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For many computational chemistry packages, being able to efficiently and effectively scale across an exascale cluster is a heroic feat. Collective experience from the Department of Energy's Exascale Computing Project suggests that achieving exascale performance requires far more planning, design, and optimization than scaling to petascale. In many cases, entire rewrites of software are necessary to address fundamental algorithmic bottlenecks. This in turn requires a tremendous amount of resources and development time, resources that cannot reasonably be afforded by every computational science project. It thus becomes imperative that computational science transition to a more sustainable paradigm. Key to such a paradigm is modular software. While the importance of modular software is widely recognized, what is perhaps not so widely appreciated is the effort still required to leverage modular software in a sustainable manner. The present manuscript introduces PluginPlay, https://github.com/NWChemEx-Project/PluginPlay, an inversion-of-control framework designed to facilitate developing, maintaining, and sustaining modular scientific software packages. This manuscript focuses on the design aspects of PluginPlay and how they specifically influence the performance of the resulting package. Although, PluginPlay serves as the framework for the NWChemEx package, PluginPlay is not tied to NWChemEx or even computational chemistry. We thus anticipate PluginPlay to prove to be a generally useful tool for a number of computational science packages looking to transition to the exascale.

Since the advent of the first computers, chemists have been at the forefront of using computers to understand and solve complex chemical problems. As the hardware and software have evolved, so have the theoretical and computational chemistry methods and algorithms. Parallel computers clearly changed the common computing paradigm in the late 1970s and 80s, and the field has again seen a paradigm shift with the advent of graphical processing units. This review explores the challenges and some of the solutions in transforming software from the terascale to the petascale and now to the upcoming exascale computers. While discussing the field in general, NWChem and its redesign, NWChemEx, will be highlighted as one of the early codesign projects to take advantage of massively parallel computers and emerging software standards to enable large scientific challenges to be tackled.

Within computational chemistry, the NWChem package has arguably been the de facto standard for running high-accuracy numerical simulations on the most powerful supercomputers. In order to better address the challenges presented by emerging exascale architectures, the decision has been made to rewrite NWChem. Design of the resulting package, NWChemEx, has been driven by exascale computing; however, significant additional design considerations have arisen from the team's involvement with the Molecular Sciences Software Institute (MolSSI). MolSSI is a National Science Foundation initiative focused on establishing coding and data standards for the computational chemistry community. As a result, NWChemEx is built upon a general computational chemistry framework called the simulation development environment (SDE) that is designed with a focus on extensibility and interoperability. The present manuscript describes the modular approach of the SDE and how it has been used to implement the self-consistent field algorithm within NWChemEx.

Energy efficiency and energy proportional computing have become major constraints in the design of modern exascale platforms. Dynamic voltage and frequency scaling (DVFS) is one of the most commonly used and effective techniques to dynamically reduce power consumption based on workload characteristics. Many energy-saving strategies, however, employ DVFS without considering its applicability level in a given multicore processor. The present work demonstrates that disregarding the DVFS granularity as a design constraint while developing energy-saving strategies may reduce the efficacy of the strategy for certain application classes. Specifically, DVFS applicability levels (called granularities) are determined here for three different Intel processor microarchitectures. Then, the degradation in energy savings is evaluated if the DVFS granularity is disregarded. Experiments were conducted on the widely used quantum chemistry packages, General Atomic and Molecular Electronic Structure System (GAMESS) and NWChem, and show that, for granularity unaware energy-saving techniques, the overall energy consumption may increase by as much as 19%. [ABSTRACT FROM AUTHOR]

A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN2-type reaction, NC- + CH3X → NCCH3 + X- (X = F, Cl). A nontotally symmetric valley-ridge inflection (VRI) point was located along the C3 v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second-order saddle point with C3 v symmetry, which connects three product minima of Cs symmetry. For X = Cl, four product minima have been observed, of which three belong to Cs symmetry and one to C3 v symmetry. The branching path from the VRI point to the lower symmetry minima was determined by a linear interpolation technique. The branching mechanism is discussed based on the reaction path curvature and net atomic charges, and the possibility of a nonotally symmetric n-furcation is discussed. © 2015 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

On-the-fly dynamics simulations werecarried out using spin-fliptime dependent density functional theory (SF-TDDFT) to examine thephotoisomerization and photocyclization mechanisms of cis-stilbene following excitation to the ππ* state. A statetracking method was devised to follow the target state among nearlydegenerate electronic states during the dynamics simulations. Thesteepest descent path from the Franck–Condon structure of cis-stilbene in the ππ* state is shown to reachthe S1-minimum of 4,4-dihydrophenanthrene (DHP) via a cis-stilbene-like structure (referred to as (S1)cis-min) on a very flat regionof the S1-potential energy surface. From the dynamics simulations,the branching ratio of the photoisomerization is calculated as trans:DHP = 35:13, in very good agreement with the experimentaldata, trans:DHP = 35:10. The discrepancy betweenthe steepest descent pathway and the significant trans-stilbene presence in the branching ratio observed experimentallyand herein computationally is clarified from an analysis of geometricalfeatures along the reaction pathway, as well as the low barrier of0.1 eV for the pathway from (S1)cis-minto the twisted pyramidal structure on the S1-potential energy surface. It is concluded that ππ*-excited cis-stilbene propagates primarily toward the twisted structuralregion due to dynamic effects, with partial branching to the DHP structuralregion via the flat-surface region around (S1)cis-min. [ABSTRACT FROM AUTHOR]

Dynamics at intersystem crossings are fundamental to many processes in chemistry, physics, and biology. The ab initio multiple spawning (AIMS) method was originally developed to describe internal conversion dynamics at conical intersections where derivative coupling is responsible for nonadiabatic transitions between electronic states with the same spin multiplicity. Here, the applicability of the AIMS method is extended to intersystem crossing dynamics in which transitions between electronic states with different spin multiplicities are mediated by relativistic spin-orbit coupling. In the direct AIMS dynamics, the nuclear wave function is expanded in the basis of frozen multidimensional Gaussians propagating on the coupled electronic potential energy surfaces calculated on the fly. The AIMS method for intersystem crossing is used to describe the nonadiabatic transitions between the 3B1 and 1A1 states of GeH2. The potential energies and gradients were obtained at the CASSCF(6,6)/6-31G(d) level of theory. The spin-orbit coupling matrix elements were calculated with the configuration interaction method using the two-electron Breit-Pauli Hamiltonian. The excited 3B1 state lifetime and intersystem crossing rate constants were estimated by fitting the AIMS state population with the first-order kinetics equation for a reversible unimolecular reaction. The obtained rate constants are compared with the values predicted by the statistical nonadiabatic transition state theory with transition probabilities calculated using the Landau-Zener and weak coupling formulas. [ABSTRACT FROM AUTHOR]

A new type of reaction pathway which involves a nontotally symmetric trifurcation was found and investigated for a typical SN 2-type reaction, NC(-)  + CH3 X → NC-CH3  + X(-) (X = F, Cl). A nontotally symmetric valley-ridge inflection (VRI) point was located along the C3 v reaction path. For X = F, the minimum energy path (MEP) starting from the transition state (TS) leads to a second-order saddle point with C3v symmetry, which connects three product minima of Cs symmetry. For X = Cl, four product minima have been observed, of which three belong to Cs symmetry and one to C3v symmetry. The branching path from the VRI point to the lower symmetry minima was determined by a linear interpolation technique. The branching mechanism is discussed based on the reaction path curvature and net atomic charges, and the possibility of a nonotally symmetric n-furcation is discussed., (© 2015 Wiley Periodicals, Inc.)