Efficient evaluation of exact exchange for periodic systems via concentric atomic density fitting.

The evaluation of the exact [Hartree-Fock (HF)] exchange operator is a crucial ingredient for the accurate description of the electronic structure in periodic systems through ab initio and hybrid density functional approaches. An efficient formulation of periodic HF exchange in a linear combination of atomic orbitals representation presented here is based on the concentric atomic density fitting approximation, a domain-free local density fitting approach in which the product of two atomic orbitals is approximated using a linear combination of fitting basis functions centered at the same nuclei as the AOs in that product. A significant reduction in the computational cost of exact exchange is demonstrated relative to the conventional approach due to avoiding the need to evaluate four-center two-electron integrals, with sub-millihartree/atom errors in absolute HF energies and good cancellation of fitting errors in relative energies. The novel aspects of the evaluation of the Coulomb contribution to the Fock operator, such as the use of real two-center multipole expansions and spheropole-compensated unit cell densities, are also described.

Massively Parallel Quantum Chemistry: A high-performance research platform for electronic structure.

The Massively Parallel Quantum Chemistry (MPQC) program is a 30-year-old project that enables facile development of electronic structure methods for molecules for efficient deployment to massively parallel computing architectures. Here, we describe the historical evolution of MPQC's design into its latest (fourth) version, the capabilities and modular architecture of today's MPQC, and how MPQC facilitates rapid composition of new methods as well as its state-of-the-art performance on a variety of commodity and high-end distributed-memory computer platforms.

Optimized Pair Natural Orbitals for the Coupled Cluster Methods.

We present the coupled-cluster singles and doubles method formulated in terms of truncated pair natural orbitals (PNO) that are optimized to minimize the effect of truncation. Compared to the standard ground-state PNO coupled-cluster approaches, in which truncated PNOs derived from first-order Møller-Plesset (MP1) amplitudes are used to compress the CC wave operator, the iteratively optimized PNOs ("iPNOs") offer moderate improvement for small PNO ranks but rapidly increase their effectiveness for large PNO ranks. The error introduced by PNO truncation in the CCSD energy is reduced by orders of magnitude in the asymptotic regime, with an insignificant increase in PNO ranks. The effect of PNO optimization is particularly effective when combined with Neese's perturbative correction for the PNO incompleteness of the CCSD energy. The use of the perturbative correction in combination with the PNO optimization procedure seems to produce the most precise approximation to the canonical CCSD energies for small and large PNO ranks. For the standard benchmark set of noncovalent binding energies, remarkable improvements with respect to the standard PNO approach range from a factor of 3 with PNO truncation threshold τPNO = 10-6 (with the maximum PNO truncation error in the binding energy of only 0.1 kcal/mol) to more than 2 orders of magnitude with τPNO = 10-9.

Clustered Low-Rank Tensor Format: Introduction and Application to Fast Construction of Hartree-Fock Exchange.

We describe the clustered low-rank (CLR) framework for block-sparse and block-low-rank tensor representation and computation. The CLR framework exploits the tensor structure revealed by basis clustering; computational savings arise from low-rank compression of tensor blocks and performing block arithmetic in the low-rank form whenever beneficial. The precision is rigorously controlled by two parameters, avoiding ad-hoc heuristics, such as domains: one controls the CLR block rank truncation, and the other controls screening of small contributions in arithmetic operations on CLR tensors to propagate sparsity through expressions. As these parameters approach zero, the CLR representation and arithmetic become exact. As a pilot application, we considered the use of the CLR format for the order-2 and order-3 tensors in the context of the density fitting (DF) evaluation of the Hartree-Fock (exact) exchange (DF-K). Even for small systems and realistic basis sets, CLR-DF-K becomes more efficient than the standard DF-K approach, and it has significantly reduced asymptotic storage and computational complexities relative to the standard [Formula: see text] and [Formula: see text] DF-K figures. CLR-DF-K is also significantly more efficient-all while negligibly affecting molecular energies and properties-than the conventional (non-DF) [Formula: see text] exchange algorithm for applications to medium-sized systems (on the order of 100 atoms) with diffuse Gaussian basis sets, a necessity for applications to negatively charged species, molecular properties, and high-accuracy correlated wave functions.