Comparison of the quadratic configuration interaction and coupled cluster approaches to electron correlation including the effect of triple excitations

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

The structures, binding energies and vibrational frequencies of Ca3 and Ca4: An application of the CCSD(T) method

The Ca3 and Ca4 metallic clusters have been investigated using state-of-the-art ab initio quantum mechanical methods. Large atomic natural orbital basis sets have been used in conjunction with the singles and doubles coupled-cluster (CCSD) method, a coupled-cluster method that includes a perturbational estimate of connected triple excitations, denoted CCSD(T), and the multireference configuration interaction (MRCI) method. The equilibrium geometries, binding energies and harmonic vibrational frequencies have been determined with each of the methods so that the accuracy of the coupled-cluster methods may be assessed. Since the CCSD(T) method reproduces the MRCI results very well, cubic and quartic force fields of Ca3 and Ca4 have been determined using this approach and used to evaluate the fundamental vibrational frequencies. The infrared intensities of both the e' mode of Ca3 and the t2 mode of Ca4 are found to be small. The results obtained in this study are compared and contrasted with those from our earlier studies on small Be and Mg clusters

Theoretical investigations of the structures and binding energies of Be(sub n) and Mg(sub n) (n = 3-5) clusters

Researchers determined the equilibrium geometries and binding energies of Be and Mg trimers, tetramers and pentamers using single and double excitation coupled cluster (CCSD) and complete active space self-consistent-field (CASSCF) multireference configuration interaction (MRCI) wave functions in conjunction with extended atomic basis sets. Best estimates of the cluster binding energies are 24, 83 and 110 kcal/mole for Be3, Be4 and Be5; and 9, 31 and 41 kcal/mole for Mg3, Mg4 and Mg5, respectively. A comparison of the MRCI and CCSD results shows that even the best single-reference approach (limited to single and double excitations) is not capable of quantitative accuracy in determining the binding energies of Be and Mg clusters

Automatically generated Coulomb fitting basis sets: design and accuracy for systems containing H to Kr

For intermediate sized chemical systems the use of an auxiliary basis set (ABS) to fit the charge density provides a useful means of accelerating the performance of various quantum chemical methods. As a consequence much effort has been devoted to the design of various ABSs. This paper explores a fundamentally new approach where the ABS is created dynamically based on the specific orbital basis set (OBS) being used. The new approach includes a parameter that is used to coalesce candidate fitting functions together but which can also be used to provide some coarse grain control over the number of functions in the ABS. The accuracy of the new automatically generated ABS (auto-ABS) is systemically studied for a variety of small systems containing the elements H-Kr. Errors in the Coulomb energy computed using auto-ABS and with a variety of OBSs are shown to be small compared to errors in the Hartree-Fock energy due to incompleteness in the OBS. In contrast to fixed size ABSs, the use of auto-ABS is shown to lead to smaller errors as the size (quality) of the OBS is expanded. The performance of auto-ABS is also compared with the use of the recently proposed universal fitting sets [Weigend, Phys. Chem. Chem. Phys. 8, 1057 (2006)] for 180 compounds containing atoms from H to Kr.This work is funded by the Australian Research Council Linkage Grant Nos. LP0347178 and LP0774896, and is in association with Gaussian Inc. and Sun Microsystems

Setting the e-Commerce Scene: A Qualitative Investigation of the Use of Nature Imagery in User Interface Design

User experience designers often employ natural landscapes as background imagery in e-commerce user interfaces (UI). However, at this stage, there is only limited work on how nature imagery in UI design affects user perception and behaviour. In this paper, we present a qualitative study involving semi-structured interviews into the use of nature imagery in UI design. Our study builds on theories in environmental psychology and seeks to develop a theoretical framework for the role of nature imagery in user perception and behaviour. Further, building on the expertise of user experience practitioners and end users, we seek to develop theoretically-grounded design guidelines for the capture, selection, and integration of nature imagery in e-commerce UI designs

Programming the Adapteva Epiphany 64-core Network-on-chip Coprocessor

In the construction of exascale computing systems energy efficiency and power consumption are two of the major challenges. Low-power high performance embedded systems are of increasing interest as building blocks for large scale high- performance systems. However, extracting maximum performance out of such systems presents many challenges. Various aspects from the hardware architecture to the programming models used need to be explored. The Epiphany architecture integrates low-power RISC cores on a 2D mesh network and promises up to 70 GFLOPS/Watt of processing efficiency. However, with just 32 KB of memory per eCore for storing both data and code, and only low level inter-core communication support, programming the Epiphany system presents several challenges. In this paper we evaluate the performance of the Epiphany system for a variety of basic compute and communication operations. Guided by this data we explore strategies for implementing scientific applications on memory constrained low-powered devices such as the Epiphany. With future systems expected to house thousands of cores in a single chip, the merits of such architectures as a path to exascale is compared to other competing systems.Comment: 14 pages, submitted to IJHPCA Journal special editio

Entanglement of Pure Two-Mode Gaussian States

The entanglement of general pure Gaussian two-mode states is examined in terms of the coefficients of the quadrature components of the wavefunction. The entanglement criterion and the entanglement of formation are directly evaluated as a function of these coefficients, without the need for deriving local unitary transformations. These reproduce the results of other methods for the special case of symmetric pure states which employ a relation between squeezed states and Einstein-Podolsky-Rosen correlations. The modification of the quadrature coefficients and the corresponding entanglement due to application of various optical elements is also derived.Comment: 12 page

Two Qubits in the Dirac Representation

A general two qubit system expressed in terms of the complete set of unit and fifteen traceless, Hermitian Dirac matrices, is shown to exhibit novel features of this system. The well-known physical interpretations associated with the relativistic Dirac equation involving the symmetry operations of time-reversal T, charge conjugation C, parity P, and their products are reinterpreted here by examining their action on the basic Bell states. The transformation properties of the Bell basis states under these symmetry operations also reveal that C is the only operator that does not mix the Bell states whereas all others do. In a similar fashion, expressing the various logic gates introduced in the subject of quantum computers in terms of the Dirac matrices shows for example, that the NOT gate is related to the product of time-reversal and parity operators.Comment: 11 page

Structure of the Phase in Pure Two-Mode Gaussian States

The two-mode relative phase associated with Gaussian states plays an important role in quantum information processes in optical, atomic and electronic systems. In this work, the origin and structure of the two-mode relative phase in pure Gaussian states is studied in terms of its dependences on the quadratures of the modes. This is done by constructing local canonical transformations to an associated two-mode squeezed state. The results are illustrated by studying the time dependence of the phase under a nonlocal unitary model evolution containing correlations between the modes. In a more general context, this approach may allow the two-mode phase to be studied in situations sensitive to different physical parameters within experimental configurations relevant to quantum information processing tasks