We consider the rank-reduced coupled-cluster theory with single and double (RR-CCSD) excitations introduced recently [Parrish et al., J. Chem. Phys. 150, 164118 (2019)]. The main feature of this method is the decomposed form of doubly excited amplitudes, which are expanded in the basis of largest magnitude eigenvectors of MP2 or MP3 amplitudes. This approach enables a substantial compression of amplitudes with only minor loss of accuracy. However, the formal scaling of the computational costs with the system size (N) is unaffected in comparison with the conventional CCSD theory (∝N6) due to the presence of some terms quadratic in amplitudes, which do not naturally factorize to a simpler form even within the rank-reduced framework. We show how to solve this problem, exploiting the fact that their effective rank increases only linearly with the system size. We provide a systematic way to approximate the problematic terms using the singular value decomposition and reduce the scaling of the RR-CCSD iterations down to the level of N5. This is combined with an iterative method of finding dominant eigenpairs of MP2 or MP3 amplitudes, which eliminates the necessity to perform the complete diagonalization, making the cost of this step proportional to the fifth power of the system size, as well. Next, we consider the evaluation of perturbative corrections to CCSD energies resulting from triply excited configurations. The triply excited amplitudes present in the CCSD(T) method are decomposed to the Tucker-3 format using the higher-order orthogonal iteration procedure. This enables us to compute the energy correction due to triple excitations non-iteratively with N6 cost. The accuracy of the resulting rank-reduced CCSD(T) method is studied for both total and relative correlation energies of a diverse set of molecules. Accuracy levels better than 99.9% can be achieved with a substantial reduction of the computational costs. Concerning the computational timings, the break-even point between the rank-reduced and conventional CCSD implementations occurs for systems with about 30–40 active electrons.
We have developed a graphical processing unit (GPU) accelerated implementation of our recently introduced rank-reduced coupled-cluster singles and doubles (RR-CCSD) method. RR-CCSD introduces a low-rank approximation of the doubles amplitudes. This is combined with a low-rank approximation of the electron repulsion integrals via Cholesky decomposition. The result of these two low-rank approximations is the replacement of the usual fourth-order CCSD tensors with products of second- and third-order tensors. In our implementation, only a single fourth-order tensor must be constructed as an intermediate during the solution of the amplitude equations. Owing in large part to the compression of the doubles amplitudes, the GPU-accelerated implementation shows excellent parallel efficiency (95% on eight GPUs). Our implementation can solve the RR-CCSD equations for up to 400 electrons and 1550 basis functions—roughly 50% larger than the largest canonical CCSD computations that have been performed on any hardware. In addition to increased scalability, the RR-CCSD computations are faster than the corresponding CCSD computations for all but the smallest molecules. We test the accuracy of RR-CCSD for a variety of chemical systems including up to 1000 basis functions and determine that accuracy to better than 0.1% error in the correlation energy can be achieved with roughly 95% compression of the ov space for the largest systems considered. We also demonstrate that conformational energies can be predicted to be within 0.1 kcal mol−1 with efficient compression applied to the wavefunction. Finally, we find that low-rank approximations of the CCSD doubles amplitudes used in the similarity transformation of the Hamiltonian prior to a conventional equation-of-motion CCSD computation will not introduce significant errors (on the order of a few hundredths of an electronvolt) into the resulting excitation energies.
Abstract We report a complete implementation of the coupled-cluster method with single, double, and triple excitations (CCSDT) in which tensor decompositions are used to reduce scaling and overall computational costs. For the decomposition of the electron repulsion integrals the standard density fitting (or Cholesky decomposition) format is used. The coupled-cluster single and double amplitudes are treated conventionally, and for the triple amplitudes tensor we employ the Tucker-3 compression formula, tijkabc ≈ tXYZ UaiX UbjY UckZ. The auxiliary quantities UaiX come from singular value decomposition (SVD) of an approximate triple amplitudes tensor based on perturbation theory. The efficiency of the proposed method relies on an observation that the dimension of the “compressed” tensor tXYZ sufficient to deliver a constant relative accuracy of the correlation energy grows only linearly with the size of the system, N. This fact, combined with proper factorization of the coupled-cluster equations, leads to practically N6 scaling of the computational costs of the proposed method, as illustrated numerically for linear alkanes with increasing chain length. This constitutes a considerable improvement over the N8 scaling of the conventional (uncompressed) CCSDT theory. The accuracy of the proposed method is verified by benchmark calculations of total and relative energies for several small molecular systems and comparison with the exact CCSDT method. The accuracy levels of 1 kJ/mol are easily achievable with reasonable SVD subspace size, and even more demanding levels of accuracy can be reached with a considerable reduction of the computational costs. Extensions of the proposed method to include higher excitations are briefly discussed, along with possible strategies of reducing other residual errors.
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.
The coupled cluster method is considered a gold standard in quantum chemistry, reliably giving energies that are exact within chemical accuracy (1.6 mhartree). However, even in the coupled cluster single-double (CCSD) approximation, where the cluster operator is truncated to include only single and double excitations, the method scales as O(N6) in the number of electrons, and the cluster operator needs to be solved for iteratively, increasing the computation time. Inspired by eigenvector continuation, we present here an algorithm making use of the Gaussian processes that provides an improved initial guess for the coupled cluster amplitudes. The cluster operator is written as a linear combination of sample cluster operators that are obtained at particular sample geometries. By reusing the cluster operators from previous calculations in that way, it is possible to obtain a start guess for the amplitudes that surpasses both MP2 guesses and “previous geometry”-guesses in terms of the number of necessary iterations. As this improved guess is very close to the exact cluster operator, it can be used directly to calculate the CCSD energy to chemical accuracy, giving approximate CCSD energies scaling as O(N5).
The efficiency of the Tucker decomposition of amplitude tensors within the single-reference relativistic coupled cluster method with single and double excitations was studied in a series of benchmark calculations for (AuCl)n chains, Aun clusters, and the cluster model of solid YbCl2. The 1 kJ/mol level of accuracy for correlation energy estimates of moderate-size systems and typical reaction energies can be achieved with relatively high compression rates of amplitude tensors via rejecting singular values smaller than ∼10-4. For the most extensive system studied (the YbCl7 cluster used for modeling of the ytterbium center in the ytterbium dichloride crystal), only ∼3% of compressed double amplitudes were shown to be significant. Thus, the rank reduction for the relativistic coupled cluster method with single and double theory, improving its computational scaling, is feasible. The advantage (if not necessity) of using the Goldstone diagrammatic technique rather than the "antisymmetrized" Brandow one is underlined. The proposed approach is promising for high-precision modeling of relatively large systems with heavy atoms.
A parallel algorithm is described for the coupled-cluster singles and doubles method augmented with a perturbative correction for triple excitations [CCSD(T)] using the resolution-of-the-identity (RI) approximation for two-electron repulsion integrals (ERIs). The algorithm bypasses the storage of four-center ERIs by adopting an integral-direct strategy. The CCSD amplitude equations are given in a compact quasi-linear form by factorizing them in terms of amplitude-dressed three-center intermediates. A hybrid MPI/OpenMP parallelization scheme is employed, which uses the OpenMP-based shared memory model for intranode parallelization and the MPI-based distributed memory model for internode parallelization. Parallel efficiency has been optimized for all terms in the CCSD amplitude equations. Two different algorithms have been implemented for the rate-limiting terms in the CCSD amplitude equations that entail and -scaling computational costs, where N O and N V denote the number of correlated occupied and virtual orbitals, respectively. One of the algorithms assembles the four-center ERIs requiring N V 4 and N O 2 N V 2 -scaling memory costs in a distributed manner on a number of MPI ranks, while the other algorithm completely bypasses the assembling of quartic memory-scaling ERIs and thus largely reduces the memory demand. It is demonstrated that the former memory-expensive algorithm is faster on a few hundred cores, while the latter memory-economic algorithm shows a better strong scaling in the limit of a few thousand cores. The program is shown to exhibit a near-linear scaling, in particular for the compute-intensive triples correction step, on up to 8000 cores. The performance of the program is demonstrated via calculations involving molecules with 24–51 atoms and up to 1624 atomic basis functions. As the first application, the complete basis set (CBS) limit for the interaction energy of the π-stacked uracil dimer from the S66 data set has been investigated. This work reports the first calculation of the interaction energy at the CCSD(T)/aug-cc-pVQZ level without local orbital approximation. The CBS limit for the CCSD correlation contribution to the interaction energy was found to be −8.01 kcal/mol, which agrees very well with the value −7.99 kcal/mol reported by Schmitz, Hättig, and Tew [ Phys. Chem. Chem. Phys. 2014, 16, 22167−22178]. The CBS limit for the total interaction energy was estimated to be −9.64 kcal/mol.