Argonne Leadership Computing Facility

We present results from our simulations of quantum chromodynamics with four flavors of quarks: $u$, $d$, $s$, and $c$. These simulations are performed with a one-loop Symanzik improved gauge action and the highly improved staggered quark action. We are generating gauge configurations with four values of the lattice spacing ranging from 0.06 to 0.15 fm, and three values of the light quark mass, including the value for which the Goldstone pion mass is equal to the physical pion mass. We discuss simulation algorithms, scale setting, taste symmetry breaking, and the autocorrelations of various quantities. We also present results for the topological susceptibility that demonstrate the improvement of the highly improved staggered quark configurations relative to those generated earlier with the asqtad improved staggered action.

Parallelizing dense matrix computations to distributed memory architectures is a well-studied subject and generally considered to be among the best understood domains of parallel computing. Two packages, developed in the mid 1990s, still enjoy regular use: ScaLAPACK and PLAPACK. With the advent of many-core architectures, which may very well take the shape of distributed memory architectures within a single processor, these packages must be revisited since the traditional MPI-based approaches will likely need to be extended. Thus, this is a good time to review lessons learned since the introduction of these two packages and to propose a simple yet effective alternative. Preliminary performance results show the new solution achieves competitive, if not superior, performance on large clusters.

For a class of 2D hybrid organic-inorganic perovskite semiconductors based on π-conjugated organic cations, we predict quantitatively how varying the organic and inorganic component allows control over the nature, energy, and localization of carrier states in a quantum-well-like fashion. Our first-principles predictions, based on large-scale hybrid density-functional theory with spin-orbit coupling, show that the interface between the organic and inorganic parts within a single hybrid can be modulated systematically, enabling us to select between different type-I and type-II energy level alignments. Energy levels, recombination properties, and transport behavior of electrons and holes thus become tunable by choosing specific organic functionalizations and juxtaposing them with suitable inorganic components.

The thermochemistry of the conversion of glucose to levulinic acid through fructofuranosyl intermediates is investigated using the high-level ab initio methods G4 and G4MP2. The calculated gas phase reaction enthalpies indicate that the first two steps involving water molecule elimination are highly endothermic, while the other steps, including additional water elimination and rehydration to form levulinic acid, are exothermic. The calculated gas phase free energies indicate that inclusion of entropic effects makes the dehydration steps more favorable, although the elimination of the first water is still endothermic. Elevated temperatures and aqueous reaction environments are also predicted to make the dehydration reaction steps thermodynamically more favorable. On the basis of these enthalpy and free energy calculations, the first dehydration step in conversion of glucose to levulinic acid is likely a key step in controlling the overall progress of the reaction. An assessment of density functional theories and other theoretical methods for the calculation of the dehydration and hydration reactions in the decomposition of glucose is also presented.

We calculate, for the first time using unquenched lattice QCD form factors, the standard model differential branching fractions $d\mathcal{B}/d{q}^{2}(B\ensuremath{\rightarrow}K{\ensuremath{\ell}}^{+}{\ensuremath{\ell}}^{\ensuremath{-}})$ for $\ensuremath{\ell}=e$, $\ensuremath{\mu}$, $\ensuremath{\tau}$ and compare with experimental measurements by Belle, BABAR, CDF, and LHCb. We report on $\mathcal{B}(B\ensuremath{\rightarrow}K{\ensuremath{\ell}}^{+}{\ensuremath{\ell}}^{\ensuremath{-}})$ in ${q}^{2}$ bins used by experiment and predict $\mathcal{B}(B\ensuremath{\rightarrow}K{\ensuremath{\tau}}^{+}{\ensuremath{\tau}}^{\ensuremath{-}})=(1.41\ifmmode\pm\else\textpm\fi{}0.15)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}$. We also calculate the ratio of branching fractions ${R}_{e}^{\ensuremath{\mu}}=1.00029(69)$ and predict ${R}_{\ensuremath{\ell}}^{\ensuremath{\tau}}=1.176(40)$, for $\ensuremath{\ell}=e$, $\ensuremath{\mu}$. Finally, we calculate the ``flat term'' in the angular distribution of the differential decay rate ${F}_{H}^{e,\ensuremath{\mu},\ensuremath{\tau}}$ in experimentally motivated ${q}^{2}$ bins.

Molecular level understanding of acid-catalysed conversion of sugar molecules to platform chemicals such as hydroxy-methyl furfural (HMF), furfuryl alcohol (FAL), and levulinic acid (LA) is essential for efficient biomass conversion. In this paper, the high-level G4MP2 method along with the SMD solvation model is employed to understand detailed reaction energetics of the acid-catalysed decomposition of glucose and fructose to HMF. Based on protonation free energies of various hydroxyl groups of the sugar molecule, the relative reactivity of gluco-pyranose, fructo-pyranose and fructo-furanose are predicted. Calculations suggest that, in addition to the protonated intermediates, a solvent assisted dehydration of one of the fructo-furanosyl intermediates is a competing mechanism, indicating the possibility of multiple reaction pathways for fructose to HMF conversion in aqueous acidic medium. Two reaction pathways were explored to understand the thermodynamics of glucose to HMF; the first one is initiated by the protonation of a C2-OH group and the second one through an enolate intermediate involving acyclic intermediates. Additionally, a pathway is proposed for the formation of furfuryl alcohol from glucose initiated by the protonation of a C2-OH position, which includes a C-C bond cleavage, and the formation of formic acid. The detailed free energy landscapes predicted in this study can be used as benchmarks for further exploring the sugar decomposition reactions, prediction of possible intermediates, and finally designing improved catalysts for biomass conversion chemistry in the future.

Conspectus Three novel fragmentation methods that are available in the electronic structure program GAMESS (general atomic and molecular electronic structure system) are discussed in this Account. The fragment molecular orbital (FMO) method can be combined with any electronic structure method to perform accurate calculations on large molecular species with no reliance on capping atoms or empirical parameters. The FMO method is highly scalable and can take advantage of massively parallel computer systems. For example, the method has been shown to scale nearly linearly on up to 131 000 processor cores for calculations on large water clusters. There have been many applications of the FMO method to large molecular clusters, to biomolecules (e.g., proteins), and to materials that are used as heterogeneous catalysts. The effective fragment potential (EFP) method is a model potential approach that is fully derived from first principles and has no empirically fitted parameters. Consequently, an EFP can be generated for any molecule by a simple preparatory GAMESS calculation. The EFP method provides accurate descriptions of all types of intermolecular interactions, including Coulombic interactions, polarization/induction, exchange repulsion, dispersion, and charge transfer. The EFP method has been applied successfully to the study of liquid water, π-stacking in substituted benzenes and in DNA base pairs, solvent effects on positive and negative ions, electronic spectra and dynamics, non-adiabatic phenomena in electronic excited states, and nonlinear excited state properties. The effective fragment molecular orbital (EFMO) method is a merger of the FMO and EFP methods, in which interfragment interactions are described by the EFP potential, rather than the less accurate electrostatic potential. The use of EFP in this manner facilitates the use of a smaller value for the distance cut-off (Rcut). Rcut determines the distance at which EFP interactions replace fully quantum mechanical calculations on fragment-fragment (dimer) interactions. The EFMO method is both more accurate and more computationally efficient than the most commonly used FMO implementation (FMO2), in which all dimers are explicitly included in the calculation. While the FMO2 method itself does not incorporate three-body interactions, such interactions are included in the EFMO method via the EFP self-consistent induction term. Several applications (ranging from clusters to proteins) of the three methods are discussed to demonstrate their efficacy. The EFMO method will be especially exciting once the analytic gradients have been completed, because this will allow geometry optimizations, the prediction of vibrational spectra, reaction path following, and molecular dynamics simulations using the method.

We study the chiral properties of an $SU(3)$ gauge theory with ${N}_{f}$ massless Dirac fermions in the fundamental representation when ${N}_{f}$ is increased from 2 to 6. For ${N}_{f}=2$, our lattice simulations lead to a value of $⟨\overline{\ensuremath{\psi}}\ensuremath{\psi}⟩/{F}^{3}$, where $F$ is the Nambu-Goldstone-boson decay constant and $⟨\overline{\ensuremath{\psi}}\ensuremath{\psi}⟩$ is the chiral condensate, which agrees with the measured QCD value. For ${N}_{f}=6$, this ratio shows significant enhancement, presaging an even larger enhancement anticipated as ${N}_{f}$ increases further, toward the critical value for transition from confinement to infrared conformality.

Over the last 20 years, the open-source community has provided more and more software on which the world’s high-performance computing systems depend for performance and productivity. The community has invested millions of dollars and years of effort to build key components. Although the investments in these separate software elements have been tremendously valuable, a great deal of productivity has also been lost because of the lack of planning, coordination, and key integration of technologies necessary to make them work together smoothly and efficiently, both within individual petascale systems and between different systems. A repository gatekeeper and an email discussion list can coordinate open-source development within a single project, but there is no global mechanism working across the community to identify critical holes in the overall software environment, spot opportunities for beneficial integration, or specify requirements for more careful coordination. It seems clear that this completely uncoordinated development model will not provide the software needed to support the unprecedented parallelism required for peta/exascale computation on millions of cores, or the flexibility required to exploit new hardware models and features, such as transactional memory, speculative execution, and GPUs. We believe the community must work together to prepare for the challenges of exascale computing, ultimately combing their efforts in a coordinated International Exascale Software Project.

Despite a recent flurry of experimental and simulation studies, an accurate estimate of the interaction strength of water molecules with hexagonal boron nitride is lacking. Here, we report quantum Monte Carlo results for the adsorption of a water monomer on a periodic hexagonal boron nitride sheet, which yield a water monomer interaction energy of -84 ± 5 meV. We use the results to evaluate the performance of several widely used density functional theory (DFT) exchange correlation functionals and find that they all deviate substantially. Differences in interaction energies between different adsorption sites are however better reproduced by DFT.

We discuss techniques for evaluating sea quark contributions to hadronic form factors on the lattice and apply these to an exploratory calculation of the strange electromagnetic, axial, and scalar form factors of the nucleon. We employ the Wilson gauge and fermion actions on an anisotropic ${24}^{3}\ifmmode\times\else\texttimes\fi{}64$ lattice, probing a range of momentum transfer with ${Q}^{2}<1\text{ }\text{ }{\mathrm{GeV}}^{2}$. The strange electric and magnetic form factors, ${G}_{E}^{s}({Q}^{2})$ and ${G}_{M}^{s}({Q}^{2})$, are found to be small and consistent with zero within the statistics of our calculation. The lattice data favor a small negative value for the strange axial form factor ${G}_{A}^{s}({Q}^{2})$ and exhibit a strong signal for the bare strange scalar matrix element $⟨N|\overline{s}s|N{⟩}_{0}$. We discuss the unique systematic uncertainties affecting the latter quantity relative to the continuum, as well as prospects for improving future determinations with Wilson-like fermions.

We calculate the spin-independent scattering cross section for direct detection that results from the electromagnetic polarizability of a composite scalar "stealth baryon" dark matter candidate, arising from a dark SU(4) confining gauge theory-"stealth dark matter." In the nonrelativistic limit, electromagnetic polarizability proceeds through a dimension-7 interaction leading to a very small scattering cross section for dark matter with weak-scale masses. This represents a lower bound on the scattering cross section for composite dark matter theories with electromagnetically charged constituents. We carry out lattice calculations of the polarizability for the lightest "baryon" states in SU(3) and SU(4) gauge theories using the background field method on quenched configurations. We find the polarizabilities of SU(3) and SU(4) to be comparable (within about 50%) normalized to the stealth baryon mass, which is suggestive for extensions to larger SU(N) groups. The resulting scattering cross sections with a xenon target are shown to be potentially detectable in the dark matter mass range of about 200-700 GeV, where the lower bound is from the existing LUX constraint while the upper bound is the coherent neutrino background. Significant uncertainties in the cross section remain due to the more complicated interaction of the polarizablity operator with nuclear structure; however, the steep dependence on the dark matter mass, 1/m(B)(6), suggests the observable dark matter mass range is not appreciably modified. We briefly highlight collider searches for the mesons in the theory as well as the indirect astrophysical effects that may also provide excellent probes of stealth dark matter.

It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require no fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.

Composite dark matter candidates, which can arise from new strongly-coupled sectors, are well-motivated and phenomenologically interesting, particularly in the context of asymmetric generation of the relic density. In this work, we employ lattice calculations to study the electromagnetic form factors of electroweak-neutral dark-matter baryons for a three-color, QCD-like theory with ${N}_{f}=2$ and 6 degenerate fermions in the fundamental representation. We calculate the (connected) charge radius and anomalous magnetic moment, both of which can play a significant role for direct detection of composite dark matter. We find minimal ${N}_{f}$ dependence in these quantities. We generate mass-dependent cross sections for dark matter-nucleon interactions and use them in conjunction with experimental results from XENON100, excluding dark matter candidates of this type with masses below 10 TeV.

Benchmark timings are presented for the fragment molecular orbital method on a Blue Gene/P computer. Algorithmic modifications that lead to enhanced performance on the Blue Gene/P architecture include strategies for the storage of fragment density matrices by process subgroups in the global address space. The computation of the atomic forces for a system with more than 3000 atoms and 44 000 basis functions, using second order perturbation theory and an augmented and polarized double-ζ basis set, takes ∼7 min on 131 072 cores.

We describe a lattice simulation of the masses and decay constants of the lowest-lying vector and axial resonances, and the electroweak S parameter, in an SU(3) gauge theory with N(f)=2 and 6 fermions in the fundamental representation. The spectrum becomes more parity doubled and the S parameter per electroweak doublet decreases when N(f) is increased from 2 to 6, motivating study of these trends as N(f) is increased further, toward the critical value for transition from confinement to infrared conformality.

The feasibility of synthesizing unnatural DNA/RNA has recently been demonstrated, giving rise to new perspectives and challenges in the emerging field of synthetic biology, DNA data storage, and even the search for extraterrestrial life in the universe. In line with this outstanding potential, solid-state nanopores have been extensively explored as promising candidates to pave the way for the next generation of label-free, fast, and low-cost DNA sequencing. In this work, we explore the sensitivity and selectivity of a graphene/h-BN based nanopore architecture towards detection and distinction of synthetic Hachimoji nucleobases. The study is based on a combination of density functional theory and the non-equilibrium Green's function formalism. Our findings show that the artificial nucleobases are weakly binding to the device, indicating a short residence time in the nanopore during translocation. Significant changes in the electron transmission properties of the device are noted depending on which artificial nucleobase resides in the nanopore, leading to a sensitivity in distinction of up to 80%. Our results thus indicate that the proposed nanopore device setup can qualitatively discriminate synthetic nucleobases, thereby opening up the feasibility of sequencing even unnatural DNA/RNA.

Using lattice simulations, we study the infrared behavior of a particularly interesting SU(2) gauge theory, with six massless Dirac fermions in the fundamental representation. We compute the running gauge coupling derived nonperturbatively from the Schrödinger functional of the theory, finding no evidence for an infrared fixed point up through gauge couplings g(2) of order 20. This implies that the theory either is governed in the infrared by a fixed point of considerable strength, unseen so far in nonsupersymmetric gauge theories, or breaks its global chiral symmetries producing a large number of composite Nambu-Goldstone bosons relative to the number of underlying degrees of freedom. Thus either of these phases exhibits novel behavior.

The complexity of scientific pursuits is increasing rapidly with aspects that require dynamic integration of experiment, observation, theory, modeling, simulation, visualization, machine learning (ML), artificial intelligence (AI), and analysis. Research projects across the Department of Energy (DOE) are increasingly data and compute intensive. Innovative research teams are accelerating the pace of discovery by using high-performance computational and data tools in their research workflows and leveraging multiple research infrastructures. Additionally, several recent high-level U.S. government reports underscore the necessity of a new advanced computing ecosystem for international competitiveness and national security. International competitors are moving forward with major research infrastructure integration efforts that seek to capture a competitive advantage in the global innovation race. Owing to its unparalleled constellation of world-class experimental and observational facilities and high-performance and extreme-scale computational, data, and networking infrastructure, DOE is positioned to be a global leader in this new era of integrated science. However, this new integration paradigm will demand continuing evolution to ensure the U.S. remains a global leader in research and innovation. The DOE Office of Science (SC) has seized on the strategic importance of integration and has adopted a vision for Integrated Research Infrastructure (IRI): To empower researchers to meld DOE’s world-class research tools, infrastructure, and user facilities seamlessly and securely in novel ways to radically accelerate discovery and innovation. To respond to the evolving computational requirements of research and the competitive international innovation landscape, experimental facilities could be connected with high performance computing resources for near real-time analysis, and resources should be provided for merging enormous and diverse data for AI/ML techniques and analysis.

The Magnéli phase Ti4O7 is an important transition metal oxide with a wide range of applications because of its interplay between charge, spin, and lattice degrees of freedom. At low temperatures, it has non-trivial magnetic states very close in energy, driven by electronic exchange and correlation interactions. We have examined three low-lying states, one ferromagnetic and two antiferromagnetic, and calculated their energies as well as Ti spin moment distributions using highly accurate quantum Monte Carlo methods. We compare our results to those obtained from density functional theory-based methods that include approximate corrections for exchange and correlation. Our results confirm the nature of the states and their ordering in energy, as compared with density-functional theory methods. However, the energy differences and spin distributions differ. A detailed analysis suggests that non-local exchange-correlation functionals, in addition to other approximations such as LDA+U to account for correlations, are needed to simultaneously obtain better estimates for spin moments, distributions, energy differences and energy gaps.