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

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

Recent Developments in the General Atomic and Molecular Electronic Structure System

A discussion of many of the recently implemented features of GAMESS (General Atomic and Molecular Electronic Structure System) and LibCChem (the C++ CPU/GPU library associated with GAMESS) is presented. These features include fragmentation methods such as the fragment molecular orbital, effective fragment potential and effective fragment molecular orbital methods, hybrid MPI/OpenMP approaches to Hartree-Fock, and resolution of the identity second order perturbation theory. Many new coupled cluster theory methods have been implemented in GAMESS, as have multiple levels of density functional/tight binding theory. The role of accelerators, especially graphical processing units, is discussed in the context of the new features of LibCChem, as it is the associated problem of power consumption as the power of computers increases dramatically. The process by which a complex program suite such as GAMESS is maintained and developed is considered. Future developments are briefly summarized

A Project Based Approach to Teaching Parallel Systems

Abstract. For several years we have delivered advanced undergraduate courses related to computational science using a traditional approach of lectures, laboratory exercises and assignments. In recent years, however, we have moved away from this towards project based approaches. In this paper we discuss our attempts to structure a course in parallel systems around a group project that required the students design, build and evaluate their own message passing environment

First principles study of gallium-cleaning for hydrogen-contaminated α-Al2O3(0001) surfaces

The use of gallium for cleaning hydrogen-contaminated Al2O 3 surfaces is explored by performing first principles density functional calculations of gallium adsorption on a hydrogen-contaminated Al-terminated α-Al2O3(0001) surface. Both physisorbed and chemisorbed H-contaminated α-Al2O 3(0001) surfaces with one monolayer (ML) gallium coverage are investigated. The thermodynamics of gallium cleaning are considered for a variety of different asymptotic products, and are found to be favorable in all cases. Physisorbed H atoms have very weak interactions with the Al 2O3 surface and can be removed easily by the Ga ML. Chemisorbed H atoms form stronger interactions with the surface Al atoms. Bonding energy analysis and departure simulations indicate, however, that chemisorbed H atoms can be effectively removed by the Ga ML. © 2013 Wiley Periodicals, Inc