We review the current capabilities of local electron correlation methods up to the coupled cluster model with single, double, and perturbative triple excitations [CCSD(T)], which is a gold standard in quantum chemistry. The main computational aspects of the local method types are assessed from the perspective of applications, but the focus is kept on how to achieve chemical accuracy (i.e., <1 kcal/mol uncertainty), as well as on the broad scope of chemical problems made accessible. The performance of state-of-the-art methods are also compared, including the most employed DLPNO and, in particular, our local natural orbital (LNO) CCSD(T) approach. The high accuracy and efficiency of the LNO method makes chemically accurate CCSD(T) computations accessible for molecules of hundreds of atoms with resources affordable to a broad computational community (days on a single CPU and 10–100 GB of memory). Recent developments in LNO-CCSD(T) enable systematic convergence and robust error estimates even for systems of complicated electronic structure or larger size (up to 1000 atoms). The predictive power of current local CCSD(T) methods, usually at about 1–2 order of magnitude higher cost than hybrid density functional theory (DFT), has become outstanding on the palette of computational chemistry applicable for molecules of practical interest. We also review more than 50 LNO-based and other advanced local-CCSD(T) applications for realistic, large systems across molecular interactions as well as main group, transition metal, bio-, and surface chemistry. The examples show that properly executed local-CCSD(T) can contribute to binding, reaction equilibrium, rate constants, etc. which are able to match measurements within the error estimates. These applications demonstrate that modern, open-access, and broadly affordable local methods, such as LNO-CCSD(T), already enable predictive computations and atomistic insight for complicated, real-life molecular processes in realistic environments.
We review the current capabilities of local electron correlation methods up to the coupled cluster model with single, double, and perturbative triple excitations [CCSD(T)], which is a gold standard in quantum chemistry. The main computational aspects of the local method types are assessed from the perspective of applications, but the focus is kept on how to achieve chemical accuracy (i.e., <1 kcal/mol uncertainty), as well as on the broad scope of chemical problems made accessible. The performance of state-of-the-art methods are also compared, including the most employed DLPNO and, in particular, our local natural orbital (LNO) CCSD(T) approach. The high accuracy and efficiency of the LNO method makes chemically accurate CCSD(T) computations accessible for molecules of hundreds of atoms with resources affordable to a broad computational community (days on a single CPU and 10–100 GB of memory). Recent developments in LNO-CCSD(T) enable systematic convergence and robust error estimates even for systems of complicated electronic structure or larger size (up to 1000 atoms). The predictive power of current local CCSD(T) methods, usually at about 1–2 order of magnitude higher cost than hybrid density functional theory (DFT), has become outstanding on the palette of computational chemistry applicable for molecules of practical interest. We also review more than 50 LNO-based and other advanced local-CCSD(T) applications for realistic, large systems across molecular interactions as well as main group, transition metal, bio-, and surface chemistry. The examples show that properly executed local-CCSD(T) can contribute to binding, reaction equilibrium, rate constants, etc. which are able to match measurements within the error estimates. These applications demonstrate that modern, open-access, and broadly affordable local methods, such as LNO-CCSD(T), already enable predictive computations and atomistic insight for complicated, real-life molecular processes in realistic environments.
Accurate correlated electronic structure methods involve a significant amount of computations and can be only employed to small molecular systems. For example, the coupled-cluster singles, doubles, and perturbative triples model (CCSD(T)), which is known as the ``gold standard" of quantum chemistry for its accuracy, usually can treat molecules with 20-30 atoms. To extend the reach of accurate correlated electronic structure methods to larger molecular systems, we work towards two directions: parallel computing and reduced-cost/scaling approaches. Parallel computing can utilize more computational resources to handle systems that demand more substantial computational efforts. Reduced-cost/scaling approaches, which introduce approximations to the existing electronic structure methods, can significantly reduce the amount of computation and storage requirements. In this work, we introduce a new distributed-memory massively parallel implementation of standard and explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) with canonical bigO{N^6} computational complexity ( C. Peng, J. A. Calvin, F. Pavov{s}evi'c, J. Zhang, and E. F. Valeev, textit{J. Phys. Chem. A} 2016, textbf{120}, 10231.), based on the TiledArray tensor framework. Excellent strong scaling is demonstrated on a multi-core shared-memory computer, a commodity distributed-memory computer, and a national-scale supercomputer. We also present a distributed-memory implementation of the density-fitting (DF) based CCSD(T) method. (C. Peng, J. A. Calvin, and E. F. Valeev, textit{in preparation for submission}) An improved parallel DF-CCSD is presented utilizing lazy evaluation for tensors with more than two unoccupied indices, which makes the DF-CCSD storage requirements always smaller than those of the non-iterative triples correction (T). Excellent strong scaling is observed on both shared-memory and distributed-memory computers equipped with conventional Intel Xeon processors and the Intel Xeon Phi (Knights Landing) processors. With the new implementation, the CCSD(T) energies can be evaluated for systems containing 200 electrons and 1000 basis functions in a few days using a small size commodity cluster, with even more massive computations possible on leadership-class computing resources. The inclusion of F12 correction to the CCSD(T) method makes it converge to basis set limit much more rapidly. The large-scale parallel explicitly correlated coupled-cluster program makes the accurate estimation of the coupled-cluster basis set limit for molecules with 20 or more atoms a routine. Thus, it can be used rigorously to test the emerging reduced-scaling coupled-cluster approaches. Moreover, we extend the pair natural orbital (PNO) approach to excited states through the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method. (C. Peng, M. C. Clement, and E. F. Valeev, textit{submitted}) We simulate the PNO-EOM-CCSD method using an existing massively parallel canonical EOM-CCSD program. We propose the use of state-averaged PNOs, which are generated from the average of the pair density of excited states, to span the PNO space of all the excited states. The doubles amplitudes in the CIS(D) method are used to compute the state-averaged pair density of excited states. The issue of incorrect states in the state-averaged pair density, caused by an energy reordering of excited states between the CIS(D) and EOM-CCSD, is resolved by simply computing more states than desired. We find that with a truncation threshold of 10−7, the truncation error for the excitation energy is already below 0.02 eV for the systems tested, while the average number of PNOs is reduced to 50-70 per pair. The accuracy of the PNO-EOM-CCSD method on local, Rydberg and charge transfer states is also investigated.
Recent developments in quantum embedding theories have provided attractive approaches to correlated calculations for large systems. In this work, we extend our previous work [ J. Chem. Theory Comput. 2019, 15, 4497–4506; J. Phys. Chem. Lett. 2019, 10, 6368–6374] on bootstrap embedding (BE) to enable correlated ab initio calculations at the coupled cluster with singles and doubles (CCSD) level for large molecules. We introduce several new algorithmic developments that significantly reduce the computational cost of BE, while maintaining its accuracy. The resulting implementation scales as O ( N 3 ) for the integral transform and O ( N ) for the CCSD calculation. Numerical results on a series of conjugated molecules suggest that BE with reasonably sized fragments can recover more than 99.5% of the total correlation energy of a full CCSD calculation, while the required computational resources (time and storage) compare favorably to one popular local correlation scheme: domain localized pair natural orbital (DLPNO). The largest BE calculation in this work involves ∼2900 basis functions and can be performed on a single node with 16 CPU cores and 64 GB of memory in a few days. We anticipate that these developments represent an important step toward the application of BE to solve practical problems.
Coupled-cluster theory with single, double, and perturbative triple excitations (CCSD(T))-often considered the "gold standard" of main-group quantum chemistry-is inapplicable to three-dimensional metals due to an infrared divergence, preventing its application to many important problems in materials science. We study the full, nonperturbative inclusion of triple excitations (CCSDT) and propose a new, iterative method, which we call ring-CCSDT, that resums the essential triple excitations with the same N^{7} run-time scaling as CCSD(T). CCSDT and ring-CCSDT are used to calculate the correlation energy of the uniform electron gas at metallic densities and the structural properties of solid lithium. Inclusion of connected triple excitations is shown to be essential to achieving high accuracy. We also investigate semiempirical CC methods based on spin-component scaling and the distinguishable cluster approximation and find that they enhance the accuracy of their parent ab initio methods.
Perhaps the most important approximations to the electronic structure problem in quantum chemistry are those based on coupled cluster and density functional theories. Coupled cluster theory has been called the ``gold standard'' of quantum chemistry due to the high accuracy that it achieves for weakly correlated systems. Kohn--Sham density functionals based on semilocal approximations are, without a doubt, the most widely used methods in chemistry and material science because of their high accuracy/cost ratio. The root of the success of coupled cluster and density functionals is their ability to efficiently describe the dynamic part of the electron correlation. However, both traditional coupled cluster and density functional approximations may fail catastrophically when substantial static correlation is present. This severely limits the applicability of these methods to a plethora of important chemical and physical problems such as, e.g., the description of bond breaking, transition states, transition metal-, lanthanide- and actinide-containing compounds, and superconductivity. In an attempt to tackle this problem, nonstandard (single-reference) coupled cluster-based techniques that aim to describe static correlation have been recently developed: pair coupled cluster doubles (pCCD) and singlet-paired coupled cluster doubles (CCD0). The ability to describe static correlation in pCCD and CCD0 comes, however, at the expense of important amounts of dynamic correlation so that the high accuracy of standard coupled cluster becomes unattainable. Thus, the reliable and efficient description of static and dynamic correlation in a simultaneous manner remains an open problem for quantum chemistry and many-body theory in general. In this thesis, different ways to combine pCCD and CCD0 with density functionals in order to describe static and dynamic correlation simultaneously (and efficiently) are explored. The combination of wavefunction and density functional methods has a long history in quantum chemistry (practical implementations have appeared in the literature since the 1970s). However, this kind of techniques have not achieved widespread use due to problems such as double counting of correlation and the symmetry dilemma---the fact that wavefunction methods respect the symmetries of Hamiltonian, while modern functionals are designed to work with broken symmetry densities. Here, particular mathematical features of pCCD and CCD0 are exploited to avoid these problems in an efficient manner. The two resulting families of approximations, denoted as pCCD+DFT and CCD0+DFT, are shown to be able to describe static and dynamic correlation in standard benchmark calculations. Furthermore, it is also shown that CCD0+DFT lends itself to combination with correlation from the direct random phase approximation (dRPA). Inclusion of dRPA in the long-range via the technique of range-separation allows for the description of dispersion correlation, the remaining part of the correlation. Thus, when combined with the dRPA, CCD0+DFT can account for all three-types of electron correlation that are necessary to accurately describe molecular systems. Lastly, applications of CCD0+DFT to actinide chemistry are considered in this work. The accuracy of CCD0+DFT for predicting equilibrium geometries and vibrational frequencies of actinide molecules and ions is assessed and compared to that of well-established quantum chemical methods. For this purpose, the f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and Thorium (ThO, ThO2+) and Nobelium (NoO, NoO2) oxides are studied. It is shown that the CCD0+DFT description of these species agrees with available experimental data and is comparable with the results given by the highest-level calculations that are possible for such heavy compounds while being, at least, an order of magnitude lower in computational cost.
We introduce a black-box auxiliary field quantum Monte Carlo (AFQMC) approach to perform highly accurate electronic structure calculations using configuration interaction singles and doubles (CISD) trial states. This method consistently provides more accurate energy estimates than coupled cluster singles and doubles with perturbative triples (CCSD(T)), often regarded as the gold standard in quantum chemistry. This level of precision is achieved at a lower asymptotic computational cost, scaling as O ( N 6 ) compared to the O ( N 7 ) scaling of CCSD(T). We provide numerical evidence supporting these findings through results for challenging main group and transition metal-containing molecules.
A well-parallelized local singles and doubles coupled-cluster (LCCSD) method using pair natural virtual orbitals (PNOs) is presented. The PNOs are constructed using large domains of projected atomic orbitals (PAOs) and orbital specific virtual orbitals (OSVs). We introduce a hierarchy of close, weak, and distant pairs, based on pair energies evaluated by local Møller–Plesset perturbation theory (LMP2). In contrast to most previous implementations of LCCSD methods, the close and weak pairs are not approximated by LMP2 but treated by higher-order methods. This leads to greatly improved accuracy for large systems, in particular when long-range dispersion interactions are important. Close pair amplitudes are optimized using approximate LCCSD equations, in which slowly decaying terms that mutually cancel at long-range are neglected. For weak pairs, the same approximations are used, but in addition, the nonlinear terms are neglected (coupled electron pair approximation). Distant pairs are treated by spin-component scaled (SCS)-LMP2 using multipole approximations. For efficiency reasons, various projection approximations are also introduced. The impact of these approximations on absolute and relative energies depends on the PNO domain sizes. The errors are found to be negligible, provided that sufficiently large PNO domains are used for close and weak pairs. For the selection of these domains the usual natural orbital occupation number criterion is found to be insufficient, and an additional energy criterion is used. For extended one-dimensional systems, the computational effort of the method scales nearly linearly with the number of correlated electrons, but the linear scaling regime is usually not reached in real-life applications for three-dimensional systems. Nevertheless, due to the parallelization that is efficient up to about 100–200 CPU cores (dependent on the molecular size), accurate calculations for three-dimensional molecules with about 100 atoms and augmented triple-ζ basis sets (e.g., cc-pVTZ-F12) can be carried out in 1–3 h of elapsed time (depending on the molecular structure and the number of CPU cores, excluding the time for Hartree–Fock). The convergence of the results with respect to the thresholds and options that control the domain, pair, and projection approximations is extensively tested. Benchmark examples for several difficult and large cases are presented, which demonstrate that the errors of relative energies (e.g., reaction energies, barrier heights) caused by the pair and projection approximations can be reduced to below 1 kJ mol –1 . The remaining errors are mainly caused by the finite PAO domains. The larger these are made, the more intramolecular or intermolecular basis set superposition errors are introduced, and the canonical results are approached only very slowly. This problem is eliminated in the explicitly correlated variant of our method (PNO-LCCSD-F12), which will be described in a separate paper, along with a larger set of benchmark calculations.