nuclear region than the ECC method.

  15. Generic, network schema agnostic sparse tensor factorization for single-pass clustering of heterogeneous information networks

    PubMed Central

    Meng, Qinggang; Deng, Su; Huang, Hongbin; Wu, Yahui; Badii, Atta

    2017-01-01

    Heterogeneous information networks (e.g. bibliographic networks and social media networks) that consist of multiple interconnected objects are ubiquitous. Clustering analysis is an effective method to understand the semantic information and interpretable structure of the heterogeneous information networks, and it has attracted the attention of many researchers in recent years. However, most studies assume that heterogeneous information networks usually follow some simple schemas, such as bi-typed networks or star network schema, and they can only cluster one type of object in the network each time. In this paper, a novel clustering framework is proposed based on sparse tensor factorization for heterogeneous information networks, which can cluster multiple types of objects simultaneously in a single pass without any network schema information. The types of objects and the relations between them in the heterogeneous information networks are modeled as a sparse tensor. The clustering issue is modeled as an optimization problem, which is similar to the well-known Tucker decomposition. Then, an Alternating Least Squares (ALS) algorithm and a feasible initialization method are proposed to solve the optimization problem. Based on the tensor factorization, we simultaneously partition different types of objects into different clusters. The experimental results on both synthetic and real-world datasets have demonstrated that our proposed clustering framework, STFClus, can model heterogeneous information networks efficiently and can outperform state-of-the-art clustering algorithms as a generally applicable single-pass clustering method for heterogeneous network which is network schema agnostic. PMID:28245222

  16. Generic, network schema agnostic sparse tensor factorization for single-pass clustering of heterogeneous information networks.

    PubMed

    Wu, Jibing; Meng, Qinggang; Deng, Su; Huang, Hongbin; Wu, Yahui; Badii, Atta

    2017-01-01

    Heterogeneous information networks (e.g. bibliographic networks and social media networks) that consist of multiple interconnected objects are ubiquitous. Clustering analysis is an effective method to understand the semantic information and interpretable structure of the heterogeneous information networks, and it has attracted the attention of many researchers in recent years. However, most studies assume that heterogeneous information networks usually follow some simple schemas, such as bi-typed networks or star network schema, and they can only cluster one type of object in the network each time. In this paper, a novel clustering framework is proposed based on sparse tensor factorization for heterogeneous information networks, which can cluster multiple types of objects simultaneously in a single pass without any network schema information. The types of objects and the relations between them in the heterogeneous information networks are modeled as a sparse tensor. The clustering issue is modeled as an optimization problem, which is similar to the well-known Tucker decomposition. Then, an Alternating Least Squares (ALS) algorithm and a feasible initialization method are proposed to solve the optimization problem. Based on the tensor factorization, we simultaneously partition different types of objects into different clusters. The experimental results on both synthetic and real-world datasets have demonstrated that our proposed clustering framework, STFClus, can model heterogeneous information networks efficiently and can outperform state-of-the-art clustering algorithms as a generally applicable single-pass clustering method for heterogeneous network which is network schema agnostic.

  17. Cross-Genome Clustering of Human and C. elegans G-Protein Coupled Receptors

    PubMed Central

    Nagarathnam, Balasubramanian; Kalaimathy, Singaravelu; Balakrishnan, Veluchamy; Sowdhamini, Ramanathan

    2012-01-01

    G-protein coupled receptors (GPCRs) are one of the largest groups of membrane proteins and are popular drug targets. The work reported here attempts to perform cross-genome phylogeny on GPCRs from two widely different taxa, human versus C. elegans genomes and to address the issues on evolutionary plasticity, to identify functionally related genes, orthologous relationship, and ligand binding properties through effective bioinformatic approaches. Through RPS blast around 1106 nematode GPCRs were given chance to associate with previously established 8 types of human GPCR profiles at varying E-value thresholds and resulted 32 clusters were illustrating co-clustering and class-specific retainsionship. In the significant thresholds, 81% of the C. elegans GPCRs were associated with 32 clusters and 27 C. elegans GPCRs (2%) inferred for orthology. 177 hypothetical proteins were observed in cluster association and could be reliably associated with one of 32 clusters. Several nematode-specific GPCR clades were observed suggesting lineage-specific functional recruitment in response to environment. PMID:22807621

  18. Electronic coupling between ligand and core energy states in dithiolate-monothiolate stabilized Au clusters.

    PubMed

    Ahuja, Tarushee; Wang, Dengchao; Tang, Zhenghua; Robinson, Donald A; Padelford, Jonathan W; Wang, Gangli

    2015-07-15

    Electron transfer activities of metal clusters are fundamentally significant and have promising potential in catalysis, charge or energy storage, sensing, biomedicine and other applications. Strong resonance coupling between the metal core energy states and the ligand molecular orbitals has not been established experimentally, albeit exciting progress has been achieved in the composition and structure determination of these types of nanomaterials recently. In this report, the coupling between core and ligand energy states is demonstrated by the rich electron transfer activities of Au130 clusters. Quantized electron transfers to the core and multi-electron transfers involving the durene-dithiolate ligands were observed at lower and higher potentials, respectively, in voltammetric studies. After a facile multi-electron oxidation from +1.34 to +1.40 V, several reversal reduction processes at more negative potentials, i.e. +0.91 V, +0.18 V and -0.34 V, were observed in an electrochemically irreversible fashion or with sluggish kinetics. The number of electrons and the shifts of the respective reduction potentials in the reversal process were attributed to the electronic coupling or energy relaxation processes. The electron transfer activities and subsequent relaxation processes are drastically reduced at lower temperatures. The time- and temperature-dependent relaxation, involving multiple energy states in the reversal reduction processes upon the oxidation of ligands, reveals the coupling between core and ligand energy states.

  19. Energetics of 1,n-didehydro-polyene diradicals and performance of reduced multireference coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Li, Xiangzhu; Paldus, Josef

    The reduced multireference coupled-cluster method with singles and doubles (RMR CCSD) and its RMR CCSD(T) version are employed to study the energetics of 1,n-didehydro-polyenes. The RMR CCSD method accounts for quasi-degeneracy by exploiting a multireference (MR) CISD wave function as an external source of the most important (primary) triples and quadruples while the subsequent perturbative correction for the secondary triples leads to RMR CCSD(T). The resulting energies are compared with those yielded by the standard single-reference (SR) CCSD and CCSD(T) approaches. We first determine the optimal geometry for each species considered. Using the CC methods just mentioned we then compute the energy of the lowest-lying singlet and triplet states, the implied singlet-triplet splitting, and determine the spin multiplicity of the ground state. We point out the relationship between the degree of the diradical character, the extent of quasi-degeneracy or the MR nature of the state considered, the distance separating the radical centers and, finally, the size of the largest doubly excited cluster amplitude in the CC wave functions.

  20. Charge cluster distribution in nanosites traversed by a single ionizing particle An experimental approach

    NASA Astrophysics Data System (ADS)

    Pszona, S.; Bantsar, A.; Kula, J.

    2008-11-01

    A method for modeling charge cluster formation by a single ionizing particle in nanoelectronic structures of few nanometres size is presented. The method is based on experimental modeling of charge formation in the equivalent gaseous nanosites irradiated by single charged particles and the subsequent scaling procedure to a needed medium. Propane irradiated by alpha particles is presented as an example.

  1. Second-order variational coupled-cluster linear-response method: A Hermitian time-dependent theory

    SciTech Connect

    Kats, Daniel; Usvyat, Denis; Schuetz, Martin

    2011-06-15

    The formalism is presented for the linear response of a time-dependent (TD) variational coupled cluster (VCC), truncated according to Moeller-Plesset perturbation theory, i.e., a TD-VCC[n] linear response, where n denotes the order of the corresponding quasienergy with respect to the fluctuation potential. The resulting eigenvalue problem determining the excitation energies is Hermitian and of the simple Tamm-Dancoff form. The VCC excitation energies are equivalent to those of the configuration-interaction singles (CIS) model, while the Casida equation for the TD-Hartree-Fock approach is an approximation to it. The TD-VCC response, the lowest-order method including electron correlation, is discussed in detail and the relations to other second-order methods, such as the CC2 linear response and the algebraic diagrammatic construction at second order [ADC(2)] are explored.

  2. Efficient Sparse Matrix Algorithm to Speed Up the Calculation of the Ladder Term in Coupled Cluster Programs.

    PubMed

    Pillió, Zoltán; Tajti, Attila; Szalay, Péter G

    2012-09-11

    A new algorithm is presented for the calculation of the ladder-type term of the coupled cluster singles and doubles (CCSD) equations using two-electron integrals in atomic orbital (AO) basis. The method is based on an orbital grouping scheme, which results in an optimal partitioning of the AO integral matrix into sparse and dense blocks allowing efficient matrix multiplication. Carefully chosen numerical tests have been performed to analyze the performance of all aspects of the new algorithm. It is shown that the suggested scheme allows an efficient utilization of modern highly parallel architectures and devices in CCSD calculations. Details of the implementation in the development version of CFOUR quantum chemical program package are also presented.

  3. Inactive excitations in Mukherjee's state-specific multireference coupled cluster theory treated with internal contraction: Development and applications

    NASA Astrophysics Data System (ADS)

    Das, Sanghamitra; Pathak, Shubhrodeep; Datta, Dipayan; Mukherjee, Debashis

    2012-04-01

    One generic difficulty of most state-specific many-body formalisms using the Jeziorski-Monkhorst ansatz: ψ = ∑μexp (Tμ)|ϕμ⟩cμ for the wave-operators is the large number of redundant cluster amplitudes. The number of cluster amplitudes up to a given rank is many more in number compared to the dimension of the Hilbert Space spanned by the virtual functions of up to the same rank of excitations. At the same time, all inactive excitations - though linearly independent - are far too numerous. It is well known from the success of the contracted multi-reference configuration interaction (MRCI(SD)) that, at least for the inactive double excitations, their model space dependence (μ-dependence) is weak. Considerable simplifications can thus be obtained by using a partially internally contracted description, which uses the physically appealing approximation of taking the inactive excitations Ti to be independent of the model space labels (μ-independent). We propose and implement in this paper such a formalism with internal contractions for inactive excitations (ICI) within Mukherjee's state-specific multi-reference coupled cluster theory (SS-MRCC) framework (referred to from now on as the ICI-SS-MRCC). To the extent the μ-independence of Ti is valid, we expect the ICI-SS-MRCC to retain the conceptual advantages of size-extensivity yet using a drastically reduced number of cluster amplitudes without sacrificing accuracy. Moreover, greater coupling is achieved between the virtual functions reached by inactive excitations as a result of the internal contraction while retaining the original coupling term for the μ-dependent excitations akin to the parent theory. Another major advantage of the ICI-SS-MRCC, unlike the other analogous internally contracted theories, such as IC-MRCISD, CASPT2, or MRMP2, is that it can use relaxed coefficients for the model functions. However, at the same time it employs projection manifolds for the virtuals obtained from inactive n hole

  4. A Comparison of Three Approaches to the Reduced-Scaling Coupled Cluster Treatment of Non-Resonant Molecular Response Properties.

    PubMed

    McAlexander, Harley R; Crawford, T Daniel

    2016-01-12

    We have investigated the performance of the reduced-scaling coupled cluster method based on projected atomic orbitals (PAOs), pair natural orbitals (PNOs), and orbital specific virtuals (OSVs) for the prediction of linear response properties. These methods introduce different degrees of controllable sparsity in the ground-state and perturbed coupled cluster wave functions, leading to localization errors in properties such as dynamic polarizabilities and specific optical rotations. Using a series of chiral test compounds, we find that the inherent costs associated with computing response properties are significantly greater than those for determining the ground-state energy. As the dimensionality of the molecular system increases-from (pseudo)linear structures, such as fluoroalkanes, to cagelike structures, such as β-pinene-the crossover point between canonical-orbital and localized-orbital algorithms increases substantially. Furthermore, both the OSV and PNO methods provide greater reduction in cost (as measured by the size of the double-excitation space) than do PAOs, and PNOs provide the greatest level of sparsity for the systems examined here. Single-excitation truncation induces much larger errors than corresponding doubles truncation due to the fact that the first-order contribution to the one-electron perturbed wave function appears in the singles amplitudes. Both the PNO and OSV methods perform reasonably well for frequency-dependent polarizabilities provided appropriate thresholds are used for the occupation-number and weak-pair cutoffs on which each method depends. Specific rotations, however, are very sensitive to wave function truncation, to the extent that aggressive thresholds can yield the incorrect sign of the rotation, due to the delicate balance of positive and negative wave function contributions to the mixed electric-/magnetic-field response.

  5. A Bayesian cluster analysis method for single-molecule localization microscopy data.

    PubMed

    Griffié, Juliette; Shannon, Michael; Bromley, Claire L; Boelen, Lies; Burn, Garth L; Williamson, David J; Heard, Nicholas A; Cope, Andrew P; Owen, Dylan M; Rubin-Delanchy, Patrick

    2016-12-01

    Cell function is regulated by the spatiotemporal organization of the signaling machinery, and a key facet of this is molecular clustering. Here, we present a protocol for the analysis of clustering in data generated by 2D single-molecule localization microscopy (SMLM)-for example, photoactivated localization microscopy (PALM) or stochastic optical reconstruction microscopy (STORM). Three features of such data can cause standard cluster analysis approaches to be ineffective: (i) the data take the form of a list of points rather than a pixel array; (ii) there is a non-negligible unclustered background density of points that must be accounted for; and (iii) each localization has an associated uncertainty in regard to its position. These issues are overcome using a Bayesian, model-based approach. Many possible cluster configurations are proposed and scored against a generative model, which assumes Gaussian clusters overlaid on a completely spatially random (CSR) background, before every point is scrambled by its localization precision. We present the process of generating simulated and experimental data that are suitable to our algorithm, the analysis itself, and the extraction and interpretation of key cluster descriptors such as the number of clusters, cluster radii and the number of localizations per cluster. Variations in these descriptors can be interpreted as arising from changes in the organization of the cellular nanoarchitecture. The protocol requires no specific programming ability, and the processing time for one data set, typically containing 30 regions of interest, is ∼18 h; user input takes ∼1 h.

  6. In Situ Characterization of Bak Clusters Responsible for Cell Death Using Single Molecule Localization Microscopy

    PubMed Central

    Nasu, Yusuke; Benke, Alexander; Arakawa, Satoko; Yoshida, Go J.; Kawamura, Genki; Manley, Suliana; Shimizu, Shigeomi; Ozawa, Takeaki

    2016-01-01

    Apoptosis plays a pivotal role in development and tissue homeostasis in multicellular organisms. Clustering of Bak proteins on the mitochondrial outer membrane is responsible for the induction of apoptosis by evoking a release of pro-apoptotic proteins from mitochondria into cytosol. However, how the protein cluster permeabilizes the mitochondrial membrane remains unclear because elucidation of the cluster characteristics such as size and protein density has been hampered by the diffraction-limited resolution of light microscopy. Here, we describe an approach to quantitatively characterize Bak clusters in situ based on single molecule localization. We showed that Bak proteins form densely packed clusters at the nanoscale on mitochondria during apoptosis. Quantitative analysis based on the localization of each Bak protein revealed that the density of Bak protein is uniform among clusters although the cluster size is highly heterogeneous. Our approach provides unprecedented information on the size and protein density of Bak clusters possibly critical for the permeabilization and is applicable for the analysis of different cluster formations. PMID:27293178

  7. Equation-of-Motion Coupled-Cluster Theory for Excitation Energies of Closed-Shell Systems with Spin-Orbit Coupling.

    PubMed

    Wang, Zhifan; Tu, Zheyan; Wang, Fan

    2014-12-09

    Excitation energies of closed-shell systems based on the equation-of-motion (EOM) coupled-cluster theory at the singles and doubles (CCSD) level with spin-orbit coupling (SOC) included in the post-Hartree-Fock treatment are implemented in the present work. SOC can be included in both the CC and EOM steps (EOM-SOC-CCSD) or only in the EOM part (SOC-EOM-CCSD). The latter approach is an economical way to account for SOC effects, but excitation energies with this approach are not size-intensive. When the unlinked term in the latter approach is neglected (cSOC-EOM-CCSD), size-intensive excitation energies can be obtained. Time-reversal symmetry and spatial symmetry are exploited to reduce the computational effort. Imposing time-reversal symmetry results in a real matrix representation for the similarity-transformed Hamiltonian, which facilitates the requirement of time-reversal symmetry for new trial vectors in Davidson's algorithm. Results on some closed-shell atoms and molecules containing heavy elements show that EOM-SOC-CCSD can provide excitation energies and spin-orbit splittings with reasonable accuracy. On the other hand, the SOC-EOM-CCSD approach is able to afford accurate estimates of SOC effects for valence electrons of systems containing elements up to the fifth row, while cSOC-EOM-CCSD is less accurate for spin-orbit splittings of transitions involving p1/2 spinors, even for Kr.

  8. Spin-orbit coupling and electron correlation at various coupled-cluster levels for closed-shell diatomic molecules.

    PubMed

    Wang, Zhifan; Wang, Fan

    2013-11-07

    In this work, equilibrium bond lengths and harmonic frequencies of some closed-shell diatomic heavy-element compounds are calculated at a series of coupled-cluster (CC) levels including CCS, CC2, CCSD and CCSD(T) with spin-orbit coupling (SOC) included in post-Hartree-Fock (HF) step. The purpose of this work is to demonstrate the performance of CC2 for heavy element compounds and to investigate the separability between SOC and electron correlation at different correlation levels. According to our calculations, CC2 results agree well with MP2 results for these molecules except for SnO, Sb2, PbO and Bi2 and the bond lengths of SnO and PbO with CC2 are overestimated by about 0.25 Å compared to when using other approaches. Furthermore, SOC effects on electron correlation are significant for Bi2 and At2 at CCSD(T) level, while this is the case only for Bi2 at CCSD level. For 5th-row element compounds, SOC effects on bond lengths and harmonic frequencies at different levels agree well with each other except for Sb2. On the other hand, SOC effects at CCSD level are in good agreement with those at CCSD(T) level for the investigated 6th-row element compounds except for At2, whereas SOC effects at low correlation levels will be different from those at CCSD(T) level to some extent.

  9. Adsorption of a single gold or silver atom on vanadium oxide clusters.

    PubMed

    Ding, Xun-Lei; Wang, Dan; Li, Rui-Jie; Liao, Heng-Lu; Zhang, Yan; Zhang, Hua-Yong

    2016-04-14

    The bonding properties between a single atom and its support have a close relationship with the stability and reactivity of single-atom catalysts. As a model system, the structural and electronic properties of bimetallic oxide clusters MV3Oy(q) (M = Au or Ag, q = 0, ±1, and y = 6-8) are systematically studied using density functional theory. The single noble metal atom Au or Ag tends to be adsorbed on the periphery of the V oxide clusters. Au prefers V sites for oxygen-poor clusters and O sites for oxygen-rich clusters, while Ag prefers O sites for most cases. According to natural population analysis, Au may possess positive or negative charges in the bimetallic oxide clusters, while Ag usually possesses positive charges. The bonding between Au and V has relatively high covalent character according to the bond order analysis. This work may provide some clues for understanding the bonding properties of single noble metal atoms on the support in practical single-atom catalysts, and serve as a starting point for further theoretical studies on the reaction mechanisms of related catalytic systems.

  10. Relaxation dynamics near the sol-gel transition: From cluster approach to mode-coupling theory

    NASA Astrophysics Data System (ADS)

    Coniglio, A.; Arenzon, J. J.; Fierro, A.; Sellitto, M.

    2014-10-01

    A long standing problem in glassy dynamics is the geometrical interpretation of clusters and the role they play in the observed scaling laws. In this context, the mode-coupling theory (MCT) of type-A transition and the sol-gel transition are both characterized by a structural arrest to a disordered state in which the long-time limit of the correlator continuously approaches zero at the transition point. In this paper, we describe a cluster approach to the sol-gel transition and explore its predictions, including universal scaling laws and a new stretched relaxation regime close to criticality. We show that while MCT consistently describes gelation at mean-field level, the percolation approach elucidates the geometrical character underlying MCT scaling laws.

  11. GPU-based single-cluster algorithm for the simulation of the Ising model

    NASA Astrophysics Data System (ADS)

    Komura, Yukihiro; Okabe, Yutaka

    2012-02-01

    We present the GPU calculation with the common unified device architecture (CUDA) for the Wolff single-cluster algorithm of the Ising model. Proposing an algorithm for a quasi-block synchronization, we realize the Wolff single-cluster Monte Carlo simulation with CUDA. We perform parallel computations for the newly added spins in the growing cluster. As a result, the GPU calculation speed for the two-dimensional Ising model at the critical temperature with the linear size L = 4096 is 5.60 times as fast as the calculation speed on a current CPU core. For the three-dimensional Ising model with the linear size L = 256, the GPU calculation speed is 7.90 times as fast as the CPU calculation speed. The idea of quasi-block synchronization can be used not only in the cluster algorithm but also in many fields where the synchronization of all threads is required.

  12. Single-Electron Transmetalation: An Enabling Technology for Secondary Alkylboron Cross-Coupling

    PubMed Central

    Primer, David N.; Karakaya, Idris; Tellis, John C.; Molander, Gary A.

    2015-01-01

    Single-electron-mediated alkyl transfer affords a novel mechanism for transmetalation, enabling cross-coupling under mild conditions. Here, general conditions are reported for cross-coupling of secondary alkyltrifluoroborates with an array of aryl bromides mediated by an Ir photoredox catalyst and a Ni cross-coupling catalyst. PMID:25650892

  13. Enhanced magnetostriction derived from magnetic single domain structures in cluster-assembled SmCo films.

    PubMed

    Bai, Yulong; Yang, Bo; Guo, Fei; Lu, Qingshan; Zhao, Shifeng

    2017-09-13

    Cluster-assembled SmCo alloy films were prepared by low energy cluster beam deposition. The structure, magnetic domain, magnetization, and magnetostriction of the films were characterized. It is shown that the as-prepared films are assembled in compact and uniformly distributed spherical cluster nanoparticles, most of which, after vacuum in-situ annealing at 700 K, aggregated to form cluster islands. These cluster islands result in transformations from superparamagnetic states to magnetic single domain (MSD) states in the films. Such MSD structures contribute to the enhanced magnetostrictive behaviors with a saturation magnetostrictive coefficient of 160×10-6 in comparison to 105×10-6 for the as-prepared films. This work demonstrates candidate materials that could be applied in nano-electro-mechanical systems (NEMS), low power information storage, and weak magnetic detecting devices. © 2017 IOP Publishing Ltd.

  14. Energy landscapes of nucleophilic substitution reactions: a comparison of density functional theory and coupled cluster methods.

    PubMed

    Swart, Marcel; Solà, Miquel; Bickelhaupt, F Matthias

    2007-07-15

    We have carried out a detailed evaluation of the performance of all classes of density functional theory (DFT) for describing the potential energy surface (PES) of a wide range of nucleophilic substitution (SN2) reactions involving, amongst others, nucleophilic attack at carbon, nitrogen, silicon, and sulfur. In particular, we investigate the ability of the local density approximation (LDA), generalized gradient approximation (GGA), meta-GGA as well as hybrid DFT to reproduce high-level coupled cluster (CCSD(T)) benchmarks that are close to the basis set limit. The most accurate GGA, meta-GGA, and hybrid functionals yield mean absolute deviations of about 2 kcal/mol relative to the coupled cluster data, for reactant complexation, central barriers, overall barriers as well as reaction energies. For the three nonlocal DFT classes, the best functionals are found to be OPBE (GGA), OLAP3 (meta-GGA), and mPBE0KCIS (hybrid DFT). The popular B3LYP functional is not bad but performs significantly worse than the best GGA functionals. Furthermore, we have compared the geometries from several density functionals with the reference CCSD(T) data. The same GGA functionals that perform best for the energies (OPBE, OLYP), also perform best for the geometries with average absolute deviations in bond lengths of 0.06 A and 0.6 degrees, even better than the best meta-GGA and hybrid functionals. In view of the reduced computational effort of GGAs with respect to meta-GGAs and hybrid functionals, let alone coupled cluster, we recommend the use of accurate GGAs such as OPBE or OLYP for the study of SN2 reactions. Copyright (c) 2007 Wiley Periodicals, Inc.

  15. Cluster synchronization in networks of identical oscillators with α -function pulse coupling

    NASA Astrophysics Data System (ADS)

    Chen, Bolun; Engelbrecht, Jan R.; Mirollo, Renato

    2017-02-01

    We study a network of N identical leaky integrate-and-fire model neurons coupled by α -function pulses, weighted by a coupling parameter K . Studies of the dynamics of this system have mostly focused on the stability of the fully synchronized and the fully asynchronous splay states, which naturally depends on the sign of K , i.e., excitation vs inhibition. We find that there is also a rich set of attractors consisting of clusters of fully synchronized oscillators, such as fixed (N -1 ,1 ) states, which have synchronized clusters of sizes N -1 and 1, as well as splay states of clusters with equal sizes greater than 1. Additionally, we find limit cycles that clarify the stability of previously observed quasiperiodic behavior. Our framework exploits the neutrality of the dynamics for K =0 which allows us to implement a dimensional reduction strategy that simplifies the dynamics to a continuous flow on a codimension 3 subspace with the sign of K determining the flow direction. This reduction framework naturally incorporates a hierarchy of partially synchronized subspaces in which the new attracting states lie. Using high-precision numerical simulations, we describe completely the sequence of bifurcations and the stability of all fixed points and limit cycles for N =2 -4 . The set of possible attracting states can be used to distinguish different classes of neuron models. For instance from our previous work [Chaos 24, 013114 (2014), 10.1063/1.4858458] we know that of the types of partially synchronized states discussed here, only the (N -1 ,1 ) states can be stable in systems of identical coupled sinusoidal (i.e., Kuramoto type) oscillators, such as θ -neuron models. Upon introducing a small variation in individual neuron parameters, the attracting fixed points we discuss here generalize to equivalent fixed points in which neurons need not fire coincidently.

  16. Independent-Cluster Parametrizations of Wave Functions in Model Field Theories III. The Coupled-Cluster Phase Spaces and Their Geometrical Structure

    NASA Astrophysics Data System (ADS)

    Arponen, J. S.; Bishop, R. F.

    1993-11-01

    In this third paper of a series we study the structure of the phase spaces of the independent-cluster methods. These phase spaces are classical symplectic manifolds which provide faithful descriptions of the quantum mechanical pure states of an arbitrary system. They are "superspaces" in the sense that the full physical many-body or field-theoretic system is described by a point of the space, in contrast to "ordinary" spaces for which the state of the physical system is described rather by the whole space itself. We focus attention on the normal and extended coupled-cluster methods (NCCM and ECCM). Both methods provide parametrizations of the Hilbert space which take into account in increasing degrees of completeness the connectivity properties of the associated perturbative diagram structure. This corresponds to an increasing incorporation of locality into the description of the quantum system. As a result the degree of nonlinearity increases in the dynamical equations that govern the temporal evolution and determine the equilibrium state. Because of the nonlinearity, the structure of the manifold becomes geometrically complicated. We analyse the neighbourhood of the ground state of the one-mode anharmonic bosonic field theory and derive the nonlinear expansion beyond the linear response regime. The expansion is given in terms of normal-mode amplitudes, which provide the best local coordinate system close to the ground state. We generalize the treatment to other nonequilibrium states by considering the similarly defined normal coordinates around the corresponding phase space point. It is pointed out that the coupled-cluster method (CCM) maps display such features as (an)holonomy, or geometric phase. For example, a physical state may be represented by a number of different points on the CCM manifold. For this reason the whole phase spaces in the NCCM or ECCM cannot be covered by a single chart. To account for this non-Euclidean nature we introduce a suitable pseudo

  17. Finite temperature vibronic spectra of harmonic surfaces: a time-dependent coupled cluster approach

    NASA Astrophysics Data System (ADS)

    Sridhar Reddy, Ch.; Durga Prasad, M.

    2015-10-01

    An algorithm to compute vibronic spectra of harmonic surfaces including Dushinsky rotation and Hertzberg-Teller terms is described. The method, inspired by thermo field dynamics, maps the thermal density matrix onto the vacuum state and uses the time-dependent coupled cluster ansatz to propagate it in time. In the Franck-Condon approximation where the dipole matrix elements are taken to be constants, this reduces to the auto correlation function of the new vacuum. In the Hertzberg-Teller approximation, the full time evolution operator is needed. This too is governed by a closed set of equations. The theoretical development is presented along with an application to anthracene.

  18. Coupled-cluster theory computation of the nuclear electric dipole polarizability

    NASA Astrophysics Data System (ADS)

    Bacca, Sonia; Miorelli, Mirko; Barnea, Nir; Hagen, Gaute; Orlandini, Giuseppina; Papenbrock, Thomas

    2016-03-01

    The electric dipole polarizability αD is strongly correlated with the size of atomic nuclei. It informs us about the neutron equation of state and links atomic nuclei to neutron stars. In recent years, scattering experiments have been used to determine the dipole polarizability in 208Pb, 120Sn and 68Ni. Combining the Lorentz integral transform with the coupled-cluster method allows us to perform ab initio computations of αD for medium mass nuclei. In Ref. we predicted the polarizability for 48Ca and presently we are investigating heavier systems such as 68Ni and 90Zn.

  19. Multireference coupled-cluster calculation of the dissociation energy profile of triplet ketene

    NASA Astrophysics Data System (ADS)

    Ogihara, Yusuke; Yamamoto, Takeshi; Kato, Shigeki

    2011-07-01

    Triplet ketene exhibits a steplike structure in the experimentally observed photodissociation rates, but its mechanism is still unknown despite many theoretical efforts. Here we revisit this problem by calculating the potential energy profile of triplet ketene with the Adamowicz and Mukherjee multireference coupled-cluster (MRCC) theories. At the MRCCSD level, the imaginary frequency of the dissociation barrier is calculated to be about 300i cm-1, which is slightly smaller than the previous estimates but is still much greater than the expected maximum value for reproducing the observed steps (100i cm-1). This implies that other types of mechanisms (including nonadiabatic ones) may be more plausible for the observed steps.

  20. Study of coupled-cluster correlations on electromagnetic transitions and hyperfine structure constants of W VI

    NASA Astrophysics Data System (ADS)

    Bhowmik, Anal; Roy, Sourav; Nath Dutta, Narendra; Majumder, Sonjoy

    2017-06-01

    This work presents precise calculations of important electromagnetic transition amplitudes along with details of their many-body correlations using the relativistic coupled-cluster method. Studies of hyperfine interaction constants, useful for plasma diagnostics, with this correlation exhaustive many-body approach, are another important area of this work. The calculated oscillator strengths of allowed transitions, amplitudes of forbidden transitions and lifetimes are compared with the other theoretical results wherever available and they show a good agreement. Hyperfine constants of different isotopes of W VI, presented in this paper, will be helpful in gaining an accurate picture of the abundances of this element in different astronomical bodies.

  1. Scalar Relativistic Equation-Of Coupled Cluster Calculations of Core-Ionized States

    NASA Astrophysics Data System (ADS)

    Cheng, Lan

    2017-06-01

    Scalar relativistic equation-of-motion coupled cluster (EOMCC) calculations of core ionization/excitation energies for a set of benchmark molecules are reported. The Arnoldi algorithm as well as the core-valence-separation (CVS) scheme have been used to expedite the convergence of the wave function for the core-ionized/excited states. Scalar relativistic effects have been accounted for using the spin-free exact two-component theory in its one-electron variant (SFX2C-1e) and their importance are assessed. Preliminary calculations of ligand core excitation spectra of transition-metal containing compounds are also presented.

  2. Coupled-cluster theory of a gas of strongly-interacting electrons in the dilute limit

    SciTech Connect

    Mihaila, Bodgan; Cardenas, Andres L

    2008-01-01

    We study the ground-state properties of a dilute gas of strongly-interacting fermions in the framework of the coupled-cluster expansion (CCE). We demonstrate that properties such as universality, opening of a gap in the excitation spectrum and applicability of s-wave approximations appear naturally in the CCE approach. In the zero-density limit, we show that the ground-state energy density depends on only one parameter which in turn may depend at most on the spatial dimensionality of the system.

  3. Single-particle selection and alignment with heavy atom cluster-antibody conjugates

    PubMed Central

    Jensen, Grant J.; Kornberg, Roger D.

    1998-01-01

    A method is proposed for selecting and aligning images of single biological particles to obtain high-resolution structural information by cryoelectron microscopy. The particles will be labeled with multiple heavy atom clusters to permit the precise determination of particle locations and relative orientations even when imaged close to focus with a low electron dose, conditions optimal for recording high-resolution detail. Heavy atom clusters should also allow selection of images free from many kinds of defects, including specimen movement and particle inhomogeneity. Heavy atom clusters may be introduced in a general way by the construction of “adaptor” molecules based on single-chain Fv antibody fragments, consisting of a constant framework region engineered for optimal cluster binding and a variable antigen binding region selected for a specific target. The success of the method depends on the mobility of the heavy atom cluster on the particle, on the precision to which clusters can be located in an image, and on the sufficiency of cluster projections alone to orient and select particles for averaging. The necessary computational algorithms were developed and implemented in simulations that address the feasibility of the method. PMID:9689068

  4. Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

    SciTech Connect

    Tecmer, Paweł Visscher, Lucas; Severo Pereira Gomes, André; Knecht, Stefan

    2014-07-28

    We present a study of the electronic structure of the [UO{sub 2}]{sup +}, [UO{sub 2}]{sup 2} {sup +}, [UO{sub 2}]{sup 3} {sup +}, NUO, [NUO]{sup +}, [NUO]{sup 2} {sup +}, [NUN]{sup −}, NUN, and [NUN]{sup +} molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin–orbit coupling and Gaunt interactions are compared to results obtained with the Dirac–Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity)

  5. Carbon Nanotube-Quantum Dot Nanohybrids: Coupling with Single-Particle Control in Aqueous Solution.

    PubMed

    Attanzio, Antonio; Sapelkin, Andrei; Gesuele, Felice; van der Zande, Arend; Gillin, William P; Zheng, Ming; Palma, Matteo

    2017-02-10

    A strategy is reported for the controlled assembly of organic-inorganic heterostructures consisting of individual single-walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT-QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD-based optoelectronic and light-energy conversion devices.

  6. Phonon induced spin relaxation times of single donors and donor clusters in silicon

    NASA Astrophysics Data System (ADS)

    Hsueh, Yuling; Buch, Holger; Hollenberg, Lloyd; Simmons, Michelle; Klimeck, Gerhard; Rahman, Rajib

    2014-03-01

    The phonon induced relaxation times (T1) of electron spins bound to single phosphorous (P) donors and P donor clusters in silicon is computed using the atomistic tight-binding method. The electron-phonon Hamiltonian is directly computed from the strain dependent tight-binding Hamiltonian, and the relaxation time is computed from Fermi's Golden Rule using the donor states and the electron-phonon Hamiltonian. The self-consistent Hartree method is used to compute the multi-electron wavefunctions in donor clusters. The method takes into account the full band structure of silicon including the spin-orbit interaction, and captures both valley repopulation and single valley g-factor shifts in a unified framework. The single donor relaxation rate varies proportionally to B5, and is of the order of seconds at B =2T, both in good agreement with experimental single donor data (A. Morello et. al., Nature 467, 687 (2010)). T1 calculations in donor clusters show variations for different electron numbers and donor numbers and locations. The computed T1 in a 4P:5e donor cluster match well with a scanning tunneling microscope patterned P donor cluster (H. Buch et. al., Nature Communications 4, 2017 (2013)).

  7. Topographic prominence as a method for cluster identification in single-molecule localisation data.

    PubMed

    Griffié, Juliette; Boelen, Lies; Burn, Garth; Cope, Andrew P; Owen, Dylan M

    2015-11-01

    Single-molecule localisation based super-resolution fluorescence imaging produces maps of the coordinates of fluorescent molecules in a region of interest. Cluster analysis algorithms provide information concerning the clustering characteristics of these molecules, often through the generation of cluster heat maps based on local molecular density. The goal of this study was to generate a new cluster analysis method based on a topographic approach. In particular, a topographic map of the level of clustering across a region is generated based on Getis' variant of Ripley's K-function. By using the relative heights (topographic prominence, TP) of the peaks in the map, cluster characteristics can be identified more accurately than by using previously demonstrated height thresholds. Analogous to geological TP, the concepts of wet and dry TP and topographic isolation are introduced to generate binary maps. The algorithm is validated using simulated and experimental data and found to significantly outperform previous cluster identification methods. Illustration of the topographic prominence based cluster analysis algorithm.

  8. Formulation and implementation of a unitary group adapted state universal multi-reference coupled cluster (UGA-SUMRCC) theory: Excited and ionized state energies

    NASA Astrophysics Data System (ADS)

    Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

    2012-08-01

    The traditional state universal multi-reference coupled cluster (SUMRCC) theory uses the Jeziorski-Monkhorst (JM) based Ansatz of the wave operator: Ω = ∑μΩμ|ϕμ⟩⟨ϕμ|, where Ωμ = exp (Tμ) is the cluster representation of the component of Ω inducing virtual excitations from the model function ϕμ. In the first formulations, ϕμs were chosen to be single determinants and Tμs were defined in terms of spinorbitals. This leads to spin-contamination for the non-singlet cases. In this paper, we propose and implement an explicitly spin-free realization of the SUMRCC theory. This method uses spin-free unitary generators in defining the cluster operators, {Tμ}, which even at singles-doubles truncation, generates non-commuting cluster operators. We propose the use of normal-ordered exponential parameterization for Ω:∑μ{exp (Tμ)}|ϕμ⟩⟨ϕμ|, where {} denotes the normal ordering with respect to a common closed shell vacuum which makes the "direct term" of the SUMRCC equations terminate at the quartic power. We choose our model functions {ϕμ} as unitary group adapted (UGA) Gel'fand states which is why we call our theory UGA-SUMRCC. In the spirit of the original SUMRCC, we choose exactly the right number of linearly independent cluster operators in {Tμ} such that no redundancies in the virtual functions lbrace χ _μ ^lrbrace are involved. Using example applications for electron detached/attached and h-p excited states relative to a closed shell ground state we discuss how to choose the most compact and non-redundant cluster operators. Although there exists a more elaborate spin-adapted JM-like ansatz of Datta and Mukherjee (known as combinatoric open-shell CC (COS-CC), its working equations are more complex. Results are compared with those from COS-CC, equation of motion coupled cluster methods, restricted open-shell Hartree-Fock coupled cluster, and full configuration interaction. We observe that our results are more accurate with respect to

  9. Formulation and implementation of a unitary group adapted state universal multi-reference coupled cluster (UGA-SUMRCC) theory: excited and ionized state energies.

    PubMed

    Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

    2012-08-21

    The traditional state universal multi-reference coupled cluster (SUMRCC) theory uses the Jeziorski-Monkhorst (JM) based Ansatz of the wave operator: Ω = Σ(μ)Ω(μ)|φ(μ)><φ(μ)|, where Ω(μ) = exp(T(μ)) is the cluster representation of the component of Ω inducing virtual excitations from the model function φ(μ). In the first formulations, φ(μ)s were chosen to be single determinants and T(μ)s were defined in terms of spinorbitals. This leads to spin-contamination for the non-singlet cases. In this paper, we propose and implement an explicitly spin-free realization of the SUMRCC theory. This method uses spin-free unitary generators in defining the cluster operators, {T(μ)}, which even at singles-doubles truncation, generates non-commuting cluster operators. We propose the use of normal-ordered exponential parameterization for Ω:Σ(μ){exp(T(μ))}|φ(μ)><φ(μ)|, where {} denotes the normal ordering with respect to a common closed shell vacuum which makes the "direct term" of the SUMRCC equations terminate at the quartic power. We choose our model functions {φ(μ)} as unitary group adapted (UGA) Gel'fand states which is why we call our theory UGA-SUMRCC. In the spirit of the original SUMRCC, we choose exactly the right number of linearly independent cluster operators in {T(μ)} such that no redundancies in the virtual functions {χ(μ)(l)} are involved. Using example applications for electron detached/attached and h-p excited states relative to a closed shell ground state we discuss how to choose the most compact and non-redundant cluster operators. Although there exists a more elaborate spin-adapted JM-like ansatz of Datta and Mukherjee (known as combinatoric open-shell CC (COS-CC), its working equations are more complex. Results are compared with those from COS-CC, equation of motion coupled cluster methods, restricted open-shell Hartree-Fock coupled cluster, and full configuration interaction. We observe that our results are more accurate with

  10. Comparison of the quadratic configuration interaction and coupled cluster approaches to electron correlation including the effect of triple excitations

    NASA Technical Reports Server (NTRS)

    Taylor, Peter R.; Lee, Timothy J.; Rendell, Alistair P.

    1990-01-01

    The recently proposed quadratic configuration interaction (QCI) method is compared with the more rigorous coupled cluster (CC) approach for a variety of chemical systems. Some of these systems are well represented by a single-determinant reference function and others are not. The finite order singles and doubles correlation energy, the perturbational triples correlation energy, and a recently devised diagnostic for estimating the importance of multireference effects are considered. The spectroscopic constants of CuH, the equilibrium structure of cis-(NO)2 and the binding energies of Be3, Be4, Mg3, and Mg4 were calculated using both approaches. The diagnostic for estimating multireference character clearly demonstrates that the QCI method becomes less satisfactory than the CC approach as non-dynamical correlation becomes more important, in agreement with a perturbational analysis of the two methods and the numerical estimates of the triple excitation energies they yield. The results for CuH show that the differences between the two methods become more apparent as the chemical systems under investigation becomes more multireference in nature and the QCI results consequently become less reliable. Nonetheless, when the system of interest is dominated by a single reference determinant both QCI and CC give very similar results.

  11. Excitons in potassium bromide: A study using embedded time-dependent density functional theory and equation-of-motion coupled cluster methods

    NASA Astrophysics Data System (ADS)

    Govind, N.; Sushko, P. V.; Hess, W. P.; Valiev, M.; Kowalski, K.

    2009-03-01

    We present a study of the lowest surface and bulk excitations of the well-studied potassium bromide (KBr) system using an embedded cluster method. The excited states of the embedded cluster are studied systematically using time-dependent density functional theory (TDDFT) and high-level equation-of-motion coupled cluster (EOMCC) methods. In particular, we have used EOMCC models with singles and doubles (EOMCCSD) and two approaches which account for the effect of triply excited configurations in non-iterative and iterative fashions. We compare and contrast the results between these theories as well as compare our results with experiment. The bulk-surface exciton shift is also calculated at the TDDFT level and compared with experiment.

  12. Single scale cluster expansions with applications to many Boson and unbounded spin systems

    NASA Astrophysics Data System (ADS)

    Lohmann, Martin

    2015-06-01

    We develop a cluster expansion to show exponential decay of correlations for quite general single scale spin systems, as they arise in lattice quantum field theory and discretized functional integral representations for observables of quantum statistical mechanics. We apply our results to the small field approximation to the coherent state correlation functions of the grand canonical Bose gas at negative chemical potential, constructed by Balaban et al. [Ann. Henri Poincaré 11, 151-350 (2010c)], and to N component unbounded spin systems with repulsive two body interaction and massive, possibly complex, covariance. Our cluster expansion is derived by a single application of the Brydges-Kennedy-Abdesselam-Rivasseau interpolation formula.

  13. Single scale cluster expansions with applications to many Boson and unbounded spin systems

    SciTech Connect

    Lohmann, Martin

    2015-06-15

    We develop a cluster expansion to show exponential decay of correlations for quite general single scale spin systems, as they arise in lattice quantum field theory and discretized functional integral representations for observables of quantum statistical mechanics. We apply our results to the small field approximation to the coherent state correlation functions of the grand canonical Bose gas at negative chemical potential, constructed by Balaban et al. [Ann. Henri Poincaré 11, 151–350 (2010c)], and to N component unbounded spin systems with repulsive two body interaction and massive, possibly complex, covariance. Our cluster expansion is derived by a single application of the Brydges-Kennedy-Abdesselam-Rivasseau interpolation formula.

  14. Single-photon multi-ports router based on the coupled cavity optomechanical system.

    PubMed

    Li, Xun; Zhang, Wen-Zhao; Xiong, Biao; Zhou, Ling

    2016-12-22

    A scheme of single-photon multi-port router is put forward by coupling two optomechanical cavities with waveguides. It is shown that the coupled two optomechanical cavities can exhibit photon blockade effect, which is generated from interference of three mode interaction. A single-photon travel along the system is calculated. The results show that the single photon can be controlled in the multi-port system because of the radiation pressure, which should be useful for constructing quantum network.

  15. Zero modes in the light-front coupled-cluster method

    SciTech Connect

    Chabysheva, Sophia S.; Hiller, John R.

    2014-01-15

    The light-front coupled-cluster (LFCC) method is a technique for solving Hamiltonian eigenvalue problems in light-front-quantized field theories. Its primary purpose is to provide a systematic sequence of solvable approximations to the original eigenvalue problem without the truncation of Fock space. Here we discuss the incorporation of zero modes, modes of zero longitudinal momentum, into the formalism of the method. Without zero modes, the light-front vacuum is trivial, and the vacuum expectation value of the field is always zero. The LFCC method with zero modes provides for vacuum structure, in the form of a generalized coherent state of zero modes, as is illustrated here in two-dimensional model field theories. -- Highlights: •Extends the light-front coupled-cluster method to include zero modes. •Illustrates with an analysis of vacuum structure for phi-3, phi-4, and Wick–Cutkosky model field theories. •Demonstrates the applicability of the LFCC method to theories with spontaneous symmetry breaking.

  16. A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

    SciTech Connect

    Feller, David Peterson, Kirk A.; Davidson, Ernest R.

    2014-09-14

    A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg {sup 1}B{sub 1u} V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10{sup 9} parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the {sup 2}B{sub 3u} and {sup 2}B{sub 3} states were also determined. In addition, the heat of formation of twisted ethylene {sup 3}A{sub 1} was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.

  17. A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques.

    PubMed

    Feller, David; Peterson, Kirk A; Davidson, Ernest R

    2014-09-14

    A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg (1)B(1u) V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10(9) parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the (2)B(3u) and (2)B3 states were also determined. In addition, the heat of formation of twisted ethylene (3)A1 was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.

  18. Cooperative lifetime reduction of single acene molecules attached to the surface of neon clusters

    NASA Astrophysics Data System (ADS)

    Müller, Markus; Izadnia, Sharareh; Vlaming, Sebastiaan M.; Eisfeld, Alexander; LaForge, Aaron; Stienkemeier, Frank

    2015-09-01

    Tetracene and pentacene molecules attached to the surface of neon clusters have been spectroscopically investigated. The fluorescence spectra indicate that the molecules are immobilized on the surface and, to a large extent, do not form complexes. By varying the number of attached molecules, laser power, or neon cluster size, we find a systematic fluorescence lifetime reduction up to a factor of 20 indicating a cooperative coupling in our system. For averaged intermolecular distances greater than 33 Å, we attribute the reduction in fluorescence lifetime to Dicke superradiance, while for smaller intermolecular distances, nonradiative decay mechanisms cause additional lifetime reduction.

  19. Reduction of the virtual space for coupled-cluster excitation energies of large molecules and embedded systems.

    PubMed

    Send, Robert; Kaila, Ville R I; Sundholm, Dage

    2011-06-07

    We investigate how the reduction of the virtual space affects coupled-cluster excitation energies at the approximate singles and doubles coupled-cluster level (CC2). In this reduced-virtual-space (RVS) approach, all virtual orbitals above a certain energy threshold are omitted in the correlation calculation. The effects of the RVS approach are assessed by calculations on the two lowest excitation energies of 11 biochromophores using different sizes of the virtual space. Our set of biochromophores consists of common model systems for the chromophores of the photoactive yellow protein, the green fluorescent protein, and rhodopsin. The RVS calculations show that most of the high-lying virtual orbitals can be neglected without significantly affecting the accuracy of the obtained excitation energies. Omitting all virtual orbitals above 50 eV in the correlation calculation introduces errors in the excitation energies that are smaller than 0.1 eV. By using a RVS energy threshold of 50 eV, the CC2 calculations using triple-ζ basis sets (TZVP) on protonated Schiff base retinal are accelerated by a factor of 6. We demonstrate the applicability of the RVS approach by performing CC2/TZVP calculations on the lowest singlet excitation energy of a rhodopsin model consisting of 165 atoms using RVS thresholds between 20 eV and 120 eV. The calculations on the rhodopsin model show that the RVS errors determined in the gas-phase are a very good approximation to the RVS errors in the protein environment. The RVS approach thus renders purely quantum mechanical treatments of chromophores in protein environments feasible and offers an ab initio alternative to quantum mechanics/molecular mechanics separation schemes.

  20. The effects of unsteady aerodynamics on single and clustered parachute systems

    SciTech Connect

    Waye, D.E.; Johnson, D.W.

    1989-01-01

    A study was performed to evaluate the performance of equivalent drag area single parachute systems and cluster parachute systems during the early inflation and initial deceleration phase. Analytical work showed that the cluster system could exhibit better performance during this unsteady aerodynamic phase due to a significant decrease in the apparent mass of air influenced by the parachutes. Two test programs have been performed in support of these assumptions. The first compared systems with parachute drag areas of approximately 750 ft/sup 2/ and a payload of 2400 lbs. The cluster system exhibited increased performance and less susceptibility to parachute collapse due to wake recontact. The second series compared systems with parachute drag areas of approximately 260 ft/sup 2/ with a payload of 800 lbs. The advantages of the cluster system were less apparent but performance was moderately improved. 4 refs., 7 figs.

  1. Computer simulation of argon cluster inside a single-walled carbon nanotube

    NASA Astrophysics Data System (ADS)

    Kośmider, M.; Dendzik, Z.; Pałucha, S.; Gburski, Z.

    2004-10-01

    Atomically detailed standard molecular dynamics simulation has been performed to study dynamics and structure properties of argon clusters (Ar 110, Ar 280, Ar 250) adsorbed inside single-walled carbon nanotubes (SWNT). The adsorption potential have been constructed as a sum of two-body interactions between the cluster atoms and SWNT atoms. We have found no liquid-like phase in all studied cases—(10,10), (15,15) and (20,0) SWNT. Movements of the argon atoms are found to be well localized in the whole range of temperatures in which the cluster retains its integrity, except of the (20,0) nanotube case, where the movements of atoms belonging to the innermost layer have been observed. The radial distribution function and the vibrational modes of the argon atoms belonging to different layers of the cluster are analyzed.

  2. Probing dynamic fluorescence properties of single and clustered quantum dots toward quantitative biomedical imaging of cells.

    PubMed

    Kang, Hyeong-Gon; Tokumasu, Fuyuki; Clarke, Matthew; Zhou, Zhenping; Tang, Jianyong; Nguyen, Tinh; Hwang, Jeeseong

    2010-01-01

    We present results on the dynamic fluorescence properties of bioconjugated nanocrystals or quantum dots (QDs) in different chemical and physical environments. A variety of QD samples was prepared and compared: isolated individual QDs, QD aggregates, and QDs conjugated to other nanoscale materials, such as single-wall carbon nanotubes (SWCNTs) and human erythrocyte plasma membrane proteins. We discuss plausible scenarios to explain the results obtained for the fluorescence characteristics of QDs in these samples, especially for the excitation time-dependent fluorescence emission from clustered QDs. We also qualitatively demonstrate enhanced fluorescence emission signals from clustered QDs and deduce that the band 3 membrane proteins in erythrocytes are clustered. This approach is promising for the development of QD-based quantitative molecular imaging techniques for biomedical studies involving biomolecule clustering.

  3. Sub-10 nm nano-gap device for single-cluster transport measurements

    SciTech Connect

    Rousseau, J. Morel, R.; Vila, L.; Brenac, A.; Marty, A.; Notin, L.; Beigné, C.

    2014-02-17

    We present a versatile procedure for the fabrication of single electron transistor (SET) devices with nanometer-sized clusters and embedded back gate electrode. The process uses sputtering gas-aggregation for the growth of clusters and e-beam lithography with double angle shadow-edge deposition to obtain electrodes separated by nano-gaps with width below 10 nm. The nano-gap width is easily controlled only by geometrical factors such as deposited thin film thickness and evaporation angles. The usefulness of this technique is demonstrated by measuring the SET behavior of a device with a 4 nm cobalt cluster embedded in alumina, where the Coulomb blockade and incremental cluster charging can be readily identified without resorting to the differential conductivity.

  4. Cluster Types of Attitudes toward Multiple Role Planning of Single, Korean, Female Undergraduates

    ERIC Educational Resources Information Center

    Woo, Young Jee; Lee, Ki-Hak

    2010-01-01

    The current study explored the attitudes that single, Korean, female college students have toward multiple role planning. Cluster groups among the participants were identified by their scores on the Korean language version (Yang, 1997) of the Attitudes Toward Multiple Role Planning (ATMRP; Weitzman, 1992) measure, and significant differences in…

  5. Molecular response properties in equation of motion coupled cluster theory: A time-dependent perspective

    NASA Astrophysics Data System (ADS)

    Coriani, Sonia; Pawłowski, Filip; Olsen, Jeppe; Jørgensen, Poul

    2016-01-01

    Molecular response properties for ground and excited states and for transitions between these states are defined by solving the time-dependent Schrödinger equation for a molecular system in a field of a time-periodic perturbation. In equation of motion coupled cluster (EOM-CC) theory, molecular response properties are commonly obtained by replacing, in configuration interaction (CI) molecular response property expressions, the energies and eigenstates of the CI eigenvalue equation with the energies and eigenstates of the EOM-CC eigenvalue equation. We show here that EOM-CC molecular response properties are identical to the molecular response properties that are obtained in the coupled cluster-configuration interaction (CC-CI) model, where the time-dependent Schrödinger equation is solved using an exponential (coupled cluster) parametrization to describe the unperturbed system and a linear (configuration interaction) parametrization to describe the time evolution of the unperturbed system. The equivalence between EOM-CC and CC-CI molecular response properties only holds when the CI molecular response property expressions—from which the EOM-CC expressions are derived—are determined using projection and not using the variational principle. In a previous article [F. Pawłowski, J. Olsen, and P. Jørgensen, J. Chem. Phys. 142, 114109 (2015)], it was stated that the equivalence between EOM-CC and CC-CI molecular response properties only held for a linear response function, whereas quadratic and higher order response functions were mistakenly said to differ in the two approaches. Proving the general equivalence between EOM-CC and CC-CI molecular response properties is a challenging task, that is undertaken in this article. Proving this equivalence not only corrects the previous incorrect statement but also first and foremost leads to a new, time-dependent, perspective for understanding the basic assumptions on which the EOM-CC molecular response property expressions

  6. New Theoretical Developments in Exploring Electronically Excited States: Including Localized Configuration Interaction Singles and Application to Large Helium Clusters

    NASA Astrophysics Data System (ADS)

    Closser, Kristina Danielle

    superpositions of atomic states with surface states appearing close to the atomic excitation energies and interior states being blue shifted by up to ≈2 eV. The dynamics resulting from excitation of He_7 were subsequently explored using ab initio molecular dynamics (AIMD). These simulations were performed with classical adiabatic dynamics coupled to a new state-following algorithm on CIS potential energy surfaces. Most clusters were found to completely dissociate and resulted in a single excited atomic state (90%), however, some trajectories formed bound, He*2 (3%), and a few yielded excited trimers (<0.5%). Comparisons were made with available experimental information on much larger clusters. Various applications of this state following algorithm are also presented. In addition to AIMD, these include excited-state geometry optimization and minimal energy path finding via the growing string method. When using state following we demonstrate that more physical results can be obtained with AIMD calculations. Also, the optimized geometries of three excited states of cytosine, two of which were not found without state following, and the minimal energy path between the lowest two singlet excited states of protonated formaldimine are offered as example applications. Finally, to address large clusters, a local variation of CIS was developed. This method exploits the properties of absolutely localized molecular orbitals (ALMOs) to limit the total number of excitations to scaling only linearly with cluster size, which results in formal scaling with the third power of the system size. The derivation of the equations and design of the algorithm are discussed in detail, and computational timings as well as a pilot application to the size dependence of the helium cluster spectrum are presented.

  7. Massively parallel implementations of coupled-cluster methods for electron spin resonance spectra. I. Isotropic hyperfine coupling tensors in large radicals

    NASA Astrophysics Data System (ADS)

    Verma, Prakash; Perera, Ajith; Morales, Jorge A.

    2013-11-01

    Coupled cluster (CC) methods provide highly accurate predictions of molecular properties, but their high computational cost has precluded their routine application to large systems. Fortunately, recent computational developments in the ACES III program by the Bartlett group [the OED/ERD atomic integral package, the super instruction processor, and the super instruction architecture language] permit overcoming that limitation by providing a framework for massively parallel CC implementations. In that scheme, we are further extending those parallel CC efforts to systematically predict the three main electron spin resonance (ESR) tensors (A-, g-, and D-tensors) to be reported in a series of papers. In this paper inaugurating that series, we report our new ACES III parallel capabilities that calculate isotropic hyperfine coupling constants in 38 neutral, cationic, and anionic radicals that include the 11B, 17O, 9Be, 19F, 1H, 13C, 35Cl, 33S,14N, 31P, and 67Zn nuclei. Present parallel calculations are conducted at the Hartree-Fock (HF), second-order many-body perturbation theory [MBPT(2)], CC singles and doubles (CCSD), and CCSD with perturbative triples [CCSD(T)] levels using Roos augmented double- and triple-zeta atomic natural orbitals basis sets. HF results consistently overestimate isotropic hyperfine coupling constants. However, inclusion of electron correlation effects in the simplest way via MBPT(2) provides significant improvements in the predictions, but not without occasional failures. In contrast, CCSD results are consistently in very good agreement with experimental results. Inclusion of perturbative triples to CCSD via CCSD(T) leads to small improvements in the predictions, which might not compensate for the extra computational effort at a non-iterative N7-scaling in CCSD(T). The importance of these accurate computations of isotropic hyperfine coupling constants to elucidate experimental ESR spectra, to interpret spin-density distributions, and to

  8. Massively parallel implementations of coupled-cluster methods for electron spin resonance spectra. I. Isotropic hyperfine coupling tensors in large radicals

    SciTech Connect

    Verma, Prakash; Morales, Jorge A.; Perera, Ajith

    2013-11-07

    Coupled cluster (CC) methods provide highly accurate predictions of molecular properties, but their high computational cost has precluded their routine application to large systems. Fortunately, recent computational developments in the ACES III program by the Bartlett group [the OED/ERD atomic integral package, the super instruction processor, and the super instruction architecture language] permit overcoming that limitation by providing a framework for massively parallel CC implementations. In that scheme, we are further extending those parallel CC efforts to systematically predict the three main electron spin resonance (ESR) tensors (A-, g-, and D-tensors) to be reported in a series of papers. In this paper inaugurating that series, we report our new ACES III parallel capabilities that calculate isotropic hyperfine coupling constants in 38 neutral, cationic, and anionic radicals that include the {sup 11}B, {sup 17}O, {sup 9}Be, {sup 19}F, {sup 1}H, {sup 13}C, {sup 35}Cl, {sup 33}S,{sup 14}N, {sup 31}P, and {sup 67}Zn nuclei. Present parallel calculations are conducted at the Hartree-Fock (HF), second-order many-body perturbation theory [MBPT(2)], CC singles and doubles (CCSD), and CCSD with perturbative triples [CCSD(T)] levels using Roos augmented double- and triple-zeta atomic natural orbitals basis sets. HF results consistently overestimate isotropic hyperfine coupling constants. However, inclusion of electron correlation effects in the simplest way via MBPT(2) provides significant improvements in the predictions, but not without occasional failures. In contrast, CCSD results are consistently in very good agreement with experimental results. Inclusion of perturbative triples to CCSD via CCSD(T) leads to small improvements in the predictions, which might not compensate for the extra computational effort at a non-iterative N{sup 7}-scaling in CCSD(T). The importance of these accurate computations of isotropic hyperfine coupling constants to elucidate

  9. Massively parallel unsupervised single-particle cryo-EM data clustering via statistical manifold learning

    PubMed Central

    Wu, Jiayi; Ma, Yong-Bei; Congdon, Charles; Brett, Bevin; Chen, Shuobing; Xu, Yaofang; Ouyang, Qi

    2017-01-01

    Structural heterogeneity in single-particle cryo-electron microscopy (cryo-EM) data represents a major challenge for high-resolution structure determination. Unsupervised classification may serve as the first step in the assessment of structural heterogeneity. However, traditional algorithms for unsupervised classification, such as K-means clustering and maximum likelihood optimization, may classify images into wrong classes with decreasing signal-to-noise-ratio (SNR) in the image data, yet demand increased computational costs. Overcoming these limitations requires further development of clustering algorithms for high-performance cryo-EM data processing. Here we introduce an unsupervised single-particle clustering algorithm derived from a statistical manifold learning framework called generative topographic mapping (GTM). We show that unsupervised GTM clustering improves classification accuracy by about 40% in the absence of input references for data with lower SNRs. Applications to several experimental datasets suggest that our algorithm can detect subtle structural differences among classes via a hierarchical clustering strategy. After code optimization over a high-performance computing (HPC) environment, our software implementation was able to generate thousands of reference-free class averages within hours in a massively parallel fashion, which allows a significant improvement on ab initio 3D reconstruction and assists in the computational purification of homogeneous datasets for high-resolution visualization. PMID:28786986

  10. Investigating the Correspondence Between Transcriptomic and Proteomic Expression Profiles Using Coupled Cluster Models.

    SciTech Connect

    Rogers, Simon; Girolami, Mark; Kolch, Walter; Waters, Katrina M.; Liu, Tao; Thrall, Brian D.; Wiley, H. S.

    2008-12-01

    Modern transcriptomics and proteomics enable us to survey the expression of RNAs and proteins at large scales. While these data are usually generated and analysed separately, there is an increasing interest in comparing and co-analysing transcriptome and proteome expression data. A major open question is whether transcriptome and proteome expression is linked and how it is coordinated. Results: Here we have developed a probabilistic clustering model that permits analysis of the links between transcriptomic and proteomic profiles in a sensible and flexible manner. Our coupled mixture model defines a prior probability distribution over the component to which a protein profile should be assigned conditioned on which component the associated mRNA profile belongs to. By providing probabilistic assignments this approach sits between the two extremes of concatenating the data on the assumption that mRNA and protein clusters would have a one-to-one relationship, and independent clustering where the mRNA profile provides no information on the protein profile and vice-versa. We apply this approach to a large dataset of quantitative transcriptomic and proteomic expression data obtained from a human breast epithelial cell line (HMEC) stimulated by epidermal growth factor (EGF) over a series of timepoints corresponding to one cell cycle. The results reveal a complex relationship between transcriptome and proteome with most mRNA clusters linked to at least two protein clusters, and vice versa. A more detailed analysis incorporating information on gene function from the gene ontology database shows that a high correlation of mRNA and protein expression is limited to the components of some molecular machines, such as the ribosome, cell adhesion complexes and the TCP-1 chaperonin involved in protein folding. Conclusions: The dynamic regulation of the transcriptome and proteome in mammalian cells in response to an acute mitogenic stimulus appears largely independent with very little

  11. Single-photon nonreciprocal transport in one-dimensional coupled-resonator waveguides

    NASA Astrophysics Data System (ADS)

    Xu, Xun-Wei; Chen, Ai-Xi; Li, Yong; Liu, Yu-xi

    2017-06-01

    We study the transport of a single photon in two coupled one-dimensional semi-infinite coupled-resonator waveguides (CRWs), in which both end sides are coupled to a dissipative cavity. We demonstrate that a single photon can transfer from one semi-infinite CRW to the other nonreciprocally. Based on such nonreciprocity, we further construct a three-port single-photon circulator by a T-shaped waveguide, in which three semi-infinite CRWs are pairwise mutually coupled to each other. The single-photon nonreciprocal transport is induced by the breaking of the time-reversal symmetry and the optimal conditions for these phenomena are obtained analytically. The CRWs with broken time-reversal symmetry will open up a kind of quantum device with versatile applications in quantum networks.

  12. Controlling photon transport in the single-photon weak-coupling regime of cavity optomechanics

    NASA Astrophysics Data System (ADS)

    Zhang, Wen-Zhao; Cheng, Jiong; Liu, Jing-Yi; Zhou, Ling

    2015-06-01

    We study the photon statistics properties of few-photon transport in an optomechanical system where an optomechanical cavity couples to two empty cavities. By analytically deriving the one- and two-photon currents in terms of a zero-time-delayed two-order correlation function, we show that a photon blockade can be achieved in both the single-photon strong-coupling regime and the single-photon weak-coupling regime due to the nonlinear interacting and multipath interference. Furthermore, our systems can be applied as a quantum optical diode, a single-photon source, and a quantum optical capacitor. It is shown that this the photon transport controlling devices based on photon antibunching does not require the stringent single-photon strong-coupling condition. Our results provide a promising platform for the coherent manipulation of optomechanics, which has potential applications for quantum information processing and quantum circuit realization.

  13. Comparison of coherently coupled multi-cavity and quantum dot embedded single cavity systems.

    PubMed

    Kocaman, Serdar; Sayan, Gönül Turhan

    2016-12-12

    Temporal group delays originating from the optical analogue to electromagnetically induced transparency (EIT) are compared in two systems. Similar transmission characteristics are observed between a coherently coupled high-Q multi-cavity array and a single quantum dot (QD) embedded cavity in the weak coupling regime. However, theoretically generated group delay values for the multi-cavity case are around two times higher. Both configurations allow direct scalability for chip-scale optical pulse trapping and coupled-cavity quantum electrodynamics (QED).

  14. Equation-of-motion coupled cluster method for high spin double electron attachment calculations

    SciTech Connect

    Musiał, Monika Lupa, Łukasz; Kucharski, Stanisław A.

    2014-03-21

    The new formulation of the equation-of-motion (EOM) coupled cluster (CC) approach applicable to the calculations of the double electron attachment (DEA) states for the high spin components is proposed. The new EOM equations are derived for the high spin triplet and quintet states. In both cases the new equations are easier to solve but the substantial simplification is observed in the case of quintets. Out of 21 diagrammatic terms contributing to the standard DEA-EOM-CCSDT equations for the R{sub 2} and R{sub 3} amplitudes only four terms survive contributing to the R{sub 3} part. The implemented method has been applied to the calculations of the excited states (singlets, triplets, and quintets) energies of the carbon and silicon atoms and potential energy curves for selected states of the Na{sub 2} (triplets) and B{sub 2} (quintets) molecules.

  15. Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals.

    PubMed

    Garza, Alejandro J; Sousa Alencar, Ana G; Scuseria, Gustavo E

    2015-12-28

    Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f(0) actinyl series (UO2(2+), NpO2(3+), PuO2(4+)), the isoelectronic NUN, and thorium (ThO, ThO(2+)) and nobelium (NoO, NoO2) oxides are studied.

  16. Use of recursively generated intermediates in state selective multireference coupled-cluster method: A numerical example

    SciTech Connect

    Ghose, K.B.; Adamowicz, L.

    1995-12-01

    The present work represents the first attempt to utilize the idea of recursively generated intermediates (RGI) in the framework of the state-selective multi-reference coupled-cluster method truncated at triple excitations [SS CCSD(T)]. The expressions for stepwise generation of intermediates are so structured that the spin and point symmetry simplifications can be easily applied during computation. Suitable modifications in SS CCSD(T) equations are introduced to allow for optional quasilinearization of nonlinear terms in difficult convergence situations. The computational code is, as expected, much faster than the SS CCSD(T) code without RGI adaptation. This has been numerically demonstrated by potential energy surface (PES) calculation of the HF molecule using a double zeta basis. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  17. Gaussian 3X (G3X) theory using coupled cluster and Brueckner doubles energies.

    SciTech Connect

    Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Pople, J. A.; Agere Systems; Northwestern Univ.

    2002-06-27

    Variations of Gaussian-3X (G3X) theory are presented having the quadratic configuration interaction (QCISD(T)) energy calculation replaced by either a coupled cluster (CCSD(T)) or Brueckner (BD(T)) energy. This modification is reported for several G3X methods including G3X, G3X(MP3), G3X(MP2), G3SX, and G3SX(MP3). In most cases the replacement of the QCISD(T) energy by one of these alternative energies results in a slight improvement in the accuracy of these methods as assessed on the G3/99 test set of molecules. These new G3X methods are useful alternatives to the G3X methods based on quadratic configuration interaction.

  18. Elastic Proton Scattering of Medium Mass Nuclei from Coupled-Cluster Theory

    SciTech Connect

    Hagen, G.; MichelN.,

    2012-01-01

    Using coupled-cluster theory and interactions from chiral effective field theory, we compute overlap functions for transfer and scattering of low-energy protons on the target nucleus 40Ca. Effects of three-nucleon forces are included phenomenologically as in-medium two-nucleon interactions. Using known asymptotic forms for one-nucleon overlap functions we derive a simple and intuitive way of computing scattering observables such as elastic scattering phase shifts and cross sections. As a first application and proof of principle, we compute phase shifts and differential interaction cross sections at energies of 9.6 and 12.44 MeV and compare with experimental data. Our computed diffraction minima are in fair agreement with experimental results, while we tend to overestimate the cross sections at large scattering angles.

  19. Computation of molecular parity violation using the coupled-cluster linear response approach

    NASA Astrophysics Data System (ADS)

    Horný, Ľuboš; Quack, Martin

    2015-07-01

    In memoriam, Nicholas C. Handy. We report the implementation of a coupled-cluster linear response approach for the computation of molecular parity violation (in the framework of the PSI3 code, in particular). The approach is applied first to molecules such as hydrogen peroxide (HOOH), hydrogen disulfide (HSSH) and dichlorinedioxide (ClOOCl), which have been studied previously. The importance of including correlation is demonstrated for these examples, also including selected variations of geometry providing parity violation as a function of torsional angles. For the substituted allenes, 1,3 difluoroallene (CHF=C=CHF), 1,fluoro,3 chloroallene (CHF=C=CHCl) and 1,3 dichloroallene (CHCl=C=CHCl), we find that in particular the last molecule may be a suitable candidate for the experimental study of molecular parity violation.

  20. Coupled-cluster method: A lattice-path-based subsystem approximation scheme for quantum lattice models

    SciTech Connect

    Bishop, R. F.; Li, P. H. Y.

    2011-04-15

    An approximation hierarchy, called the lattice-path-based subsystem (LPSUBm) approximation scheme, is described for the coupled-cluster method (CCM). It is applicable to systems defined on a regular spatial lattice. We then apply it to two well-studied prototypical (spin-(1/2) Heisenberg antiferromagnetic) spin-lattice models, namely, the XXZ and the XY models on the square lattice in two dimensions. Results are obtained in each case for the ground-state energy, the ground-state sublattice magnetization, and the quantum critical point. They are all in good agreement with those from such alternative methods as spin-wave theory, series expansions, quantum Monte Carlo methods, and the CCM using the alternative lattice-animal-based subsystem (LSUBm) and the distance-based subsystem (DSUBm) schemes. Each of the three CCM schemes (LSUBm, DSUBm, and LPSUBm) for use with systems defined on a regular spatial lattice is shown to have its own advantages in particular applications.

  1. A light-front coupled-cluster method for the nonperturbative solution of quantum field theories

    NASA Astrophysics Data System (ADS)

    Chabysheva, Sophia S.; Hiller, John R.

    2012-05-01

    We propose a new method for the nonperturbative solution of quantum field theories and illustrate its use in the context of a light-front analog to the Greenberg-Schweber model. The method is based on light-front quantization and uses the exponential-operator technique of the many-body coupled-cluster method. The formulation produces an effective Hamiltonian eigenvalue problem in the valence Fock sector of the system of interest, combined with nonlinear integral equations to be solved for the functions that define the effective Hamiltonian. The method avoids the Fock-space truncations usually used in nonperturbative light-front Hamiltonian methods and, therefore, does not suffer from the spectator dependence, Fock-sector dependence, and uncanceled divergences caused by such truncations.

  2. Synergy between pair coupled cluster doubles and pair density functional theory

    SciTech Connect

    Garza, Alejandro J.; Bulik, Ireneusz W.; Henderson, Thomas M.; Scuseria, Gustavo E.

    2015-01-28

    Pair coupled cluster doubles (pCCD) has been recently studied as a method capable of accounting for static correlation with low polynomial cost. We present three combinations of pCCD with Kohn–Sham functionals of the density and on-top pair density (the probability of finding two electrons on top of each other) to add dynamic correlation to pCCD without double counting. With a negligible increase in computational cost, these pCCD+DFT blends greatly improve upon pCCD in the description of typical problems where static and dynamic correlations are both important. We argue that—as a black-box method with low scaling, size-extensivity, size-consistency, and a simple quasidiagonal two-particle density matrix—pCCD is an excellent match for pair density functionals in this type of fusion of multireference wavefunctions with DFT.

  3. Quantum optical circulator controlled by a single chirally coupled atom.

    PubMed

    Scheucher, Michael; Hilico, Adèle; Will, Elisa; Volz, Jürgen; Rauschenbeutel, Arno

    2016-12-23

    Integrated nonreciprocal optical components, which have an inherent asymmetry between their forward and backward propagation direction, are key for routing signals in photonic circuits. Here, we demonstrate a fiber-integrated quantum optical circulator operated by a single atom. Its nonreciprocal behavior arises from the chiral interaction between the atom and the transversally confined light. We demonstrate that the internal quantum state of the atom controls the operation direction of the circulator and that it features a strongly nonlinear response at the single-photon level. This enables, for example, photon number-dependent routing and novel quantum simulation protocols. Furthermore, such a circulator can in principle be prepared in a coherent superposition of its operational states and may become a key element for quantum information processing in scalable integrated optical circuits. Copyright © 2016, American Association for the Advancement of Science.

  4. Frozen natural orbitals for ionized states within equation-of-motion coupled-cluster formalism.

    PubMed

    Landau, Arie; Khistyaev, Kirill; Dolgikh, Stanislav; Krylov, Anna I

    2010-01-07

    The frozen natural orbital (FNO) approach, which has been successfully used in ground-state coupled-cluster calculations, is extended to open-shell ionized electronic states within equation-of-motion coupled-cluster (EOM-IP-CC) formalism. FNOs enable truncation of the virtual orbital space significantly reducing the computational cost with a negligible decline in accuracy. Implementation of the MP2-based FNO truncation scheme within EOM-IP-CC is presented and benchmarked using ionized states of beryllium, dihydrogen dimer, water, water dimer, nitrogen, and uracil dimer. The results show that the natural occupation threshold, i.e., percentage of the total natural occupation recovered in the truncated virtual orbital space, provides a more robust truncation criterion as compared to the fixed percentage of virtual orbitals retained. Employing 99%-99.5% natural occupation threshold, which results in the virtual space reduction by 70%-30%, yields errors below 1 kcal/mol. Moreover, the total energies exhibit linear dependence as a function of the percentage of the natural occupation retained allowing for extrapolation to the full virtual space values. The capabilities of the new method are demonstrated by the calculation of the 12 lowest vertical ionization energies (IEs) and the lowest adiabatic IE of guanine. In addition to IE calculations, we present the scans of potential energy surfaces (PESs) for ionized (H(2)O)(2) and (H(2))(2). The scans demonstrate that the FNO truncation does not introduce significant nonparallelity errors and accurately describes the PESs shapes and the corresponding energy differences, e.g., dissociation energies.

  5. Spatial distribution of particles sputtered from single crystals by gas cluster ions

    NASA Astrophysics Data System (ADS)

    Nazarov, A. V.; Chernysh, V. S.; Nordlund, K.; Djurabekova, F.; Zhao, J.

    2017-09-01

    The results of molecular dynamics simulations of the bombardment of the Cu (100) and Mo (100) single-crystals by 10 keV Ar cluster ions of different sizes are presented in this paper. Spatial distributions of sputtered material were calculated. The anisotropy of the angular distributions of sputtered atoms was revealed. It was found that the character of the anisotropy is different for Cu and Mo targets. The reasons leading to this anisotropy are discussed according to the dependences of the angular distributions on the cluster size and on the target material.

  6. Surface-Wave Coupling to Single Phononic Subwavelength Resonators

    NASA Astrophysics Data System (ADS)

    Benchabane, Sarah; Salut, Roland; Gaiffe, Olivier; Soumann, Valérie; Addouche, Mahmoud; Laude, Vincent; Khelif, Abdelkrim

    2017-09-01

    We propose to achieve manipulation of mechanical vibrations at the micron scale by exploiting the interaction of individual, isolated mechanical resonators with surface acoustic waves. We experimentally investigate a sample consisting of cylindrical pillars individually grown by focused-ion-beam-induced deposition on a piezoelectric substrate, exhibiting different geometrical parameters and excited by a long-wavelength surface elastic wave. The mechanical displacement is strongly confined in the resonators, as shown by field maps obtained by laser scanning interferometry. A tenfold displacement field enhancement compared to the vibration at the surface is obtained, revealing that the energy is efficiently coupled. The spatial distribution of the elastic energy at the surface is governed by the geometrical characteristics of the resonators and can therefore be controlled by frequency tuning the elastic wave source. The results show the potential of the proposed approach to achieve dynamic control of surface phonons at the microscale or nanoscale.

  7. Thermal Stabilization of Metal–Organic Framework-Derived Single-Site Catalytic Clusters Through Nanocasting

    SciTech Connect

    Malonzo, Camille D.; Shaker, Sammy M.; Prinslow, Steven D.; Platero-Prats, Ana E.; Gallington, Leighanne C.; Ren, Limin; Borycz, Joshua; Thompson, Anthony B.; Wang, Timothy C.; Farha, Omar K.; Hupp, Joseph T.; Lu, Connie C.; Chapman, Karena W.; Myers, Jason C.; Penn, R. Lee; Gagliardi, Laura; Tsapatsis, Michael; Stein, Andreas

    2016-03-02

    Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOP-based catalytic single sites, preventing their aggregation even after exposure to air at 600 degrees C. We describe the nanocasting of NU-1000, a MOP with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 degrees C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

  8. Thermal Stabilization of Metal-Organic Framework-Derived Single-Site Catalytic Clusters through Nanocasting.

    PubMed

    Malonzo, Camille D; Shaker, Sammy M; Ren, Limin; Prinslow, Steven D; Platero-Prats, Ana E; Gallington, Leighanne C; Borycz, Joshua; Thompson, Anthony B; Wang, Timothy C; Farha, Omar K; Hupp, Joseph T; Lu, Connie C; Chapman, Karena W; Myers, Jason C; Penn, R Lee; Gagliardi, Laura; Tsapatsis, Michael; Stein, Andreas

    2016-03-02

    Metal-organic frameworks (MOFs) provide convenient systems for organizing high concentrations of single catalytic sites derived from metallic or oxo-metallic nodes. However, high-temperature processes cause agglomeration of these nodes, so that the single-site character and catalytic activity are lost. In this work, we present a simple nanocasting approach to provide a thermally stable secondary scaffold for MOF-based catalytic single sites, preventing their aggregation even after exposure to air at 600 °C. We describe the nanocasting of NU-1000, a MOF with 3 nm channels and Lewis-acidic oxozirconium clusters, with silica. By condensing tetramethylorthosilicate within the NU-1000 pores via a vapor-phase HCl treatment, a silica layer is created on the inner walls of NU-1000. This silica layer provides anchoring sites for the oxozirconium clusters in NU-1000 after the organic linkers are removed at high temperatures. Differential pair distribution functions obtained from synchrotron X-ray scattering confirmed that isolated oxozirconium clusters are maintained in the heated nanocast materials. Pyridine adsorption experiments and a glucose isomerization reaction demonstrate that the clusters remain accessible to reagents and maintain their acidic character and catalytic activity even after the nanocast materials have been heated to 500-600 °C in air. Density functional theory calculations show a correlation between the Lewis acidity of the oxozirconium clusters and their catalytic activity. The ability to produce MOF-derived materials that retain their catalytic properties after exposure to high temperatures makes nanocasting a useful technique for obtaining single-site catalysts suitable for high-temperature reactions.

  9. Relativistic coupled-cluster calculations of {sup 20}Ne, {sup 40}Ar, {sup 84}Kr, and {sup 129}Xe: Correlation energies and dipole polarizabilities

    SciTech Connect

    Mani, B. K.; Angom, D.; Latha, K. V. P.

    2009-12-15

    We have carried out a detailed and systematic study of the correlation energies of inert gas atoms Ne, Ar, Kr, and Xe using relativistic many-body perturbation theory and relativistic coupled-cluster theory. In the relativistic coupled-cluster calculations, we implement perturbative triples and include these in the correlation energy calculations. We then calculate the dipole polarizability of the ground states using perturbed coupled-cluster theory.

  10. Characterization of a Single Genomic Locus Encoding the Clustered Protocadherin Receptor Diversity in Xenopus tropicalis

    PubMed Central

    Etlioglu, Hakki E.; Sun, Wei; Huang, Zengjin; Chen, Wei; Schmucker, Dietmar

    2016-01-01

    Clustered protocadherins (cPcdhs) constitute the largest subgroup of the cadherin superfamily, and in mammals are grouped into clusters of α-, β-, and γ-types. Tens of tandemly arranged paralogous Pcdh genes of the Pcdh clusters generate a substantial diversity of receptor isoforms. cPcdhs are known to have important roles in neuronal development, and genetic alterations of cPcdhs have been found to be associated with several neurological diseases. Here, we present a first characterization of cPcdhs in Xenopus tropicalis. We determined and annotated all cPcdh isoforms, revealing that they are present in a single chromosomal locus. We validated a total of 96 isoforms, which we show are organized in three distinct clusters. The X. tropicalis cPcdh locus is composed of one α- and two distinct γ-Pcdh clusters (pcdh-γ1 and pcdh-γ2). Bioinformatics analyses assisted by genomic BAC clone sequencing showed that the X. tropicalis α- and γ-Pcdhs are conserved at the cluster level, but, unlike mammals, X. tropicalis does not contain a β-Pcdh cluster. In contrast, the number of γ-Pcdh isoforms has expanded, possibly due to lineage-specific gene duplications. Interestingly, the number of X. tropicalis α-Pcdhs is identical between X. tropicalis and mouse. Moreover, we find highly conserved as well as novel promoter elements potentially involved in regulating the cluster-specific expression of cPcdh isoforms. This study provides important information for the understanding of the evolutionary history of cPcdh genes and future mechanistic studies. It provides an annotated X. tropicalis cPcdh genomic map and a first molecular characterization essential for functional and comparative studies. PMID:27261006

  11. Cyclic single-molecule magnets: from the odd-numbered heptanuclear to a dimer of heptanuclear dysprosium clusters.

    PubMed

    Tian, Haiquan; Bao, Song-Song; Zheng, Li-Min

    2016-02-07

    A heptanuclear and a dimer of heptanuclear dysprosium clusters (Dy7 and Dy14) have been successfully synthesized by ingenious coalescence of the single and double pyrazinyl hydrazone as well as phosphonate ligands. The complexes feature the largest odd-numbered cyclic lanthanide clusters reported thus far. Both exhibit single molecule magnet behaviors at low temperature.

  12. Incorporating a completely renormalized coupled cluster approach into a composite method for thermodynamic properties and reaction paths

    NASA Astrophysics Data System (ADS)

    Nedd, Sean A.; DeYonker, Nathan J.; Wilson, Angela K.; Piecuch, Piotr; Gordon, Mark S.

    2012-04-01

    The correlation consistent composite approach (ccCA), using the S4 complete basis set two-point extrapolation scheme (ccCA-S4), has been modified to incorporate the left-eigenstate completely renormalized coupled cluster method, including singles, doubles, and non-iterative triples (CR-CC(2,3)) as the highest level component. The new ccCA-CC(2,3) method predicts thermodynamic properties with an accuracy that is similar to that of the original ccCA-S4 method. At the same time, the inclusion of the single-reference CR-CC(2,3) approach provides a ccCA scheme that can correctly treat reaction pathways that contain certain classes of multi-reference species such as diradicals, which would normally need to be treated by more computationally demanding multi-reference methods. The new ccCA-CC(2,3) method produces a mean absolute deviation of 1.7 kcal/mol for predicted heats of formation at 298 K, based on calibration with the G2/97 set of 148 molecules, which is comparable to that of 1.0 kcal/mol obtained using the ccCA-S4 method, while significantly improving the performance of the ccCA-S4 approach in calculations involving more demanding radical and diradical species. Both the ccCA-CC(2,3) and ccCA-S4 composite methods are used to characterize the conrotatory and disrotatory isomerization pathways of bicyclo[1.1.0]butane to trans-1,3-butadiene, for which conventional coupled cluster methods, such as the CCSD(T) approach used in the ccCA-S4 model and, in consequence, the ccCA-S4 method itself might fail by incorrectly placing the disrotatory pathway below the conrotatory one. The ccCA-CC(2,3) scheme provides correct pathway ordering while providing an accurate description of the activation and reaction energies characterizing the lowest-energy conrotatory pathway. The ccCA-CC(2,3) method is thus a viable method for the analyses of reaction mechanisms that have significant multi-reference character, and presents a generally less computationally intensive alternative to

  13. Estimating Single and Multiple Target Locations Using K-Means Clustering with Radio Tomographic Imaging in Wireless Sensor Networks

    DTIC Science & Technology

    2015-03-26

    ESTIMATING SINGLE AND MULTIPLE TARGET LOCATIONS USING K-MEANS CLUSTERING WITH RADIO TOMOGRAPHIC IMAGING IN WIRELESS SENSOR NETWORKS THESIS Jeffrey K...AND MULTIPLE TARGET LOCATIONS USING K-MEANS CLUSTERING WITH RADIO TOMOGRAPHIC IMAGING IN WIRELESS SENSOR NETWORKS THESIS Presented to the Faculty...SINGLE AND MULTIPLE TARGET LOCATIONS USING K-MEANS CLUSTERING WITH RADIO TOMOGRAPHIC IMAGING IN WIRELESS SENSOR NETWORKS Jeffrey K. Nishida, B.S.E.E

  14. Switching dynamics of single and coupled VO2-based oscillators as elements of neural networks

    NASA Astrophysics Data System (ADS)

    Velichko, Andrey; Belyaev, Maksim; Putrolaynen, Vadim; Pergament, Alexander; Perminov, Valentin

    2017-01-01

    In the present paper, we report on the switching dynamics of both single and coupled VO2-based oscillators, with resistive and capacitive coupling, and explore the capability of their application in oscillatory neural networks. Based on these results, we further select an adequate SPICE model to describe the modes of operation of coupled oscillator circuits. Physical mechanisms influencing the time of forward and reverse electrical switching, that determine the applicability limits of the proposed model, are identified. For the resistive coupling, it is shown that synchronization takes place at a certain value of the coupling resistance, though it is unstable and a synchronization failure occurs periodically. For the capacitive coupling, two synchronization modes, with weak and strong coupling, are found. The transition between these modes is accompanied by chaotic oscillations. A decrease in the width of the spectrum harmonics in the weak-coupling mode, and its increase in the strong-coupling one, is detected. The dependences of frequencies and phase differences of the coupled oscillatory circuits on the coupling capacitance are found. Examples of operation of coupled VO2 oscillators as a central pattern generator are demonstrated.

  15. Single-ion magnetic anisotropy and isotropic magnetic couplings in the metal-organic framework Fe2(dobdc).

    PubMed

    Maurice, Rémi; Verma, Pragya; Zadrozny, Joseph M; Luo, Sijie; Borycz, Joshua; Long, Jeffrey R; Truhlar, Donald G; Gagliardi, Laura

    2013-08-19

    The metal-organic framework Fe2(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate), often referred to as Fe-MOF-74, possesses many interesting properties such as a high selectivity in olefin/paraffin separations. This compound contains open-shell Fe(II) ions with open coordination sites which may have large single-ion magnetic anisotropies, as well as isotropic couplings between the nearest and next nearest neighbor magnetic sites. To complement a previous analysis of experimental data made by considering only isotropic couplings [Bloch et al. Science 2012, 335, 1606], the magnitude of the main magnetic interactions are here assessed with quantum chemical calculations performed on a finite size cluster. It is shown that the single-ion anisotropy is governed by same-spin spin-orbit interactions (i.e., weak crystal-field regime), and that this effect is not negligible compared to the nearest neighbor isotropic couplings. Additional magnetic data reveal a metamagnetic behavior at low temperature. This effect can be attributed to various microscopic interactions, and the most probable scenarios are discussed.

  16. Emergent properties of nuclei from ab initio coupled-cluster calculations

    SciTech Connect

    Hagen, G.; Hjorth-Jensen, M.; Jansen, G. R.; Papenbrock, T.

    2016-05-17

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. Our endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. We review some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLO${}_{{\\rm{sat}}}$ is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 56Ni. We derive an efficient scheme for including continuum effects in coupled-cluster computations of nuclei based on chiral nucleon–nucleon and three-nucleon forces, and present new results for unbound states in the neutron-rich isotopes of oxygen and calcium. Finally, the coupling to the continuum impacts the energies of the ${J}^{\\pi }=1/{2}^{-},3/{2}^{-},7/{2}^{-},3/{2}^{+}$ states in ${}^{\\mathrm{17,23,25}}$O, and—contrary to naive shell-model expectations—the level ordering of the ${J}^{\\pi }=3/{2}^{+},5/{2}^{+},9/{2}^{+}$ states in ${}^{\\mathrm{53,55,61}}$Ca.

  17. Emergent properties of nuclei from ab initio coupled-cluster calculations

    SciTech Connect

    Hagen, G.; Hjorth-Jensen, M.; Jansen, G. R.; Papenbrock, T.

    2016-05-17

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. Our endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. We review some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLO${}_{{\\rm{sat}}}$ is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 56Ni. We derive an efficient scheme for including continuum effects in coupled-cluster computations of nuclei based on chiral nucleon–nucleon and three-nucleon forces, and present new results for unbound states in the neutron-rich isotopes of oxygen and calcium. Finally, the coupling to the continuum impacts the energies of the ${J}^{\\pi }=1/{2}^{-},3/{2}^{-},7/{2}^{-},3/{2}^{+}$ states in ${}^{\\mathrm{17,23,25}}$O, and—contrary to naive shell-model expectations—the level ordering of the ${J}^{\\pi }=3/{2}^{+},5/{2}^{+},9/{2}^{+}$ states in ${}^{\\mathrm{53,55,61}}$Ca.

  18. Emergent properties of nuclei from ab initio coupled-cluster calculations

    NASA Astrophysics Data System (ADS)

    Hagen, G.; Hjorth-Jensen, M.; Jansen, G. R.; Papenbrock, T.

    2016-06-01

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. This endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. This paper reviews some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLO{}{{sat}} is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 56Ni. We derive an efficient scheme for including continuum effects in coupled-cluster computations of nuclei based on chiral nucleon-nucleon and three-nucleon forces, and present new results for unbound states in the neutron-rich isotopes of oxygen and calcium. The coupling to the continuum impacts the energies of the {J}π =1/{2}-,3/{2}-,7/{2}-,3/{2}+ states in {}{17,23,25}O, and—contrary to naive shell-model expectations—the level ordering of the {J}π =3/{2}+,5/{2}+,9/{2}+ states in {}{53,55,61}Ca. ).

  19. A coupled cluster and Møller-Plesset perturbation theory study of the pressure induced phase transition in the LiH crystal

    SciTech Connect

    Grüneis, Andreas

    2015-09-14

    We employ Hartree–Fock, second-order Møller-Plesset perturbation, coupled cluster singles and doubles (CCSD) as well as CCSD plus perturbative triples (CCSD(T)) theory to study the pressure induced transition from the rocksalt to the cesium chloride crystal structure in LiH. We show that the calculated transition pressure converges rapidly in this series of increasingly accurate many-electron wave function based theories. Using CCSD(T) theory, we predict a transition pressure for the structural phase transition in the LiH crystal of 340 GPa. Furthermore, we investigate the potential energy surface for this transition in the parameter space of the Buerger path.

  20. Structure of Low-Lying Excited States of Guanine in DNA and Solution: Combined Molecular Mechanics and High-Level Coupled Cluster Studies

    DOE PAGES

    Kowalski, Karol; Valiev, Marat

    2007-01-01

    High-level ab-initio equation-of-motion coupled-cluster methods with singles, doubles, and noniterative triples are used, in conjunction with the combined quantum mechanical molecular mechanics approach, to investigate the structure of low-lying excited states of the guanine base in DNA and solvated environments. Our results indicate that while the excitation energy of the first excited state is barely changed compared to its gas-phase counterpart, the excitation energy of the second excited state is blue-shifted by 0.24 eV.

  1. Single photon transport in two waveguides chirally coupled by a quantum emitter.

    PubMed

    Cheng, Mu-Tian; Ma, Xiao-San; Zhang, Jia-Yan; Wang, Bing

    2016-08-22

    We investigate single photon transport in two waveguides coupled to a two-level quantum emitter (QE). With the deduced analytical scattering amplitudes, we show that under condition of the chiral coupling between the QE and the photon in the two waveguides, the QE can play the role of ideal quantum router to redirect a single photon incident from one waveguide into the other waveguide with a probability of 100% in the ideal condition. The influences of cross coupling between two waveguides and dissipations on the routing are also shown.

  2. Rotationally induced magnetic chirality in clusters of single-domain permalloy islands and gapped nanorings

    NASA Astrophysics Data System (ADS)

    Zhang, Sheng; Li, Jie; Bartell, Jason; Lammert, Paul; Crespi, Vincent; Schiffer, Peter

    2011-03-01

    We have studied magnetic moment configurations of clusters of single-domain ferromagnetic islands in different geometries. The magnetic moments of these clusters are imaged by MFM after rotational demagnetization, following our previous protocols. We observed that two types of the clusters showed a significant imbalance of their two-fold degenerate ground states after demagnetization, and this inequality is correlated to the rotational direction of the demagnetization. A similar imbalance was also found in nano-scale rings with a small gap: the chirality of their magnetic state can be precisely controlled by the rotational direction during demagnetization. We acknowledge the financial support from DOE and Army Research Office. We are grateful to Prof. Chris Leighton and Mike Erickson for assistance with sample preparation.

  3. CIDR: Ultrafast and accurate clustering through imputation for single-cell RNA-seq data.

    PubMed

    Lin, Peijie; Troup, Michael; Ho, Joshua W K

    2017-03-28

    Most existing dimensionality reduction and clustering packages for single-cell RNA-seq (scRNA-seq) data deal with dropouts by heavy modeling and computational machinery. Here, we introduce CIDR (Clustering through Imputation and Dimensionality Reduction), an ultrafast algorithm that uses a novel yet very simple implicit imputation approach to alleviate the impact of dropouts in scRNA-seq data in a principled manner. Using a range of simulated and real data, we show that CIDR improves the standard principal component analysis and outperforms the state-of-the-art methods, namely t-SNE, ZIFA, and RaceID, in terms of clustering accuracy. CIDR typically completes within seconds when processing a data set of hundreds of cells and minutes for a data set of thousands of cells. CIDR can be downloaded at https://github.com/VCCRI/CIDR .

  4. Single cluster dynamics for the infinite range O(n) model

    NASA Astrophysics Data System (ADS)

    Brower, R. C.; Gross, N. A.; Moriarty, K. J. M.; Tamayo, P.

    1994-03-01

    This paper presents a study of Wolff's single cluster acceleration algorithm for O( n) models in the infinite range or mean-field limit. Numerical results for n = 2, 3 and 4 are consistent with the complete elimination of critical slowing down. Also a heuristic argument is advanced to support the value of z = 0 for the dynamic critical exponent. A new cluster growth algorithm is formulated for the infinite range model that has optimal efficiency of O(inN) in the system size N for the Swendsen-Wang update scheme. Using an asymptotically correct version of this cluster method, we are able to perform simulations for the Wolff update scheme up to 262,144 spins for 10 5 time steps for the O( N) models.

  5. Structures and magnetic properties of an antiferromagnetically coupled polymeric copper(II) complex and ferromagnetically coupled hexanuclear nickel(II) clusters.

    PubMed

    Tandon, Santokh S; Bunge, Scott D; Sanchiz, Joaquin; Thompson, Laurence K

    2012-03-05

    Reactions between 2,6-diformyl-4-methylphenol (DFMF) and tris(hydroxymethyl) aminomethane (THMAM = H(3)L2) in the presence of copper(II) salts, CuX(2) (X = CH(3)CO(2)(-), BF(4)(-), ClO(4)(-), Cl(-), NO(3)(-)) and Ni(CH(3)CO(2))(2) or Ni(ClO(4))(2)/NaC(6)H(5)CO(2), sodium azide (NaN(3)), and triethylamine (TEA), in one pot self-assemble giving a coordination polymer consisting of repeating pentanuclear copper(II) clusters {[Cu(2)(H(5)L(2-))(μ-N(3))](2)[Cu(N(3))(4)]·2CH(3)OH}(n) (1) and hexanuclear Ni(II) complexes [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(CH(3)CO(2))(2)]·6C(3)H(7)NO·C(2)H(5)OH (2) and [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(C(6)H(5)CO(2))(2)]·3C(3)H(7)NO·3H(2)O·CH(3)OH (3). In 1, H(5)L(2-) and in 2 and 3 H(3)L1(-) and HL2(2-) represent doubly deprotonated, singly deprotonated, and doubly deprotonated Schiff-base ligands H(7)L and H(4)L1 and a tripodal ligand H(3)L2, respectively. 1 has a novel double-stranded ladder-like structure in which [Cu(N(3))(4)](2-) anions link single chains comprised of dinuclear cationic subunits [Cu(2)(H(5)L(2-))(μ-N(3))](+), forming a 3D structure of interconnected ladders through H bonding. Nickel(II) clusters 2 and 3 have very similar neutral hexanuclear cores in which six nickel(II) ions are bonded to two H(4)L1, two H(3)L2, four μ-azido, and two μ-CH(3)CO(2)(-)/μ-C(6)H(5)CO(2)(-) ligands. In each structure two terminal dinickel (Ni(2)) units are connected to the central dinickel unit through four doubly bridging end-on (EO) μ-azido and four triply bridging μ(3)-methoxy bridges organizing into hexanuclear units. In each terminal dinuclear unit two nickel centers are bridged through one μ-phenolate oxygen from H(3)L1(-), one μ(3)-methoxy oxygen from HL2(2-), and one μ-CH(3)CO(2)(-) (2)/μ-C(6)H(5)CO(2)(-) (3) ion. Bulk magnetization measurements on 1 show moderately strong antiferromagnetic coupling within the [Cu(2)] building block (J(1) = -113.5 cm(-1)). Bulk magnetization measurements on 2

  6. Post-seismic reloading and temporal clustering on a single fault

    NASA Astrophysics Data System (ADS)

    DiCaprio, Christopher J.; Simons, Mark; Kenner, Shelley J.; Williams, Charles A.

    2008-02-01

    Geological studies show evidence for temporal clustering of large earthquakes on individual fault systems. Since post-seismic deformation due to the inelastic rheology of the lithosphere may result in a variable loading rate on a fault throughout the interseismic period, it is reasonable to expect that the rheology of the non-seismogenic lower crust and mantle lithosphere may play a role in controlling earthquake recurrence times. We study this phenomenon using a 2-D, finite element method continuum model of the lithosphere containing a single strike-slip fault. This model builds on a previous study using a 1-D spring-dashpot-slider analogue of a single fault system to study the role of Maxwell viscoelastic relaxation in producing non-periodic earthquakes. In our 2-D model, the seismogenic portion of the fault slips when a predetermined yield stress is exceeded; stress accumulated on the seismogenic fault is shed to the viscoelastic layers below and recycled back to the seismogenic fault through viscoelastic relaxation. We find that random variation of the fault yield stress from one earthquake to the next can cause the earthquake sequence to be clustered; the amount of clustering depends on a non-dimensional number, W, called the Wallace number defined as the standard deviation of the randomly varied fault yield stress divided by the effective viscosity of the system times the tectonic loading rate. A new clustering metric based on the bimodal distribution of interseismic intervals allows us to investigate clustering behaviour of systems over a wide range of model parameters and those with multiple viscoelastic layers. For models with W ≥ 1 clustering increases with increasing W, while those with W <= 1 are unclustered, or quasi-periodic.

  7. Single-stranded DNA transposition is coupled to host replication

    PubMed Central

    Hoang, Bao Ton; Pasternak, Cécile; Siguier, Patricia; Guynet, Catherine; Hickman, Alison Burgess; Dyda, Fred; Sommer, Suzanne; Chandler, Michael

    2010-01-01

    DNA transposition has contributed significantly to evolution of eukaryotes and prokaryotes. Insertion sequences (IS) are the simplest prokaryotic transposons and are divided into families based on their organization and transposition mechanism. Here, we describe a link between transposition of IS608 and ISDra2, both members of the IS200/IS605 family which uses obligatory single-stranded (ss) DNA intermediates, and the host replication fork. Replication direction through the IS plays a crucial role in excision: activity is maximal when the “top” IS strand is located on the lagging-strand template. Excision is stimulated upon transient inactivation of replicative helicase function or inhibition of Okazaki fragment synthesis. IS608 insertions also exhibit an orientation preference for the lagging-strand template and insertion can be specifically directed to stalled replication forks. An in silico genomic approach provides evidence that dissemination of other IS200/IS605 family members is also linked to host replication. PMID:20691900

  8. Hybrid Circuit Quantum Electrodynamics: Coupling a Single Silicon Spin Qubit to a Photon

    DTIC Science & Technology

    2015-01-01

    geometry developed by the Princeton group to study spin-cavity coupling in InAs nanowires . The sample, shown in Fig. 1, couples an InAs spin-orbit qubit...electric field amplitude of 0.2 V/m (4, 6). It is this electric field that couples to the charge trapped in the InAs nanowire quantum dot. Figure 1...Superconducting resonator architecture. A) A Nb stripline resonator supports a 6 GHz resonant frequency. B) We couple a single InAs nanowire double

  9. Assisted reproduction in a cohort of same-sex male couples and single men.

    PubMed

    Grover, Stephanie A; Shmorgun, Ziva; Moskovtsev, Sergey I; Baratz, Ari; Librach, Clifford L

    2013-08-01

    To date, there is limited published data on same-sex male couples and single men using assisted reproduction treatment to build their families. The objective of this retrospective study was to better understand treatment considerations and outcomes for this population when using assisted reproduction treatment. A total of 37 same-sex male couples and eight single men (seven homosexual and one heterosexual) who attended the CReATe Fertility Centre for assisted reproduction services were studied. There was a 21-fold increase in the number of same-sex male couples and single men undergoing assisted reproduction treatment since 2003. The mean age was 46years (24-58). Twenty-eight couples (76%) chose to use spermatozoa from both partners to fertilize their donated oocytes. Most men (32 same-sex male couples and seven single men; 87%) obtained oocytes from an anonymous donor, whereas five couples and one single man (13%) had a known donor. Anonymous donors who were open to be contacted by the child after the age of 18 were selected by 67% of patients. Of all 25 deliveries, eight (32%) were sets of twins. All of the twins were half genetic siblings.

  10. Dual-wavelength single-frequency laser emission in asymmetric coupled microdisks

    NASA Astrophysics Data System (ADS)

    Wang, Haotian; Liu, Sheng; Chen, Lin; Shen, Deyuan; Wu, Xiang

    2016-12-01

    The gain and loss in a microcavity laser play an important role for the modulation of laser spectrum. We show that dual-wavelength single mode lasing can be achieved in an asymmetric coupled system consisted of two size-mismatched microdisks. The amount of eigenmodes in this coupled-microdisk system is reduced relying on the Vernier effect. Then a single mode is selected to lase by controlling the gain branching in the supermodes. The supermodes are formed by the coupling between different transverse whispering-gallery modes (WGMs). When the gain/loss status between the two mirodisks is changed through selectively pumping process, the modulated gain branching for various supermodes leads to the switchable single-frequency laser emission. The results obtained in this work will provide the further understand for the spectral modulation mechanism in the coupled microcavity laser system.

  11. Dual-wavelength single-frequency laser emission in asymmetric coupled microdisks

    PubMed Central

    Wang, Haotian; Liu, Sheng; Chen, Lin; Shen, Deyuan; Wu, Xiang

    2016-01-01

    The gain and loss in a microcavity laser play an important role for the modulation of laser spectrum. We show that dual-wavelength single mode lasing can be achieved in an asymmetric coupled system consisted of two size-mismatched microdisks. The amount of eigenmodes in this coupled-microdisk system is reduced relying on the Vernier effect. Then a single mode is selected to lase by controlling the gain branching in the supermodes. The supermodes are formed by the coupling between different transverse whispering-gallery modes (WGMs). When the gain/loss status between the two mirodisks is changed through selectively pumping process, the modulated gain branching for various supermodes leads to the switchable single-frequency laser emission. The results obtained in this work will provide the further understand for the spectral modulation mechanism in the coupled microcavity laser system. PMID:27905506

  12. Cloning large gene clusters from E. coli using in vitro single-strand overlapping annealing.

    PubMed

    Wang, Rui-Yan; Shi, Zhen-Yu; Chen, Jin-Chun; Chen, Guo-Qiang

    2012-07-20

    Despite recent advances in genomic sequencing and DNA chemical synthesis, construction of large gene clusters containing DNA fragments is still a difficult and expensive task. To tackle this problem, we developed a gene cluster extraction method based on in vitro single-strand overlapping annealing (SSOA). It starts with digesting the target gene cluster in an existing genome, followed by recovering digested chromosome fragments. Subsequently, the single-strand DNA overhangs formed from the digestion process would be specifically annealed and covalently joined together with a circular and a linear vector, respectively. The SSOA method was successfully applied to clone a 18 kb DNA fragment encoding NADH:ubiquinone oxidoreductase. Genomic DNA fragments of different sizes including 11.86, 18.33, 28.67, 34.56, and 55.99 kb were used to test the cloning efficiency. Combined with genetic information from KEGG and the KEIO strain collection, this method will be useful to clone any specific region of an E. coli genome at sizes less than ~28 kb. The method provides a cost-effective way for genome assembly, alternative to chemically synthesized gene clusters.

  13. Microfluidic cell isolation technology for drug testing of single tumor cells and their clusters

    PubMed Central

    Bithi, Swastika S.; Vanapalli, Siva A.

    2017-01-01

    Drug assays with patient-derived cells such as circulating tumor cells requires manipulating small sample volumes without loss of rare disease-causing cells. Here, we report an effective technology for isolating and analyzing individual tumor cells and their clusters from minute sample volumes using an optimized microfluidic device integrated with pipettes. The method involves using hand pipetting to create an array of cell-laden nanoliter-sized droplets immobilized in a microfluidic device without loss of tumor cells during the pipetting process. Using this technology, we demonstrate single-cell analysis of tumor cell response to the chemotherapy drug doxorubicin. We find that even though individual tumor cells display diverse uptake profiles of the drug, the onset of apoptosis is determined by accumulation of a critical intracellular concentration of doxorubicin. Experiments with clusters of tumor cells compartmentalized in microfluidic drops reveal that cells within a cluster have higher viability than their single-cell counterparts when exposed to doxorubicin. This result suggests that circulating tumor cell clusters might be able to better survive chemotherapy drug treatment. Our technology is a promising tool for understanding tumor cell-drug interactions in patient-derived samples including rare cells. PMID:28150812

  14. Lampreys have a single gene cluster for the fast skeletal myosin heavy chain gene family.

    PubMed

    Ikeda, Daisuke; Ono, Yosuke; Hirano, Shigeki; Kan-no, Nobuhiro; Watabe, Shugo

    2013-01-01

    Muscle tissues contain the most classic sarcomeric myosin, called myosin II, which consists of 2 heavy chains (MYHs) and 4 light chains. In the case of humans (tetrapod), a total of 6 fast skeletal-type MYH genes (MYHs) are clustered on a single chromosome. In contrast, torafugu (teleost) contains at least 13 fast skeletal MYHs, which are distributed in 5 genomic regions; the MYHs are clustered in 3 of these regions. In the present study, the evolutionary relationship among fast skeletal MYHs is elucidated by comparing the MYHs of teleosts and tetrapods with those of cyclostome lampreys, one of two groups of extant jawless vertebrates (agnathans). We found that lampreys contain at least 3 fast skeletal MYHs, which are clustered in a head-to-tail manner in a single genomic region. Although there was apparent synteny in the corresponding MYH cluster regions between lampreys and tetrapods, phylogenetic analysis indicated that lamprey and tetrapod MYHs have independently duplicated and diversified. Subsequent transgenic approaches showed that the 5'-flanking sequences of Japanese lamprey fast skeletal MYHs function as a regulatory sequence to drive specific reporter gene expression in the fast skeletal muscle of zebrafish embryos. Although zebrafish MYH promoters showed apparent activity to direct reporter gene expression in myogenic cells derived from mice, promoters from Japanese lamprey MYHs had no activity. These results suggest that the muscle-specific regulatory mechanisms are partially conserved between teleosts and tetrapods but not between cyclostomes and tetrapods, despite the conserved synteny.

  15. Lampreys Have a Single Gene Cluster for the Fast Skeletal Myosin Heavy Chain Gene Family

    PubMed Central

    Ikeda, Daisuke; Ono, Yosuke; Hirano, Shigeki; Kan-no, Nobuhiro; Watabe, Shugo

    2013-01-01

    Muscle tissues contain the most classic sarcomeric myosin, called myosin II, which consists of 2 heavy chains (MYHs) and 4 light chains. In the case of humans (tetrapod), a total of 6 fast skeletal-type MYH genes (MYHs) are clustered on a single chromosome. In contrast, torafugu (teleost) contains at least 13 fast skeletal MYHs, which are distributed in 5 genomic regions; the MYHs are clustered in 3 of these regions. In the present study, the evolutionary relationship among fast skeletal MYHs is elucidated by comparing the MYHs of teleosts and tetrapods with those of cyclostome lampreys, one of two groups of extant jawless vertebrates (agnathans). We found that lampreys contain at least 3 fast skeletal MYHs, which are clustered in a head-to-tail manner in a single genomic region. Although there was apparent synteny in the corresponding MYH cluster regions between lampreys and tetrapods, phylogenetic analysis indicated that lamprey and tetrapod MYHs have independently duplicated and diversified. Subsequent transgenic approaches showed that the 5′-flanking sequences of Japanese lamprey fast skeletal MYHs function as a regulatory sequence to drive specific reporter gene expression in the fast skeletal muscle of zebrafish embryos. Although zebrafish MYH promoters showed apparent activity to direct reporter gene expression in myogenic cells derived from mice, promoters from Japanese lamprey MYHs had no activity. These results suggest that the muscle-specific regulatory mechanisms are partially conserved between teleosts and tetrapods but not between cyclostomes and tetrapods, despite the conserved synteny. PMID:24376886

  16. Specific incorporation of chalcogenide bridge atoms in molybdenum/tungsten-iron-sulfur single cubane clusters.

    PubMed

    Majumdar, Amit; Holm, R H

    2011-11-07

    An extensive series of heterometal-iron-sulfur single cubane-type clusters with core oxidation levels [MFe(3)S(3)Q](3+,2+) (M = Mo, W; Q = S, Se) has been prepared by means of a new method of cluster self-assembly. The procedure utilizes the assembly system [((t)Bu(3)tach)M(VI)S(3)]/FeCl(2)/Na(2)Q/NaSR in acetonitrile/THF and affords product clusters in 30-50% yield. The trisulfido precursor acts as a template, binding Fe(II) under reducing conditions and supplying the MS(3) unit of the product. The system leads to specific incorporation of a μ(3)-chalcogenide from an external source (Na(2)Q) and affords the products [((t)Bu(3)tach)MFe(3)S(3)QL(3)](0/1-) (L = Cl(-), RS(-)), among which are the first MFe(3)S(3)Se clusters prepared. Some 16 clusters have been prepared, 13 of which have been characterized by X-ray structure determinations including the incomplete cubane [((t)Bu(3)tach)MoFe(2)S(3)Cl(2)(μ(2)-SPh)], a possible trapped intermediate in the assembly process. Comparisons of structural and electronic features of clusters differing only in atom Q at one cubane vertex are provided. In comparative pairs of complexes differing only in Q, placement of one selenide atom in the core increases core volumes by about 2% over the Q = S case, sets the order Q = Se > S in Fe-Q bond lengths and Q = S > Se in Fe-Q-Fe bond angles, causes small positive shifts in redox potentials, and has an essentially nil effect on (57)Fe isomer shifts. Iron mean oxidation states and charge distributions are assigned to most clusters from isomer shifts. ((t)Bu(3)tach = 1,3,5-tert-butyl-1,3,5-triazacyclohexane). © 2011 American Chemical Society

  17. Single-photon multi-ports router based on the coupled cavity optomechanical system

    PubMed Central

    Li, Xun; Zhang, Wen-Zhao; Xiong, Biao; Zhou, Ling

    2016-01-01

    A scheme of single-photon multi-port router is put forward by coupling two optomechanical cavities with waveguides. It is shown that the coupled two optomechanical cavities can exhibit photon blockade effect, which is generated from interference of three mode interaction. A single-photon travel along the system is calculated. The results show that the single photon can be controlled in the multi-port system because of the radiation pressure, which should be useful for constructing quantum network. PMID:28004773

  18. Single-Quantum Coherence Filter for Strongly Coupled Spin Systems for Localized 1H NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Trabesinger, Andreas H.; Mueller, D. Christoph; Boesiger, Peter

    2000-08-01

    A pulse sequence for localized in vivo1H NMR spectroscopy is presented, which selectively filters single-quantum coherence built up by strongly coupled spin systems. Uncoupled and weakly coupled spin systems do not contribute to the signal output. Analytical calculations using a product operator description of the strongly coupled AB spin system as well as in vitro tests demonstrate that the proposed filter produces a signal output for a strongly coupled AB spin system, whereas the resonances of a weakly coupled AX spin system and of uncoupled spins are widely suppressed. As a potential application, the detection of the strongly coupled AA‧BB‧ spin system of taurine at 1.5 T is discussed.

  19. Affective synchrony in dual- and single-smoker couples: further evidence of "symptom-system fit"?

    PubMed

    Rohrbaugh, Michael J; Shoham, Varda; Butler, Emily A; Hasler, Brant P; Berman, Jeffrey S

    2009-03-01

    Couples in which one or both partners smoked despite one of them having a heart or lung problem discussed a health-related disagreement before and during a period of laboratory smoking. Immediately afterwards, the partners in these 25 couples used independent joysticks to recall their continuous emotional experience during the interaction while watching themselves on video. A couple-level index of affective synchrony, reflecting correlated moment-to-moment change in the two partners' joystick ratings, tended to increase from baseline to smoking for 9 dual-smoker couples but decrease for 16 single-smoker couples. Results suggest that coregulation of shared emotional experience could be a factor in smoking persistence, particularly when both partners in a couple smoke. Relationship-focused interventions addressing this fit between symptom and system may help smokers achieve stable cessation.

  20. Gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster level

    NASA Astrophysics Data System (ADS)

    Gauss, Jürgen; Ruud, Kenneth; Kállay, Mihály

    2007-08-01

    An implementation of the gauge-origin independent calculation of magnetizabilities and rotational g tensors at the coupled-cluster (CC) level is presented. The properties of interest are obtained as second derivatives of the energy with respect to the external magnetic field (in the case of the magnetizability) or with respect to magnetic field and rotational angular momentum (in the case of the rotational g tensor), while gauge-origin independence and fast basis-set convergence are ensured by using gauge-including atomic orbitals (London atomic orbitals) as well as their extension to treat rotational perturbations (rotational London atomic orbitals). The implementation within our existing CC analytic second-derivative code is described, focusing on the required modifications concerning integral evaluation and treatment of the unperturbed and perturbed two-particle density matrices. An extensive set of test calculations for LiH and BH (up to the full configuration-interaction limit), for a series of simple hydrides (HF, H2O, NH3, and CH4) as well as the more challenging molecules CO, N2, and O3 [employing the CC singles and doubles (CCSD) and the CCSD approximation augmented by a perturbative treatment of triple excitations] demonstrates the importance of electron correlation for high-accuracy predictions of magnetizabilities and rotational g tensors.

  1. An accurate potential energy surface for the F + H2 → HF + H reaction by the coupled-cluster method.

    PubMed

    Chen, Jun; Sun, Zhigang; Zhang, Dong H

    2015-01-14

    A three dimensional potential energy surface for the F + H2 → HF + H reaction has been computed by the spin unrestricted coupled cluster method with singles, doubles, triples, and perturbative quadruples [UCCSDT(2)Q] using the augmented correlation-consistent polarised valence quadruple zeta basis set for the fluorine atom and the correlation-consistent polarised valence quadruple zeta basis set for the hydrogen atom. All the calculations are based on the restricted open-shell Hartree-Fock orbitals, together with the frozen core approximations, and the UCCSD(T)/complete basis set (CBS) correction term was included. The global potential energy surface was calculated by fitting the sampled ab initio points without any scaling factor for the correlation energy part using a neutral network function method. Extensive dynamics calculations have been carried out on the potential energy surface. The reaction rate constants, integral cross sections, product rotational states distribution, and forward and backward scattering as a function of collision energy of the F + HD → HF + D, F + HD → DF + H, and F + H2 reaction, were calculated by the time-independent quantum dynamics scattering theory using the new surface. The satisfactory agreement with the reported experimental observations previously demonstrates the accuracy of the new potential energy surface.

  2. Mechanism of Olefin Asymmetric Hydrogenation Catalyzed by Iridium Phosphino-Oxazoline: A Pair Natural Orbital Coupled Cluster Study.

    PubMed

    Sparta, Manuel; Riplinger, Christoph; Neese, Frank

    2014-03-11

    Since the development of chiral phosphino-oxazoline iridium catalysts, which hydrogenate unfunctionalized alkenes enantioselectively, the asymmetric hydrogenation of prochiral olefins has become important in the production of chiral compounds. For the last 10 years, details of the mechanism, including formal oxidation state assignment of the metal center and the nature of intermediates and transition states have been debated. Various contributions have been given from a theoretical point of view, but due to the size of the structures, these have been forced to rely on density functional theory (DFT) methods. In our investigation of the catalytic cycle, we employ both DFT and a correlated ab initio method, namely, the newly implemented domain-based local pair natural orbital coupled-cluster theory with single and double excitations and the inclusion of perturbative triples correction (DLPNO-CCSD(T)). Our results show that the most likely active paths involve the formation of an intermediate Ir(V) species. Furthermore, we have been able to predict the absolute configuration of the major products, and where comparison to experiment is possible, the results of our calculations agree with the enantiomeric excess obtained from hydrogenating five prochiral substrates. This work also shows that it is now possible to study catalytic reactions with untruncated models (having up to 88 atoms) at the CCSD(T) level of theory.

  3. Relativistic coupled-cluster-theory analysis of unusually large correlation effects in the determination of gj factors in Ca+

    NASA Astrophysics Data System (ADS)

    Sahoo, B. K.; Kumar, Pradeep

    2017-07-01

    We investigate roles of electron correlation effects in the determination of the gj factors of the 4 s 2S1 /2 , 4 p 2P1 /2 , 4 p 2P3 /2 , 3 d 2D3 /2 , and 3 d 2D5 /2 states, representing different parities and angular momenta, of the Ca+ ion. Correlation contributions are highlighted with respect to the mean-field values evaluated using the Dirac-Hartree-Fock method, relativistic second-order many-body theory, and relativistic coupled-cluster (RCC) theory with the single- and double-excitation approximation considering only the linear terms and also accounting for all the nonlinear terms. This shows that it is difficult to achieve results below 10-5 precision employing an approximate perturbative approach. We also find that contributions through the nonlinear terms and higher-level excitations such as triple excitations, estimated perturbatively in the RCC method, are found to be crucial to attain precise values of the gj factors in the considered states of the Ca+ ion.

  4. Using Clustered Climate Regimes to Analyze and Compare Predictions from Fully Coupled General Circulation Models

    SciTech Connect

    Hoffman, Forrest M; Hargrove, William Walter; Erickson III, David J; Oglesby, Robert J

    2005-01-01

    Changes in Earth's climate in response to atmospheric greenhouse gas buildup impact the health of terrestrial ecosystems and the hydrologic cycle. The environmental conditions influential to plant and animal life are often mapped as ecoregions, which are land areas having similar combinations of environmental characteristics. This idea is extended to establish regions of similarity with respect to climatic characteristics that evolve through time using a quantitative statistical clustering technique called Multivariate Spatio-Temporal Clustering (MSTC). MSTC was applied to the monthly time series output from a fully coupled general circulation model (GCM) called the Parallel Climate Model (PCM). Results from an ensemble of five 99-yr Business-As-Usual (BAU) transient simulations from 2000 to 2098 were analyzed. MSTC establishes an exhaustive set of recurring climate regimes that form a 'skeleton' through the 'observations' (model output) throughout the occupied portion of the climate phase space formed by the characteristics being considered. MSTC facilitates direct comparison of ensemble members and ensemble and temporal averages since the derived climate regimes provide a basis for comparison. Moreover, by mapping all land cells to discrete climate states, the dynamic behavior of any part of the system can be studied by its time-varying sequence of climate state occupancy. MSTC is a powerful tool for model developers and environmental decision makers who wish to understand long, complex time series predictions of models. Strong predicted interannual trends were revealed in this analysis, including an increase in global desertification; a decrease in the cold, dry high-latitude conditions typical of North American and Asian winters; and significant warming in Antarctica and western Greenland.

  5. Higher-Order Equation-of-Motion Coupled-Cluster Methods for Ionization Processes

    SciTech Connect

    Kamiya, Muneaki; Hirata, So

    2006-08-21

    Compact algebraic equations defining the equation-of-motion coupled-cluster (EOM-CC) methods for ionization potentials (IP-EOM-CC) have been derived and computer implemented by virtue of a symbolic algebra system largely automating these processes. Models with connected cluster excitation operators truncated after double, triple, or quadruple level and with linear ionization operators truncated after two-hole-one-particle (2h1p), three-hole-two-particle (3h2p), or four-hole-three-particle (4h3p) level (abbreviated as IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively) have been realized into parallel algorithms taking advantage of spin, spatial, and permutation symmetries with optimal size dependence of the computational costs. They are based on spin-orbital formalisms and can describe both {alpha} and {beta} and ionizations from open-shell (doublet, triplet, etc.) reference states into ionized states with various spin magnetic quantum numbers. The application of these methods to Koopmans and satellite ionizations of N{sub 2} and CO (with the ambiguity due to finite basis sets eliminated by extrapolation) has shown that IP-EOM-CCSD frequently accounts for orbital relaxation inadequately and displays errors exceeding a couple of eV. However, these errors can be systematically reduced to tenths or even hundredths of an eV by IP-EOM-CCSDT or CCSDTQ. Comparison of spectroscopic parameters of the FH{sup +} and NH{sup +} radicals between IP-EOM-CC and experiments has also underscored the importance of higher-order IP-EOM-CC treatments. For instance, the harmonic frequencies of the {tilde A} {sup 2}{Sigma}{sup -} state of NH{sup +}+ are predicted to be 1285, 1723, and 1705 cm{sup -1} by IP-EOM-CCSD, CCSDT, and CCSDTQ, respectively, as compared to the observed value of 1707 cm{sup -1}. The small adiabatic energy separation (observed 0.04 eV) between the {tilde X} {sup 2}II and {tilde a} {sup 4}{sigma}{sup -} states of NH{sup +} also requires IP-EOM-CCSDTQ for a quantitative

  6. Application of a convergent, composite coupled cluster approach to bound state, adiabatic electron affinities in atoms and small molecules.

    PubMed

    Feller, David

    2016-01-07

    Benchmark quality adiabatic electron affinities for a collection of atoms and small molecules were obtained with the Feller-Peterson-Dixon composite coupled cluster theory method. Prior applications of this method demonstrated its ability to accurately predict atomization energies/heats of formation for more than 170 molecules. In the current work, the 1-particle expansion involved very large correlation consistent basis sets, ranging up to aug-cc-pV9Z (aug-cc-pV10Z for H and H2), with the goal of minimizing the residual basis set truncation error that must otherwise be approximated with extrapolation formulas. The n-particle expansion begins with coupled cluster calculations through iterative single and double excitations plus a quasiperturbative treatment of "connected" triple excitations (CCSD(T)) pushed to the complete basis set limit followed by CCSDT, CCSDTQ, or CCSDTQ5 corrections. Due to the small size of the systems examined here, it was possible in many cases to extend the n-particle expansion to the full configuration interaction wave function limit. Additional, smaller corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, and non-adiabatic effects were also included. The overall root mean square (RMS) deviation was 0.005 eV (0.12 kcal/mol). This level of agreement was comparable to what was found with molecular heats of formation. A 95% confidence level corresponds to roughly twice the RMS value or 0.01 eV. While the atomic electron affinities are known experimentally to high accuracy, the molecular values are less certain. This contributes to the difficulty of gauging the accuracy of the theoretical results. A limited number of electron affinities were determined with the explicitly correlated CCSD(T)-F12b method. After extending the VnZ-F12 orbital basis sets with additional diffuse functions, the F12b method was found to accurately reproduce the best F/F(-) value obtained with standard

  7. Application of a convergent, composite coupled cluster approach to bound state, adiabatic electron affinities in atoms and small molecules

    NASA Astrophysics Data System (ADS)

    Feller, David

    2016-01-01

    Benchmark quality adiabatic electron affinities for a collection of atoms and small molecules were obtained with the Feller-Peterson-Dixon composite coupled cluster theory method. Prior applications of this method demonstrated its ability to accurately predict atomization energies/heats of formation for more than 170 molecules. In the current work, the 1-particle expansion involved very large correlation consistent basis sets, ranging up to aug-cc-pV9Z (aug-cc-pV10Z for H and H2), with the goal of minimizing the residual basis set truncation error that must otherwise be approximated with extrapolation formulas. The n-particle expansion begins with coupled cluster calculations through iterative single and double excitations plus a quasiperturbative treatment of "connected" triple excitations (CCSD(T)) pushed to the complete basis set limit followed by CCSDT, CCSDTQ, or CCSDTQ5 corrections. Due to the small size of the systems examined here, it was possible in many cases to extend the n-particle expansion to the full configuration interaction wave function limit. Additional, smaller corrections associated with core/valence correlation, scalar relativity, anharmonic zero point vibrational energies, and non-adiabatic effects were also included. The overall root mean square (RMS) deviation was 0.005 eV (0.12 kcal/mol). This level of agreement was comparable to what was found with molecular heats of formation. A 95% confidence level corresponds to roughly twice the RMS value or 0.01 eV. While the atomic electron affinities are known experimentally to high accuracy, the molecular values are less certain. This contributes to the difficulty of gauging the accuracy of the theoretical results. A limited number of electron affinities were determined with the explicitly correlated CCSD(T)-F12b method. After extending the VnZ-F12 orbital basis sets with additional diffuse functions, the F12b method was found to accurately reproduce the best F/F- value obtained with standard

  8. Inversed Vernier effect based single-mode laser emission in coupled microdisks.

    PubMed

    Li, Meng; Zhang, Nan; Wang, Kaiyang; Li, Jiankai; Xiao, Shumin; Song, Qinghai

    2015-09-02

    Recently, on-chip single-mode laser emissions in coupled microdisks have attracted considerable research attention due to their wide applications. While most of single-mode lasers in coupled microdisks or microrings have been qualitatively explained by either Vernier effect or inversed Vernier effect, none of them have been experimentally confirmed. Here, we studied the mechanism of single-mode laser operation in coupled microdisks. We found that the mode numbers had been significantly reduced to nearly single-mode within a large pumping power range from threshold to gain saturation. The detail laser spectra showed that the largest gain and the first lasing peak were mainly generated by one disk and the laser intensity was proportional to the wavelength detuning of two set of modes. The corresponding theoretical analysis showed that the experimental observations were dominated by internal coupling within one cavity, which was similar to the recently explored inversed Vernier effect in two coupled microrings. We believe our finding will be important for understanding the previous experimental findings and the development of on-chip single-mode laser.

  9. Inversed Vernier effect based single-mode laser emission in coupled microdisks

    NASA Astrophysics Data System (ADS)

    Li, Meng; Zhang, Nan; Wang, Kaiyang; Li, Jiankai; Xiao, Shumin; Song, Qinghai

    2015-09-01

    Recently, on-chip single-mode laser emissions in coupled microdisks have attracted considerable research attention due to their wide applications. While most of single-mode lasers in coupled microdisks or microrings have been qualitatively explained by either Vernier effect or inversed Vernier effect, none of them have been experimentally confirmed. Here, we studied the mechanism of single-mode laser operation in coupled microdisks. We found that the mode numbers had been significantly reduced to nearly single-mode within a large pumping power range from threshold to gain saturation. The detail laser spectra showed that the largest gain and the first lasing peak were mainly generated by one disk and the laser intensity was proportional to the wavelength detuning of two set of modes. The corresponding theoretical analysis showed that the experimental observations were dominated by internal coupling within one cavity, which was similar to the recently explored inversed Vernier effect in two coupled microrings. We believe our finding will be important for understanding the previous experimental findings and the development of on-chip single-mode laser.

  10. Social capital and inequality in health between single and couple parents in Sweden.

    PubMed

    Westin, Marcus; Westerling, Ragnar

    2007-01-01

    To study whether social capital is associated with health among parents and if so, whether existing inequalities in health between single and couple parents could be better understood by introducing social capital as a possible mechanism for how health is distributed. At total of 2,500 parents with children in the age range of 4-16 years were randomized from existing national registers and asked to participate in a nationally distributed postal questionnaire; 1,589 parents participated (277 single and 1,312 couple), giving a response rate of 64%. The questionnaire contained questions regarding sociodemographic and socioeconomic characteristics, self-rated health, emotional and instrumental social support, civic and social participation, and trust. Social capital was measured by different levels of civic and social participation and trust. A multivariate analysis was used in order to find possible associations between social capital and health, when adjusted for social support, sociodemographic and socioeconomic characteristics. A low level of social capital (both social participation and trust), when adjusted for social support, socioeconomic and sociodemographic variables, was clearly and positively associated with less than good self-rated health. Social capital was unevenly distributed between single and couple mothers. Social capital is positively associated with self-rated health, at an individual level. The uneven distribution of social capital between single and couple mothers may be of some importance when trying to further understand and possibly alter the inequality in health that exists between single and couple parents.

  11. Inversed Vernier effect based single-mode laser emission in coupled microdisks

    PubMed Central

    Li, Meng; Zhang, Nan; Wang, Kaiyang; Li, Jiankai; Xiao, Shumin; Song, Qinghai

    2015-01-01

    Recently, on-chip single-mode laser emissions in coupled microdisks have attracted considerable research attention due to their wide applications. While most of single-mode lasers in coupled microdisks or microrings have been qualitatively explained by either Vernier effect or inversed Vernier effect, none of them have been experimentally confirmed. Here, we studied the mechanism of single-mode laser operation in coupled microdisks. We found that the mode numbers had been significantly reduced to nearly single-mode within a large pumping power range from threshold to gain saturation. The detail laser spectra showed that the largest gain and the first lasing peak were mainly generated by one disk and the laser intensity was proportional to the wavelength detuning of two set of modes. The corresponding theoretical analysis showed that the experimental observations were dominated by internal coupling within one cavity, which was similar to the recently explored inversed Vernier effect in two coupled microrings. We believe our finding will be important for understanding the previous experimental findings and the development of on-chip single-mode laser. PMID:26330218

  12. The spin-free analogue of Mukherjee's state-specific multireference coupled cluster theory.

    PubMed

    Datta, Dipayan; Mukherjee, Debashis

    2011-02-07

    In this paper, we develop a rigorously spin-adapted version of Mukherjee's state-specific multireference coupled cluster theory (SS-MRCC, also known as Mk-MRCC) [U. S. Mahapatra, B. Datta, and D. Mukherjee, J. Chem. Phys. 110, 6171 (1999)] for reference spaces comprising open-shell configurations. The principal features of our approach are as follows: (1) The wave operator Ω is written as Ω = ∑(μ)Ω(μ)|φ(μ)>c(μ), where {φ(μ)} is the set of configuration state functions spanning a complete active space. (2) In contrast to the Jeziorski-Monkhorst Ansatz in spin-orbital basis, we write Ω(μ) as a power series expansion of cluster operators R(μ) defined in terms of spin-free unitary generators. (3) The operators R(μ) are either closed-shell-like n hole-n particle excitations (denoted as T(μ)) or they involve valence (active) destruction operators (denoted as S(μ)); these latter type of operators can have active-active scatterings, which can also carry the same active orbital labels (such S(μ)'s are called to have spectator excitations). (4) To simulate multiple excitations involving powers of cluster operators, we allow the S(μ)'s carrying the same active orbital labels to contract among themselves. (5) We exclude S(μ)'s with direct spectator scatterings. (6) Most crucially, the factors associated with contracted composites are chosen as the inverse of the number of ways the S(μ)'s can be joined among one another leading to the same excitation. The factors introduced in (6) have been called the automorphic factors by us. One principal thrust of this paper is to show that the use of the automorphic factors imparts a remarkable simplicity to the final amplitude equations: the equations consist of terms that are at most quartic in cluster amplitudes, barring only a few. In close analogy to the Mk-MRCC theory, the inherent linear dependence of the cluster amplitudes leading to redundancy is resolved by invoking sufficiency conditions, which are exact

  13. Emergent properties of nuclei from ab initio coupled-cluster calculations

    DOE PAGES

    Hagen, G.; Hjorth-Jensen, M.; Jansen, G. R.; ...

    2016-05-17

    Emergent properties such as nuclear saturation and deformation, and the effects on shell structure due to the proximity of the scattering continuum and particle decay channels are fascinating phenomena in atomic nuclei. In recent years, ab initio approaches to nuclei have taken the first steps towards tackling the computational challenge of describing these phenomena from Hamiltonians with microscopic degrees of freedom. Our endeavor is now possible due to ideas from effective field theories, novel optimization strategies for nuclear interactions, ab initio methods exhibiting a soft scaling with mass number, and ever-increasing computational power. We review some of the recent accomplishments. We also present new results. The recently optimized chiral interaction NNLOmore » $${}_{{\\rm{sat}}}$$ is shown to provide an accurate description of both charge radii and binding energies in selected light- and medium-mass nuclei up to 56Ni. We derive an efficient scheme for including continuum effects in coupled-cluster computations of nuclei based on chiral nucleon–nucleon and three-nucleon forces, and present new results for unbound states in the neutron-rich isotopes of oxygen and calcium. Finally, the coupling to the continuum impacts the energies of the $${J}^{\\pi }=1/{2}^{-},3/{2}^{-},7/{2}^{-},3/{2}^{+}$$ states in $${}^{\\mathrm{17,23,25}}$$O, and—contrary to naive shell-model expectations—the level ordering of the $${J}^{\\pi }=3/{2}^{+},5/{2}^{+},9/{2}^{+}$$ states in $${}^{\\mathrm{53,55,61}}$$Ca.« less

  14. A comparison of the coupled cluster and internally contracted averaged coupled-pair functional levels of theory for the calculation of the MCH2(+) binding energies for M = Sc to Cu

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Scuseria, Gustavo E.

    1992-01-01

    The correlation contribution to the M-C binding energy for the MCH2(+) systems can exceed 100 kcal/mol. At the self-consistent field (SCF) level, these systems can be more than 50 kcal/mol above the fragment energies. In spite of the poor zeroth-order reference, the coupled cluster single and double excitation method with a perturbational estimate of triple excitations, CCSD(T), method is shown to provide an accurate description of these systems. The maximum difference between the CCSD(T) and internally contracted averaged coupled-pair functional binding energies is 1.5 kcal/mol for CrCH2(+), with the remaining systems agreeing to within 1.0 kcal/mol.

  15. An explicitly spin-free compact open-shell coupled cluster theory using a multireference combinatoric exponential ansatz: formal development and pilot applications.

    PubMed

    Datta, Dipayan; Mukherjee, Debashis

    2009-07-28

    In this paper, we present a comprehensive account of an explicitly spin-free compact state-universal multireference coupled cluster (CC) formalism for computing the state energies of simple open-shell systems, e.g., doublets and biradicals, where the target open-shell states can be described by a few configuration state functions spanning a model space. The cluster operators in this formalism are defined in terms of the spin-free unitary generators with respect to the common closed-shell component of all model functions (core) as vacuum. The spin-free cluster operators are either closed-shell-like n hole-n particle excitations (denoted by T(mu)) or involve excitations from the doubly occupied (nonvalence) orbitals to the singly occupied (valence) orbitals (denoted by S(e)(mu)). In addition, there are cluster operators with exchange spectator scatterings involving the valence orbitals (denoted by S(re)(mu)). We propose a new multireference cluster expansion ansatz for the wave operator with the above generally noncommuting cluster operators which essentially has the same physical content as the Jeziorski-Monkhorst ansatz with the commuting cluster operators defined in the spin-orbital basis. The T(mu) operators in our ansatz are taken to commute with all other operators, while the S(e)(mu) and S(re)(mu) operators are allowed to contract among themselves through the spectator valence orbitals. An important innovation of this ansatz is the choice of an appropriate automorphic factor accompanying each contracted composite of cluster operators in order to ensure that each distinct excitation generated by this composite appears only once in the wave operator. The resulting CC equations consist of two types of terms: a "direct" term and a "normalization" term containing the effective Hamiltonian operator. It is emphasized that the direct term is almost quartic in the cluster amplitudes, barring only a handful of terms and termination of the normalization term depends on

  16. Highly Efficient and Scalable Compound Decomposition of Two-Electron Integral Tensor and Its Application in Coupled Cluster Calculations.

    PubMed

    Peng, Bo; Kowalski, Karol

    2017-09-12

    The representation and storage of two-electron integral tensors are vital in large-scale applications of accurate electronic structure methods. Low-rank representation and efficient storage strategy of integral tensors can significantly reduce the numerical overhead and consequently time-to-solution of these methods. In this work, by combining pivoted incomplete Cholesky decomposition (CD) with a follow-up truncated singular vector decomposition (SVD), we develop a decomposition strategy to approximately represent the two-electron integral tensor in terms of low-rank vectors. A systematic benchmark test on a series of 1-D, 2-D, and 3-D carbon-hydrogen systems demonstrates high efficiency and scalability of the compound two-step decomposition of the two-electron integral tensor in our implementation. For the size of the atomic basis set, Nb, ranging from ∼100 up to ∼2,000, the observed numerical scaling of our implementation shows [Formula: see text] versus [Formula: see text] cost of performing single CD on the two-electron integral tensor in most of the other implementations. More importantly, this decomposition strategy can significantly reduce the storage requirement of the atomic orbital (AO) two-electron integral tensor from [Formula: see text] to [Formula: see text] with moderate decomposition thresholds. The accuracy tests have been performed using ground- and excited-state formulations of coupled cluster formalism employing single and double excitations (CCSD) on several benchmark systems including the C60 molecule described by nearly 1,400 basis functions. The results show that the decomposition thresholds can be generally set to 10(-4) to 10(-3) to give acceptable compromise between efficiency and accuracy.

  17. Probing the Higgs self coupling via single Higgs production at the LHC

    SciTech Connect

    Degrassi, G.; Giardino, P. P.; Maltoni, F.; Pagani, D.

    2016-12-16

    Here, we propose a method to determine the trilinear Higgs self coupling that is alternative to the direct measurement of Higgs pair production total cross sections and differential distributions. Furthermore, the method relies on the effects that electroweak loops featuring an anomalous trilinear coupling would imprint on single Higgs production at the LHC. We first calculate these contributions to all the phenomenologically relevant Higgs production (ggF, VBF, WH, ZH, t$\\bar{t}$ ) and decay (γγ,WW*/ZZ*→ 4f, b$\\bar{b}$,ττ) modes at the LHC and then estimate the sensitivity to the trilinear coupling via a one-parameter fit to the single Higgs measurements at the LHC 8 TeV. We also found that the bounds on the self coupling are already competitive with those from Higgs pair production and will be further improved in the current and next LHC runs.

  18. Probing the Higgs self coupling via single Higgs production at the LHC

    DOE PAGES

    Degrassi, G.; Giardino, P. P.; Maltoni, F.; ...

    2016-12-16

    Here, we propose a method to determine the trilinear Higgs self coupling that is alternative to the direct measurement of Higgs pair production total cross sections and differential distributions. Furthermore, the method relies on the effects that electroweak loops featuring an anomalous trilinear coupling would imprint on single Higgs production at the LHC. We first calculate these contributions to all the phenomenologically relevant Higgs production (ggF, VBF, WH, ZH, tmore » $$\\bar{t}$$ ) and decay (γγ,WW*/ZZ*→ 4f, b$$\\bar{b}$$,ττ) modes at the LHC and then estimate the sensitivity to the trilinear coupling via a one-parameter fit to the single Higgs measurements at the LHC 8 TeV. We also found that the bounds on the self coupling are already competitive with those from Higgs pair production and will be further improved in the current and next LHC runs.« less

  19. Probing the Higgs self coupling via single Higgs production at the LHC

    NASA Astrophysics Data System (ADS)

    Degrassi, G.; Giardino, P. P.; Maltoni, F.; Pagani, D.

    2016-12-01

    We propose a method to determine the trilinear Higgs self coupling that is alternative to the direct measurement of Higgs pair production total cross sections and differential distributions. The method relies on the effects that electroweak loops featuring an anomalous trilinear coupling would imprint on single Higgs production at the LHC. We first calculate these contributions to all the phenomenologically relevant Higgs production ( ggF, VBF, WH, ZH, toverline{t}H ) and decay (γ γ, W{W}^{ast }/Z{Z}^{ast}to 4f,boverline{b},τ τ ) modes at the LHC and then estimate the sensitivity to the trilinear coupling via a one-parameter fit to the single Higgs measurements at the LHC 8 TeV. We find that the bounds on the self coupling are already competitive with those from Higgs pair production and will be further improved in the current and next LHC runs.

  20. Enantioselective self-assembly of triangular Dy3 clusters with single-molecule magnet behavior.

    PubMed

    Lin, Shuang-Yan; Wang, Chao; Zhao, Lang; Tang, Jinkui

    2014-12-01

    Three pairs of enantiopure chiral triangular Ln3 clusters, [Ln3LRRRRRR/SSSSSS(μ3-OH)2(H2O)2(SCN)4]⋅xCH3OH⋅yH2O (R-Dy3, Ln=Dy, x=6, y=0; S-Dy3, Ln=Dy, x=6, y=1; R-Ho3, Ln=Ho, x=6, y=1; S-Ho3, Ln=Ho, x=6, y=1; R-Er3, Ln=Er, x=6, y=0; S-Er3, Ln=Er, x=6, y=1), have been successfully synthesized by a rational enantioselective synthetic strategy. The core of triangular Ln3 is bound in the central N6O3 of the macrocyclic ligand, and the coordination spheres of Ln ions are completed by four SCN(-) anions and two H2O molecules in axial positions of the macrocycle. The circular dichroism (CD) and vibrational circular dichroism (VCD) spectra of the enantiomers demonstrate that the chirality is successfully transferred from the ligands to the resulting Ln3 clusters. Ac susceptibility measurements reveal that single-molecule magnet behavior occurs for both enantiopure clusters of R-Dy3 and S-Dy3. This work is one of the few examples of the successful design of a pair of triangular Dy3 clusters showing simultaneously slow magnetic relaxation and optical activity, and this might open up new opportunities to develop novel multifunctional materials.

  1. Single pin BWR benchmark problem for coupled Monte Carlo - Thermal hydraulics analysis

    SciTech Connect

    Ivanov, A.; Sanchez, V.; Hoogenboom, J. E.

    2012-07-01

    As part of the European NURISP research project, a single pin BWR benchmark problem was defined. The aim of this initiative is to test the coupling strategies between Monte Carlo and subchannel codes developed by different project participants. In this paper the results obtained by the Delft Univ. of Technology and Karlsruhe Inst. of Technology will be presented. The benchmark problem was simulated with the following coupled codes: TRIPOLI-SUBCHANFLOW, MCNP-FLICA, MCNP-SUBCHANFLOW, and KENO-SUBCHANFLOW. (authors)

  2. Cross-scale Efficient Tensor Contractions for Coupled Cluster Computations Through Multiple Programming Model Backends

    SciTech Connect

    Ibrahim, Khaled Z.; Epifanovsky, Evgeny; Williams, Samuel W.; Krylov, Anna I.

    2016-07-26

    Coupled-cluster methods provide highly accurate models of molecular structure by explicit numerical calculation of tensors representing the correlation between electrons. These calculations are dominated by a sequence of tensor contractions, motivating the development of numerical libraries for such operations. While based on matrix-matrix multiplication, these libraries are specialized to exploit symmetries in the molecular structure and in electronic interactions, and thus reduce the size of the tensor representation and the complexity of contractions. The resulting algorithms are irregular and their parallelization has been previously achieved via the use of dynamic scheduling or specialized data decompositions. We introduce our efforts to extend the Libtensor framework to work in the distributed memory environment in a scalable and energy efficient manner. We achieve up to 240 speedup compared with the best optimized shared memory implementation. We attain scalability to hundreds of thousands of compute cores on three distributed-memory architectures, (Cray XC30&XC40, BlueGene/Q), and on a heterogeneous GPU-CPU system (Cray XK7). As the bottlenecks shift from being compute-bound DGEMM's to communication-bound collectives as the size of the molecular system scales, we adopt two radically different parallelization approaches for handling load-imbalance. Nevertheless, we preserve a uni ed interface to both programming models to maintain the productivity of computational quantum chemists.

  3. Closed-shell ring coupled cluster doubles theory with range separation applied on weak intermolecular interactions.

    PubMed

    Toulouse, Julien; Zhu, Wuming; Savin, Andreas; Jansen, Georg; Ángyán, János G

    2011-08-28

    We explore different variants of the random phase approximation to the correlation energy derived from closed-shell ring-diagram approximations to coupled cluster doubles theory. We implement these variants in range-separated density-functional theory, i.e., by combining the long-range random phase approximations with short-range density-functional approximations. We perform tests on the rare-gas dimers He(2), Ne(2), and Ar(2), and on the weakly interacting molecular complexes of the S22 set of Jurečka et al. [P. Jurečka, J. Šponer, J. Černý, and P. Hobza, Phys. Chem. Chem. Phys. 8, 1985 (2006)]. The two best variants correspond to the ones originally proposed by Szabo and Ostlund [A. Szabo and N. S. Ostlund, J. Chem. Phys. 67, 4351 (1977)]. With range separation, they reach mean absolute errors on the equilibrium interaction energies of the S22 set of about 0.4 kcal/mol, corresponding to mean absolute percentage errors of about 4%, with the aug-cc-pVDZ basis set.

  4. Perturbative universal state-selective correction for state-specific multi-reference coupled cluster methods

    NASA Astrophysics Data System (ADS)

    Brabec, Jiri; Banik, Subrata; Kowalski, Karol; Pittner, Jiří

    2016-10-01

    In this work, we report an extension of our previous development of the universal state-selective (USS) multireference coupled-cluster (MRCC) formalism. It was shown [Brabec et al., J. Chem. Phys. 136, 124102 (2012)] and [Banik et al., J. Chem. Phys. 142, 114106 (2015)] that the USS(2) approach significantly improves the accuracy of Brillouin-Wigner and Mukherjee MRCC formulations, however, the numerical and storage costs associated with calculating highly excited intermediates pose a significant challenge, which can restrict the applicability of the USS(2) method. Therefore, we introduce a perturbative variant of the USS(2) approach (USS(pt)), which substantially reduces numerical overhead of the full USS(2) correction while preserving its accuracy. Since the new USS(pt) implementation calculates the triple and quadruple projections in on-the-fly manner, the memory bottleneck associated with the need of storing expensive recursive intermediates is entirely eliminated. On the example of several benchmark systems, we demonstrate accuracies of USS(pt) and USS(2) approaches and their efficiency in describing quasidegenerate electronic states. It is also shown that the USS(pt) method significantly alleviates problems associated with the lack of invariance of MRCC theories upon the rotation of active orbitals.

  5. The isomerization barrier in cyanocyclobutadienes: an ab initio multireference average quadratic coupled cluster study.

    PubMed

    Eckert-Maksić, Mirjana; Lischka, Hans; Maksić, Zvonimir B; Vazdar, Mario

    2009-07-23

    The energy profiles of the isomerization of mono, di-, and tetracyano-substituted cyclobutadienes (CBDs) are computed at the multireference average quadratic coupled cluster/complete active space self-consistent field level of theory. It was found that the energy barrier heights for the automerization reaction are 2.6 (tetracyano-CBD), 5.1 (1,3-dicyano-CBD), and 6.4 (cyano-CBD) kcal mol(-1), implying that they are lowered relative to that in the parent CBD (6.4 kcal mol(-1)), the monosubstituted derivative being an exception. Since the free CBD shuttles between two equivalent structures even at low temperature of 10 K, it follows that bond-stretch isomerism does not take place in cyanocyclobutadienes. Instead, these compounds exhibit rapid fluxional interconversion at room temperature between two bond-stretch isomers by the double bond flipping mechanism. The reason behind the decrease in the barrier heights is identified as a slightly enhanced resonance effect at the saddle points separating two (equivalent) bond-stretch isomers, compared to that in the equilibrium structures, predominantly due to the diradical character of the former. It is also shown that the energy gap between the singlet ground state saddle point structure and the first triplet equilibrium geometry decreases upon multiple substitution by the cyano groups. The splitting of the S and T energy is small being within the range of 6.5-8.2 kcal mol(-1).

  6. Relativistic multireference coupled-cluster theory based on a B -spline basis: Application to atomic francium

    NASA Astrophysics Data System (ADS)

    Tang, Yong-Bo; Lou, Bing-Qiong; Shi, Ting-Yun

    2017-08-01

    In this paper, we report the relativistic Fock space multireference coupled-cluster method for atomic structure calculations. We use the no-pair Dirac-Coulomb-Breit Hamiltonian, together with a finite B -spline basis set to expand the large and small components of the Dirac wave function. Our method is applied to calculate ionization energies, reduced matrix elements, lifetimes, and polarizabilities for many states of atomic francium. To evaluate uncertainties of our results and investigate the role of electron correlation effects, we carry out calculations using approximated models at different levels. The quality of our calculations is assessed by comparing with available experimental results, showing a good agreement. In addition, the tune-out wavelengths of the ground state in the range of 340-800 nm, the magic wavelengths for the transition 7 s -8 s in the range of 800-1500 nm and the transition 7 s -7 p in the range of 600-1500 nm are determined by evaluating the dynamic polarizabilities of the 7 s , 8 s , and 7 p states for a linearly polarized light. These tune-out and magic wavelengths may be useful for laser cooling and trapping of the Fr atom, and for related high-precision trapping measurements.

  7. Comparison of explicitly correlated local coupled-cluster methods with various choices of virtual orbitals.

    PubMed

    Krause, Christine; Werner, Hans-Joachim

    2012-06-07

    Explicitly correlated local coupled-cluster (LCCSD-F12) methods with pair natural orbitals (PNOs), orbital specific virtual orbitals (OSVs), and projected atomic orbitals (PAOs) are compared. In all cases pair-specific virtual subspaces (domains) are used, and the convergence of the correlation energy as a function of the domain sizes is studied. Furthermore, the performance of the methods for reaction energies of 52 reactions involving 58 small and medium sized molecules is investigated. It is demonstrated that for all choices of virtual orbitals much smaller domains are needed in the explicitly correlated methods than without the explicitly correlated terms, since the latter correct a large part of the domain error, as found previously. For PNO-LCCSD-F12 with VTZ-F12 basis sets on the average only 20 PNOs per pair are needed to obtain reaction energies with a root mean square deviation of less than 1 kJ mol(-1) from complete basis set estimates. With OSVs or PAOs at least 4 times larger domains are needed for the same accuracy. A new hybrid method that combines the advantages of the OSV and PNO methods is proposed and tested. While in the current work the different local methods are only simulated using a conventional CCSD program, the implications for low-order scaling local implementations of the various methods are discussed.

  8. Stochastic multi-reference perturbation theory with application to the linearized coupled cluster method

    NASA Astrophysics Data System (ADS)

    Jeanmairet, Guillaume; Sharma, Sandeep; Alavi, Ali

    2017-01-01

    In this article we report a stochastic evaluation of the recently proposed multireference linearized coupled cluster theory [S. Sharma and A. Alavi, J. Chem. Phys. 143, 102815 (2015)]. In this method, both the zeroth-order and first-order wavefunctions are sampled stochastically by propagating simultaneously two populations of signed walkers. The sampling of the zeroth-order wavefunction follows a set of stochastic processes identical to the one used in the full configuration interaction quantum Monte Carlo (FCIQMC) method. To sample the first-order wavefunction, the usual FCIQMC algorithm is augmented with a source term that spawns walkers in the sampled first-order wavefunction from the zeroth-order wavefunction. The second-order energy is also computed stochastically but requires no additional overhead outside of the added cost of sampling the first-order wavefunction. This fully stochastic method opens up the possibility of simultaneously treating large active spaces to account for static correlation and recovering the dynamical correlation using perturbation theory. The method is used to study a few benchmark systems including the carbon dimer and aromatic molecules. We have computed the singlet-triplet gaps of benzene and m-xylylene. For m-xylylene, which has proved difficult for standard complete active space self consistent field theory with perturbative correction, we find the singlet-triplet gap to be in good agreement with the experimental values.

  9. Relativistic state-specific multireference coupled cluster theory description for bond-breaking energy surfaces

    NASA Astrophysics Data System (ADS)

    Ghosh, Anirban; Chaudhuri, Rajat K.; Chattopadhyay, Sudip

    2016-09-01

    A four-component (4c) relativistic state specific multireference coupled cluster (4c-SSMRCC) method has been developed and applied to compute the ground state spectroscopic constants of Ag2, Cu2, Au2, and I2. The reference functions used in these calculations are obtained using computationally inexpensive improved virtual orbital-complete active space configuration interaction scheme. Rigorous size-extensivity and insensitivity towards the intruder state problem make our method an interesting choice for the calculation of the dissociation energy surface. To the best of our knowledge, this study is the first implementation of the SSMRCC within the relativistic framework. The overall agreement of our results, employing the smallest model space, with both theoretical and experimental reference values indicates that the 4c-SSMRCC method can be fruitfully used to describe electronic structures and associated properties of systems containing heavy elements. We observe a relativistic bond stabilization for the coinage metal dimers while the I-I bond is weakened by the relativistic effects.

  10. Cross-scale efficient tensor contractions for coupled cluster computations through multiple programming model backends

    DOE PAGES

    Ibrahim, Khaled Z.; Epifanovsky, Evgeny; Williams, Samuel; ...

    2017-03-08

    Coupled-cluster methods provide highly accurate models of molecular structure through explicit numerical calculation of tensors representing the correlation between electrons. These calculations are dominated by a sequence of tensor contractions, motivating the development of numerical libraries for such operations. While based on matrix–matrix multiplication, these libraries are specialized to exploit symmetries in the molecular structure and in electronic interactions, and thus reduce the size of the tensor representation and the complexity of contractions. The resulting algorithms are irregular and their parallelization has been previously achieved via the use of dynamic scheduling or specialized data decompositions. We introduce our efforts tomore » extend the Libtensor framework to work in the distributed memory environment in a scalable and energy-efficient manner. We achieve up to 240× speedup compared with the optimized shared memory implementation of Libtensor. We attain scalability to hundreds of thousands of compute cores on three distributed-memory architectures (Cray XC30 and XC40, and IBM Blue Gene/Q), and on a heterogeneous GPU-CPU system (Cray XK7). As the bottlenecks shift from being compute-bound DGEMM's to communication-bound collectives as the size of the molecular system scales, we adopt two radically different parallelization approaches for handling load-imbalance, tasking and bulk synchronous models. Nevertheless, we preserve a unified interface to both programming models to maintain the productivity of computational quantum chemists.« less

  11. Ultrafast time measurements by time-correlated single photon counting coupled with superconducting single photon detector

    SciTech Connect

    Shcheslavskiy, V. Becker, W.; Morozov, P.; Divochiy, A.

    2016-05-15

    Time resolution is one of the main characteristics of the single photon detectors besides quantum efficiency and dark count rate. We demonstrate here an ultrafast time-correlated single photon counting (TCSPC) setup consisting of a newly developed single photon counting board SPC-150NX and a superconducting NbN single photon detector with a sensitive area of 7 × 7 μm. The combination delivers a record instrument response function with a full width at half maximum of 17.8 ps and system quantum efficiency ∼15% at wavelength of 1560 nm. A calculation of the root mean square value of the timing jitter for channels with counts more than 1% of the peak value yielded about 7.6 ps. The setup has also good timing stability of the detector–TCSPC board.

  12. Coupling Emission from Single Localized Defects in Two-Dimensional Semiconductor to Surface Plasmon Polaritons.

    PubMed

    Cai, Tao; Dutta, Subhojit; Aghaeimeibodi, Shahriar; Yang, Zhili; Nah, Sanghee; Fourkas, John T; Waks, Edo

    2017-10-10

    Coupling of an atom-like emitter to surface plasmons provides a path toward significant optical nonlinearity, which is essential in quantum information processing and quantum networks. A large coupling strength requires nanometer-scale positioning accuracy of the emitter near the surface of the plasmonic structure, which is challenging. We demonstrate the coupling of single localized defects in a tungsten diselenide (WSe2) monolayer self-aligned to the surface plasmon mode of a silver nanowire. The silver nanowire induces a strain gradient on the monolayer at the overlapping area, leading to the formation of localized defect emission sites that are intrinsically close to the surface plasmon. We measured an average coupling efficiency with a lower bound of 26% ± 11% from the emitter into the plasmonic mode of the silver nanowire. This technique offers a way to achieve efficient coupling between plasmonic structures and localized defects of two-dimensional semiconductors.

  13. Single-molecule strong coupling at room temperature in plasmonic nanocavities

    PubMed Central

    Chikkaraddy, Rohit; de Nijs, Bart; Benz, Felix; Barrow, Steven J.; Scherman, Oren A.; Rosta, Edina; Demetriadou, Angela; Fox, Peter; Hess, Ortwin; Baumberg, Jeremy J.

    2016-01-01

    Emitters placed in an optical cavity experience an environment that changes their coupling to light. In the weak-coupling regime light extraction is enhanced, but more profound effects emerge in the single-molecule strong-coupling regime where mixed light-matter states form1,2. Individual two-level emitters in such cavities become non-linear for single photons, forming key building blocks for quantum information systems as well as ultra-low power switches and lasers3–6. Such cavity quantum electrodynamics has until now been the preserve of low temperatures and complex fabrication, severely compromising their use5,7,8. Here, by scaling the cavity volume below 40 nm3 and using host-guest chemistry to align 1-10 protectively-isolated methylene-blue molecules, we reach the strong-coupling regime at room temperature and in ambient conditions. Dispersion curves from >50 plasmonic nanocavities display characteristic anticrossings, with Rabi frequencies of 300 meV for 10 molecules decreasing to 90 meV for single molecules, matching quantitative models. Statistical analysis of vibrational spectroscopy time-series and dark-field scattering spectra provide evidence of single-molecule strong coupling. This dressing of molecules with light can modify photochemistry, opening up the exploration of complex natural processes such as photosynthesis9 and pathways towards manipulation of chemical bonds10. PMID:27296227

  14. Time evolution of a single spin inhomogeneously coupled to an interacting spin environment.

    PubMed

    Huang, Zhen; Sadiek, Gehad; Kais, Sabre

    2006-04-14

    We study the time evolution of a single spin coupled by exchange interaction to an environment of interacting spin bath modeled by the XY Hamiltonian. By evaluating the spin correlator of the single spin, we observed that the decay rate of the spin oscillations strongly depends on the relative magnitude of the exchange coupling between the single spin and its nearest neighbor J(') and coupling among the spins in the environment J. The decoherence time varies significantly based on the relative coupling magnitudes of J and J('). The decay rate law has a Gaussian profile when the two exchange couplings are of the same order J(') approximately J but converts to exponential and then a power law as we move to the regimes of J(')>J and J(')single spin to the environmental spins with a certain speed. The effect of varying the anisotropic parameter, external magnetic field, and temperature on the decaying rate of the spin state is also discussed.

  15. Efficient coupling of starlight into single mode photonics using Adaptive Injection (AI)

    NASA Astrophysics Data System (ADS)

    Norris, Barnaby; Cvetojevic, Nick; Gross, Simon; Arriola, Alexander; Tuthill, Peter; Lawrence, Jon; Richards, Samuel; Goodwin, Michael; Zheng, Jessica

    2016-08-01

    Using single-mode fibres in astronomy enables revolutionary techniques including single-mode interferometry and spectroscopy. However, injection of seeing-limited starlight into single mode photonics is extremely difficult. One solution is Adaptive Injection (AI). The telescope pupil is segmented into a number of smaller subapertures each with size r0, such that seeing can be approximated as a single tip / tilt / piston term for each subaperture, and then injected into a separate fibre via a facet of a segmented MEMS deformable mirror. The injection problem is then reduced to a set of individual tip tilt loops, resulting in high overall coupling efficiency.

  16. Strong coupling of a single electron in silicon to a microwave photon

    NASA Astrophysics Data System (ADS)

    Mi, X.; Cady, J. V.; Zajac, D. M.; Deelman, P. W.; Petta, J. R.

    2017-01-01

    Silicon is vital to the computing industry because of the high quality of its native oxide and well-established doping technologies. Isotopic purification has enabled quantum coherence times on the order of seconds, thereby placing silicon at the forefront of efforts to create a solid-state quantum processor. We demonstrate strong coupling of a single electron in a silicon double quantum dot to the photonic field of a microwave cavity, as shown by the observation of vacuum Rabi splitting. Strong coupling of a quantum dot electron to a cavity photon would allow for long-range qubit coupling and the long-range entanglement of electrons in semiconductor quantum dots.

  17. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

    2016-11-01

    Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

  18. Nondestructive photon detection using a single rare-earth ion coupled to a photonic cavity

    NASA Astrophysics Data System (ADS)

    O'Brien, Chris; Zhong, Tian; Faraon, Andrei; Simon, Christoph

    2016-10-01

    We study the possibility of using single rare-earth ions coupled to a photonic cavity with high cooperativity for performing nondestructive measurements of photons, which would be useful for global quantum networks and photonic quantum computing. We calculate the achievable fidelity as a function of the parameters of the rare-earth ion and photonic cavity, which include the ion's optical and spin dephasing rates, the cavity linewidth, the single-photon coupling to the cavity, and the detection efficiency. We suggest a promising experimental realization using current state-of-the-art technology in Nd:YVO4.

  19. Transverse single-mode edge-emitting lasers based on coupled waveguides.

    PubMed

    Gordeev, Nikita Yu; Payusov, Alexey S; Shernyakov, Yuri M; Mintairov, Sergey A; Kalyuzhnyy, Nikolay A; Kulagina, Marina M; Maximov, Mikhail V

    2015-05-01

    We report on the transverse single-mode emission from InGaAs/GaAs quantum well edge-emitting lasers with broadened waveguide. The lasers are based on coupled large optical cavity (CLOC) structures where high-order vertical modes of the broad active waveguide are suppressed due to their resonant tunneling into a coupled single-mode passive waveguide. The CLOC lasers have shown stable Gaussian-shaped vertical far-field profiles with a reduced divergence of ∼22° FWHM (full width at half-maximum) in CW (continuous-wave) operation.

  20. Surface acoustic wave regulated single photon emission from a coupled quantum dot-nanocavity system

    NASA Astrophysics Data System (ADS)

    Weiß, M.; Kapfinger, S.; Reichert, T.; Finley, J. J.; Wixforth, A.; Kaniber, M.; Krenner, H. J.

    2016-07-01

    A coupled quantum dot-nanocavity system in the weak coupling regime of cavity-quantumelectrodynamics is dynamically tuned in and out of resonance by the coherent elastic field of a fSAW ≃ 800 MHz surface acoustic wave. When the system is brought to resonance by the sound wave, light-matter interaction is strongly increased by the Purcell effect. This leads to a precisely timed single photon emission as confirmed by the second order photon correlation function, g(2). All relevant frequencies of our experiment are faithfully identified in the Fourier transform of g(2), demonstrating high fidelity regulation of the stream of single photons emitted by the system.

  1. Photon Emission and Absorption of a Single Ion Coupled to an Optical-Fiber Cavity

    NASA Astrophysics Data System (ADS)

    Steiner, M.; Meyer, H. M.; Reichel, J.; Köhl, M.

    2014-12-01

    We present a light-matter interface which consists of a single 174Yb+ ion coupled to an optical fiber cavity. We observe that photons at 935 nm are mainly emitted into the cavity mode and that correlations between the polarization of the photon and the spin state of the ion are preserved despite the intrinsic coupling into a single-mode fiber. Complementary, when a faint coherent light field is injected into the cavity mode, we find enhanced and polarization dependent absorption by the ion.

  2. Cathodic Aromatic C,C Cross-Coupling Reaction via Single Electron Transfer Pathway.

    PubMed

    Qu, Yang; Tateno, Hiroyuki; Matsumura, Yoshimasa; Kashiwagi, Tsuneo; Atobe, Mahito

    2017-03-07

    We have successfully developed a novel cathodic cross-coupling reaction of aryl halides with arenes. Utilization of the cathodic single electron transfer (SET) mechanism for activation of aryl halides enables the cross-coupling reaction to proceed without the need for any transition metal catalysts or single electron donors in a mild condition. The SET from a cathode to an aryl halide initiates a radical chain by giving an anion radical of the aryl halide. The following propagation cycle also consists entirely of anion radical intermediates.

  3. Development and applications of a unitary group adapted state specific multi-reference coupled cluster theory with internally contracted treatment of inactive double excitations.

    PubMed

    Sinha, Debalina; Maitra, Rahul; Mukherjee, Debashis

    2012-09-07

    Any multi-reference coupled cluster (MRCC) development based on the Jeziorski-Monkhorst (JM) multi-exponential ansatz for the wave-operator Ω suffers from spin-contamination problem for non-singlet states. We have very recently proposed a spin-free unitary group adapted (UGA) analogue of the JM ansatz, where the cluster operators are defined in terms of spin-free unitary generators and a normal ordered, rather than ordinary, exponential parametrization of Ω is used. A consequence of the latter choice is the emergence of the "direct term" of the MRCC equations that terminates at exactly the quartic power of the cluster amplitudes. Our UGA-MRCC ansatz has been utilized to generate both the spin-free state specific (SS) and the state universal MRCC formalisms. It is well-known that the SSMRCC theory requires suitable sufficiency conditions to resolve the redundancy of the cluster amplitudes. In this paper, we propose an alternative variant of the UGA-SSMRCC theory, where the sufficiency conditions are used for all cluster operators containing active orbitals and the single excitations with inactive orbitals, while the inactive double excitations are assumed to be independent of the model functions they act upon. The working equations for the inactive double excitations are thus derived in an internally contracted (IC) manner in the sense that the matrix elements entering the MRCC equations involve excitations from an entire combination of the model functions. We call this theory as UGA-ICID-MRCC, where ICID is the acronym for "Internally Contracted treatment of Inactive Double excitations." Since the number of such excitations are the most numerous, choosing them to be independent of the model functions will lead to very significant reduction in the number of cluster amplitudes for large active spaces, and is worth exploring. Moreover, unlike for the excitations involving active orbitals, where there is inadequate coupling between the model and the virtual functions

  4. Accounting for Limited Detection Efficiency and Localization Precision in Cluster Analysis in Single Molecule Localization Microscopy

    PubMed Central

    Shivanandan, Arun; Unnikrishnan, Jayakrishnan; Radenovic, Aleksandra

    2015-01-01

    Single Molecule Localization Microscopy techniques like PhotoActivated Localization Microscopy, with their sub-diffraction limit spatial resolution, have been popularly used to characterize the spatial organization of membrane proteins, by means of quantitative cluster analysis. However, such quantitative studies remain challenged by the techniques’ inherent sources of errors such as a limited detection efficiency of less than 60%, due to incomplete photo-conversion, and a limited localization precision in the range of 10 – 30nm, varying across the detected molecules, mainly depending on the number of photons collected from each. We provide analytical methods to estimate the effect of these errors in cluster analysis and to correct for them. These methods, based on the Ripley’s L(r) – r or Pair Correlation Function popularly used by the community, can facilitate potentially breakthrough results in quantitative biology by providing a more accurate and precise quantification of protein spatial organization. PMID:25794150

  5. A clustering approach to multireference alignment of single-particle projections in electron microscopy

    PubMed Central

    Sorzano, C.O.S.; Bilbao-Castro, J.R.; Shkolnisky, Y.; Alcorlo, M.; Melero, R.; Caffarena-Fernández, G.; Li, M.; Xu, G.; Marabini, R.; Carazo, J.M.

    2010-01-01

    Two-dimensional analysis of projections of single particles acquired by an electron microscope is a useful tool to help identifying the different kinds of projections present in a dataset and their different projection directions. Such analysis is also useful to distinguish between different kinds of particles or different particle conformations. In this paper we introduce a new algorithm for performing two-dimensional multireference alignment and classification that is based on a Hierarchical clustering approach using correntropy (instead of the more traditional correlation) and a modified criterion for the definition of the clusters specially suited for cases in which the Signal-to-Noise Ratio of the differences between classes is low. We show that our algorithm offers an improved sensitivity over current methods in use for distinguishing between different projection orientations and different particle conformations. This algorithm is publicly available through the software package Xmipp. PMID:20362059

  6. Benchmark calculations on the nuclear quadrupole-coupling parameters for open-shell molecules using non-relativistic and scalar-relativistic coupled-cluster methods

    SciTech Connect

    Cheng, Lan

    2015-08-14

    Quantum-chemical computations of nuclear quadrupole-coupling parameters for 24 open-shell states of small molecules based on non-relativistic and spin-free exact two-component (SFX2C) relativistic equation-of-motion coupled-cluster (EOM-CC) as well as spin-orbital-based restricted open-shell Hartree-Fock coupled-cluster (ROHF-CC) methods are reported. Relativistic effects, the performance of the EOM-CC and ROHF-CC methods for treating electron correlation, as well as basis-set convergence have been carefully analyzed. Consideration of relativistic effects is necessary for accurate calculations on systems containing third-row (K-Kr) and heavier elements, as expected, and the SFX2C approach is shown to be a useful cost-effective option here. Further, it is demonstrated that the EOM-CC methods constitute flexible and accurate alternatives to the ROHF-CC methods in the calculations of nuclear quadrupole-coupling parameters for open-shell states.

  7. Application of Coupled-Cluster Methods to the Prediction and Interpretation of the Spectra of Molecules of Interest in Atmospheric Chemistry

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Arnold, James O. (Technical Monitor)

    1994-01-01

    The quality of fundamental vibrational frequencies determined using the CCSD(T) method (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) is shown to be very good, usually predicting band centers to within +/-8/cm. This approach is applied to several molecules of interest in atmospheric chemistry, including HNO, NO2(+), H2CO, and HOCl. The HNO molecule displays a large and unusual anharmonicity in the H-N stretch. For the calculation of ultraviolet (UV) spectra, the linear response CCSD (LRCCSD) approach (which is equivalent to EOM-CCSD) has been shown to yield vertical excitation energies that are accurate to approximately 0.1 eV for singly excited electronic states. This method together with more approximate methods is used to examine the UV spectra of several molecules important in stratospheric chemistry, including HOCl, Cl2O, ClOOCl, ClOOH, and HOOH.

  8. Application of Coupled-Cluster Methods to the Prediction and Interpretation of the Spectra of Molecules of Interest in Atmospheric Chemistry

    NASA Technical Reports Server (NTRS)

    Lee, Timothy J.; Arnold, James O. (Technical Monitor)

    1994-01-01

    The quality of fundamental vibrational frequencies determined using the CCSD(T) method (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations) is shown to be very good, usually predicting band centers to within +/-8/cm. This approach is applied to several molecules of interest in atmospheric chemistry, including HNO, NO2(+), H2CO, and HOCl. The HNO molecule displays a large and unusual anharmonicity in the H-N stretch. For the calculation of ultraviolet (UV) spectra, the linear response CCSD (LRCCSD) approach (which is equivalent to EOM-CCSD) has been shown to yield vertical excitation energies that are accurate to approximately 0.1 eV for singly excited electronic states. This method together with more approximate methods is used to examine the UV spectra of several molecules important in stratospheric chemistry, including HOCl, Cl2O, ClOOCl, ClOOH, and HOOH.

  9. Communication: spin-orbit splittings in degenerate open-shell states via Mukherjee's multireference coupled-cluster theory: a measure for the coupling contribution.

    PubMed

    Mück, Leonie Anna; Gauss, Jürgen

    2012-03-21

    We propose a generally applicable scheme for the computation of spin-orbit (SO) splittings in degenerate open-shell systems using multireference coupled-cluster (MRCC) theory. As a specific method, Mukherjee's version of MRCC (Mk-MRCC) in conjunction with an effective mean-field SO operator is adapted for this purpose. An expression for the SO splittings is derived and implemented using Mk-MRCC analytic derivative techniques. The computed SO splittings are found to be in satisfactory agreement with experimental data. Due to the symmetry properties of the SO operator, SO splittings can be considered a quality measure for the coupling between reference determinants in Jeziorski-Monkhorst based MRCC methods. We thus provide numerical insights into the coupling problem of Mk-MRCC theory. © 2012 American Institute of Physics

  10. Single-photon transport through a waveguide coupling to a quadratic optomechanical system

    NASA Astrophysics Data System (ADS)

    Qiao, Lei

    2017-07-01

    We study the coherent transport of a single photon, which propagates in a one-dimensional waveguide and is scattered by a quadratic optomechanical system. Our approach, which is based on the Lippmann-Schwinger equation, gives an analytical solution to describe the single-photon transmission and reflection properties. We analyze the transport spectra and find they are not only related to the optomechanical system's energy-level structure, but also dependent on the optomechanical system's inherent parameters. For the existence of atomic degrees of freedom, we get a Rabi-splitting-like or an electromagnetically induced transparency (EIT)-like spectrum, depending on the atom-cavity coupling strength. Here, we focus on the single-photon strong-coupling regime so that single-quantum effects could be seen.

  11. Mode coupling in hybrid square-rectangular lasers for single mode operation

    SciTech Connect

    Ma, Xiu-Wen; Huang, Yong-Zhen Yang, Yue-De; Xiao, Jin-Long; Weng, Hai-Zhong; Xiao, Zhi-Xiong

    2016-08-15

    Mode coupling between a square microcavity and a Fabry-Pérot (FP) cavity is proposed and demonstrated for realizing single mode lasers. The modulations of the mode Q factor as simulation results are observed and single mode operation is obtained with a side mode suppression ratio of 46 dB and a single mode fiber coupling loss of 3.2 dB for an AlGaInAs/InP hybrid laser as a 300-μm-length and 1.5-μm-wide FP cavity connected to a vertex of a 10-μm-side square microcavity. Furthermore, tunable single mode operation is demonstrated with a continuous wavelength tuning range over 10 nm. The simple hybrid structure may shed light on practical applications of whispering-gallery mode microcavities in large-scale photonic integrated circuits and optical communication and interconnection.

  12. Mode coupling in hybrid square-rectangular lasers for single mode operation

    NASA Astrophysics Data System (ADS)

    Ma, Xiu-Wen; Huang, Yong-Zhen; Yang, Yue-De; Xiao, Jin-Long; Weng, Hai-Zhong; Xiao, Zhi-Xiong

    2016-08-01

    Mode coupling between a square microcavity and a Fabry-Pérot (FP) cavity is proposed and demonstrated for realizing single mode lasers. The modulations of the mode Q factor as simulation results are observed and single mode operation is obtained with a side mode suppression ratio of 46 dB and a single mode fiber coupling loss of 3.2 dB for an AlGaInAs/InP hybrid laser as a 300-μm-length and 1.5-μm-wide FP cavity connected to a vertex of a 10-μm-side square microcavity. Furthermore, tunable single mode operation is demonstrated with a continuous wavelength tuning range over 10 nm. The simple hybrid structure may shed light on practical applications of whispering-gallery mode microcavities in large-scale photonic integrated circuits and optical communication and interconnection.

  13. Two semiconductor ring lasers coupled by a single-waveguide for optical memory operation

    NASA Astrophysics Data System (ADS)

    Van der Sande, Guy; Coomans, Werner; Gelens, Lendert

    2014-05-01

    Semiconductor ring lasers are semiconductor lasers where the laser cavity consists of a ring-shaped waveguide. SRLs are highly integrable and scalable, making them ideal candidates for key components in photonic integrated circuits. SRLs can generate light in two counterpropagating directions between which bistability has been demonstrated. Hence, information can be coded into the emission direction. This bistable operation allows SRLs to be used in systems for all-optical switching and as all-optical memories. For the demonstration of fast optical flip-flop operation, Hill et al. [Nature 432, 206 (2004)] fabricated two SRLs coupled by a single waveguide, rather than a solitary SRL. Nevertheless, the literature shows that a single SRL can also function perfectly as an all-optical memory. In our recent paper [W. Coomans et al., Phys. Rev. A 88, 033813, (2013)], we have raised the question whether coupling two SRLs to realize a single optical memory has any advantage over using a solitary SRL, taking into account the obvious disadvantage of a doubled footprint and power consumption. To provide the answer, we have presented in that paper a numerical study of the dynamical behavior of semiconductor ring lasers coupled by a single bus waveguide, both when weakly coupled and when strongly coupled. We have provided a detailed analysis of the multistable landscape in the coupled system, analyzed the stability of all solutions and related the internal dynamics in the individual lasers to the field effectively measured at the output of the waveguide. We have shown which coupling phases generally promote instabilities and therefore need to be avoided in the design. Regarding all-optical memory operation, we have demonstrated that there is no real advantage for bistable memory operation compared to using a solitary SRL. An increased power suppression ratio has been found to be mainly due to the destructive interference of the SRL fields at the low power port. Also

  14. Architecture of CoNx single clusters on nanocarbon as excellent oxygen reduction catalysts with high-efficient atomic utilization.

    PubMed

    He, Ting; Xue, Hui; Wang, Xiaojuan; He, Shuanghua; Lei, Yulai; Zhang, Yuyuan; Shen, Rujuan; Zhang, Yi; Xiang, Juan

    2017-06-22

    A new strategy to fabricate CoNx single cluster supported nanocarbon catalysts (C/P/2Co600) with enhanced atomic utilization towards the oxygen reduction reaction (ORR) is reported. N-Coordination protection and low-temperature pyrolysis are the two key factors for the formation of CoNx single clusters on nanocarbon supports. Morphological and structural identification confirmed the simultaneous anchoring of homo-dispersed CoNx single clusters and N-doping on the nanocarbon under relatively mild thermal treatment conditions. Expectedly, the obtained single cluster catalyst with a trace amount of metal atoms exhibited excellent ORR performance including a positive half-wave potential (0.846 V), a high mass activity (0.98 A mgCo(-1), ampere per milligram of cobalt) and outstanding chemical durability after 8000 potential cycles. We believe that our findings provide a new route for the rational design of low-cost and highly active ORR catalytic materials.

  15. Single quantum dot coupled to a scanning optical antenna: a tunable superemitter.

    PubMed

    Farahani, J N; Pohl, D W; Eisler, H-J; Hecht, B

    2005-07-01

    The interaction of a single quantum dot with a bowtie antenna is demonstrated for visible light. The antenna is generated at the apex of a Si3N4 atomic force microscopy tip by focused ion beam milling. When scanned over the quantum dot, its photoluminescence is enhanced while its excited-state lifetime is decreased. Our observations demonstrate that the relaxation channels of a single quantum emitter can be controlled by coupling to an efficiently radiating metallic nanoantenna.

  16. Sparse maps—A systematic infrastructure for reduced-scaling electronic structure methods. II. Linear scaling domain based pair natural orbital coupled cluster theory

    SciTech Connect

    Riplinger, Christoph; Pinski, Peter; Becker, Ute; Neese, Frank E-mail: evaleev@vt.edu; Valeev, Edward F. E-mail: evaleev@vt.edu

    2016-01-14

    Domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations (DLPNO-CCSD(T)) is a highly efficient local correlation method. It is known to be accurate and robust and can be used in a black box fashion in order to obtain coupled cluster quality total energies for large molecules with several hundred atoms. While previous implementations showed near linear scaling up to a few hundred atoms, several nonlinear scaling steps limited the applicability of the method for very large systems. In this work, these limitations are overcome and a linear scaling DLPNO-CCSD(T) method for closed shell systems is reported. The new implementation is based on the concept of sparse maps that was introduced in Part I of this series [P. Pinski, C. Riplinger, E. F. Valeev, and F. Neese, J. Chem. Phys. 143, 034108 (2015)]. Using the sparse map infrastructure, all essential computational steps (integral transformation and storage, initial guess, pair natural orbital construction, amplitude iterations, triples correction) are achieved in a linear scaling fashion. In addition, a number of additional algorithmic improvements are reported that lead to significant speedups of the method. The new, linear-scaling DLPNO-CCSD(T) implementation typically is 7 times faster than the previous implementation and consumes 4 times less disk space for large three-dimensional systems. For linear systems, the performance gains and memory savings are substantially larger. Calculations with more than 20 000 basis functions and 1000 atoms are reported in this work. In all cases, the time required for the coupled cluster step is comparable to or lower than for the preceding Hartree-Fock calculation, even if this is carried out with the efficient resolution-of-the-identity and chain-of-spheres approximations. The new implementation even reduces the error in absolute correlation energies by about a factor of two, compared to the already accurate

  17. Sparse maps—A systematic infrastructure for reduced-scaling electronic structure methods. II. Linear scaling domain based pair natural orbital coupled cluster theory

    NASA Astrophysics Data System (ADS)

    Riplinger, Christoph; Pinski, Peter; Becker, Ute; Valeev, Edward F.; Neese, Frank

    2016-01-01

    Domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations (DLPNO-CCSD(T)) is a highly efficient local correlation method. It is known to be accurate and robust and can be used in a black box fashion in order to obtain coupled cluster quality total energies for large molecules with several hundred atoms. While previous implementations showed near linear scaling up to a few hundred atoms, several nonlinear scaling steps limited the applicability of the method for very large systems. In this work, these limitations are overcome and a linear scaling DLPNO-CCSD(T) method for closed shell systems is reported. The new implementation is based on the concept of sparse maps that was introduced in Part I of this series [P. Pinski, C. Riplinger, E. F. Valeev, and F. Neese, J. Chem. Phys. 143, 034108 (2015)]. Using the sparse map infrastructure, all essential computational steps (integral transformation and storage, initial guess, pair natural orbital construction, amplitude iterations, triples correction) are achieved in a linear scaling fashion. In addition, a number of additional algorithmic improvements are reported that lead to significant speedups of the method. The new, linear-scaling DLPNO-CCSD(T) implementation typically is 7 times faster than the previous implementation and consumes 4 times less disk space for large three-dimensional systems. For linear systems, the performance gains and memory savings are substantially larger. Calculations with more than 20 000 basis functions and 1000 atoms are reported in this work. In all cases, the time required for the coupled cluster step is comparable to or lower than for the preceding Hartree-Fock calculation, even if this is carried out with the efficient resolution-of-the-identity and chain-of-spheres approximations. The new implementation even reduces the error in absolute correlation energies by about a factor of two, compared to the already accurate previous

  18. Sparse maps--A systematic infrastructure for reduced-scaling electronic structure methods. II. Linear scaling domain based pair natural orbital coupled cluster theory.

    PubMed

    Riplinger, Christoph; Pinski, Peter; Becker, Ute; Valeev, Edward F; Neese, Frank

    2016-01-14

    Domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations (DLPNO-CCSD(T)) is a highly efficient local correlation method. It is known to be accurate and robust and can be used in a black box fashion in order to obtain coupled cluster quality total energies for large molecules with several hundred atoms. While previous implementations showed near linear scaling up to a few hundred atoms, several nonlinear scaling steps limited the applicability of the method for very large systems. In this work, these limitations are overcome and a linear scaling DLPNO-CCSD(T) method for closed shell systems is reported. The new implementation is based on the concept of sparse maps that was introduced in Part I of this series [P. Pinski, C. Riplinger, E. F. Valeev, and F. Neese, J. Chem. Phys. 143, 034108 (2015)]. Using the sparse map infrastructure, all essential computational steps (integral transformation and storage, initial guess, pair natural orbital construction, amplitude iterations, triples correction) are achieved in a linear scaling fashion. In addition, a number of additional algorithmic improvements are reported that lead to significant speedups of the method. The new, linear-scaling DLPNO-CCSD(T) implementation typically is 7 times faster than the previous implementation and consumes 4 times less disk space for large three-dimensional systems. For linear systems, the performance gains and memory savings are substantially larger. Calculations with more than 20 000 basis functions and 1000 atoms are reported in this work. In all cases, the time required for the coupled cluster step is comparable to or lower than for the preceding Hartree-Fock calculation, even if this is carried out with the efficient resolution-of-the-identity and chain-of-spheres approximations. The new implementation even reduces the error in absolute correlation energies by about a factor of two, compared to the already accurate

  19. Accurate dipole polarizabilities for water clusters n=2-12 at the coupled-cluster level of theory and benchmarking of various density functionals.

    SciTech Connect

    Hammond, J.; Govind, N.; Kowalski, K.; Autschbach, J.; Xantheas, S.; PNNL; Univ. of Buffalo

    2009-12-07

    The static dipole polarizabilities of water clusters (2 {le} N {le} 12) are determined at the coupled-cluster level of theory (CCSD). For the dipole polarizability of the water monomer it was determined that the role of the basis set is more important than that of electron correlation and that the basis set augmentation converges with two sets of diffuse functions. The CCSD results are used to benchmark a variety of density functionals while the performance of several families of basis sets (Dunning, Pople, and Sadlej) in producing accurate values for the polarizabilities was also examined. The Sadlej family of basis sets was found to produce accurate results when compared to the ones obtained with the much larger Dunning basis sets. It was furthermore determined that the PBE0 density functional with the aug-cc-pVDZ basis set produces overall remarkably accurate polarizabilities at a moderate computational cost.

  20. Accurate dipole polarizabilities for water clusters n =2-12 at the coupled-cluster level of theory and benchmarking of various density functionals

    NASA Astrophysics Data System (ADS)

    Hammond, Jeff R.; Govind, Niranjan; Kowalski, Karol; Autschbach, Jochen; Xantheas, Sotiris S.

    2009-12-01

    The static dipole polarizabilities of water clusters (2≤N≤12) are determined at the coupled-cluster level of theory (CCSD). For the dipole polarizability of the water monomer it was determined that the role of the basis set is more important than that of electron correlation and that the basis set augmentation converges with two sets of diffuse functions. The CCSD results are used to benchmark a variety of density functionals while the performance of several families of basis sets (Dunning, Pople, and Sadlej) in producing accurate values for the polarizabilities was also examined. The Sadlej family of basis sets was found to produce accurate results when compared to the ones obtained with the much larger Dunning basis sets. It was furthermore determined that the PBE0 density functional with the aug-cc-pVDZ basis set produces overall remarkably accurate polarizabilities at a moderate computational cost.