Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory.

Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment of molecular polaritons requires the treatment of matter and photon degrees of freedom on equal quantum mechanical footing. In the limit of molecular electronic strong or ultrastrong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach we refer to as ab initio cavity quantum electrodynamics, where the photon degrees of freedom are treated at the level of cavity quantum electrodynamics. Here, we present an approach called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory to provide ground- and excited-state polaritonic surfaces with a balanced description of strong correlation effects among electronic and photonic degrees of freedom. This method provides a platform for ab initio cavity quantum electrodynamics when both strong electron correlation and strong light-matter coupling are important and is an important step toward computational approaches that yield multiple polaritonic potential energy surfaces and couplings that can be leveraged for ab initio molecular dynamics simulations of polariton chemistry.

A Perspective on Sustainable Computational Chemistry Software Development and Integration.

The power of quantum chemistry to predict the ground and excited state properties of complex chemical systems has driven the development of computational quantum chemistry software, integrating advances in theory, applied mathematics, and computer science. The emergence of new computational paradigms associated with exascale technologies also poses significant challenges that require a flexible forward strategy to take full advantage of existing and forthcoming computational resources. In this context, the sustainability and interoperability of computational chemistry software development are among the most pressing issues. In this perspective, we discuss software infrastructure needs and investments with an eye to fully utilize exascale resources and provide unique computational tools for next-generation science problems and scientific discoveries.

TAMM: Tensor algebra for many-body methods.

Tensor algebra operations such as contractions in computational chemistry consume a significant fraction of the computing time on large-scale computing platforms. The widespread use of tensor contractions between large multi-dimensional tensors in describing electronic structure theory has motivated the development of multiple tensor algebra frameworks targeting heterogeneous computing platforms. In this paper, we present Tensor Algebra for Many-body Methods (TAMM), a framework for productive and performance-portable development of scalable computational chemistry methods. TAMM decouples the specification of the computation from the execution of these operations on available high-performance computing systems. With this design choice, the scientific application developers (domain scientists) can focus on the algorithmic requirements using the tensor algebra interface provided by TAMM, whereas high-performance computing developers can direct their attention to various optimizations on the underlying constructs, such as efficient data distribution, optimized scheduling algorithms, and efficient use of intra-node resources (e.g., graphics processing units). The modular structure of TAMM allows it to support different hardware architectures and incorporate new algorithmic advances. We describe the TAMM framework and our approach to the sustainable development of scalable ground- and excited-state electronic structure methods. We present case studies highlighting the ease of use, including the performance and productivity gains compared to other frameworks.

Real-Time Equation-of-Motion Coupled-Cluster Cumulant Green's Function Method: Heterogeneous Parallel Implementation Based on the Tensor Algebra for Many-Body Methods Infrastructure.

We report the implementation of the real-time equation-of-motion coupled-cluster (RT-EOM-CC) cumulant Green's function method [ J. Chem. Phys. 2020, 152, 174113] within the Tensor Algebra for Many-body Methods (TAMM) infrastructure. TAMM is a massively parallel heterogeneous tensor library designed for utilizing forthcoming exascale computing resources. The two-body electron repulsion matrix elements are Cholesky-decomposed, and we imposed spin-explicit forms of the various operators when evaluating the tensor contractions. Unlike our previous real algebra Tensor Contraction Engine (TCE) implementation, the TAMM implementation supports fully complex algebra. The RT-EOM-CC singles (S) and doubles (D) time-dependent amplitudes are propagated using a first-order Adams-Moulton method. This new implementation shows excellent scalability tested up to 500 GPUs using the Zn-porphyrin molecule with 655 basis functions, with parallel efficiencies above 90% up to 400 GPUs. The TAMM RT-EOM-CCSD was used to study core photoemission spectra in the formaldehyde and ethyl trifluoroacetate (ESCA) molecules. Simulations of the latter involve as many as 71 occupied and 649 virtual orbitals. The relative quasiparticle ionization energies and overall spectral functions agree well with available experimental results.

Real-time equation-of-motion CC cumulant and CC Green's function simulations of photoemission spectra of water and water dimer.

Newly developed coupled-cluster (CC) methods enable simulations of ionization potentials and spectral functions of molecular systems in a wide range of energy scales ranging from core-binding to valence. This paper discusses the results obtained with the real-time equation-of-motion CC cumulant (RT-EOM-CC) approach and CC Green's function (CCGF) approaches in applications to the water and water dimer molecules. We compare the ionization potentials obtained with these methods for the valence region with the results obtained with the coupled-cluster with singles, doubles, and perturbative triples formulation as a difference of energies for N and N - 1 electron systems. All methods show good agreement with each other. They also agree well with the experiment with errors usually below 0.1 eV for the ionization potentials. We also analyze unique features of the spectral functions, associated with the position of satellite peaks, obtained with the RT-EOM-CC and CCGF methods employing single and double excitations, as a function of the monomer OH bond length and the proton transfer coordinate in the dimer. Finally, we analyze the impact of the basis set effects on the quality of calculated ionization potentials and find that the basis set effects are less pronounced for the augmented-type sets.

From NWChem to NWChemEx: Evolving with the Computational Chemistry Landscape.

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.