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mrcc is a versatile suite of quantum chemistry programs designed for accurate ab initio and density functional theory (DFT) calculations. This contribution outlines the general features and recent developments of the package. The most popular features include the open-ended coupled-cluster (CC) code, state-of-the-art CC singles and doubles with perturbative triples [CCSD(T)], second-order algebraic-diagrammatic construction, and combined wave function theory-DFT approaches. Cost-reduction techniques are implemented, such as natural orbital (NO), local NO (LNO), and natural auxiliary function approximations, which significantly decrease the computational demands of these methods. This paper also details the method developments made over the past five years, including efficient schemes to approach the complete basis set limit for CCSD(T) and the extension of our LNO-CCSD(T) method to open-shell systems. Additionally, we discuss the new approximations introduced to accelerate the self-consistent field procedure and the cost-reduction techniques elaborated for analytic gradient calculations at various levels. Furthermore, embedding techniques and novel range-separated double-hybrid functionals are presented for excited-state calculations, while the extension of the theories established to describe core excitations and ionized states is also discussed. For academic purposes, the program and its source code are available free of charge, and its commercial use is also facilitated.

Parallel algorithms to accelerate explicitly correlated second-order Mo̷ller-Plesset (MP2) and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] calculations and benchmarks on extended molecular systems are reported. A hybrid Open Multi-Processing (OpenMP)/Message Passing Interface (MPI) parallel approach is used to distribute the computational load among processor cores and compute nodes. The intermediates at both the MP2 and the CCSD(T) levels are expressed in a density fitting formalism, using only three-index quantities to decrease the amount of data to be stored and communicated. To further reduce compute time, the frozen natural orbital, the natural auxiliary function, and the natural auxiliary basis schemes are implemented in a hybrid parallel manner. The combination of these three approximations and our recent size-consistent explicitly correlated triples correction with the new hybrid parallelization offers a unique accuracy-over-cost performance among explicitly correlated CC methods. Our comprehensive benchmarks demonstrate excellent parallel scaling of the cost-determining operations up to hundreds of processor cores. As demonstrated on the noncovalent interaction energy of the corannulene dimer, highly accurate explicitly correlated CCSD(T) calculations can be carried out for systems of 60 atoms and 2500 orbitals, which were beyond computational limits without local correlation approximations. This enables various applications, such as benchmarking of or, for certain size ranges, replacing local CCSD(T) or density functional methods as well as the further advancement of robust thermochemistry protocols designed for larger molecules of ca. 20-50 atoms.

We implement Epstein-Nesbet perturbative corrections in the third-order for the initiator approximation of the configuration space quantum Monte Carlo. An improved sampling algorithm is proposed to address the stochastic noise of the corrections. The stochastic error for the perturbative corrections is considerably larger than that for the reference energy, and it fails to provide reasonable results unless a very long imaginary time integration is performed. The new sampling algorithm accumulates rejected walkers from multiple independent steps to cover a larger portion of the secondary space. The performance of the perturbative corrections is demonstrated for small molecules.

MRCC is a package of ab initio and density functional quantum chemistry programs for accurate electronic structure calculations. The suite has efficient implementations of both low- and high-level correlation methods, such as second-order Møller-Plesset (MP2), random-phase approximation (RPA), second-order algebraic-diagrammatic construction [ADC(2)], coupled-cluster (CC), configuration interaction (CI), and related techniques. It has a state-of-the-art CC singles and doubles with perturbative triples [CCSD(T)] code, and its specialties, the arbitrary-order iterative and perturbative CC methods developed by automated programming tools, enable achieving convergence with regard to the level of correlation. The package also offers a collection of multi-reference CC and CI approaches. Efficient implementations of density functional theory (DFT) and more advanced combined DFT-wave function approaches are also available. Its other special features, the highly competitive linear-scaling local correlation schemes, allow for MP2, RPA, ADC(2), CCSD(T), and higher-order CC calculations for extended systems. Local correlation calculations can be considerably accelerated by multi-level approximations and DFT-embedding techniques, and an interface to molecular dynamics software is provided for quantum mechanics/molecular mechanics calculations. All components of MRCC support shared-memory parallelism, and multi-node parallelization is also available for various methods. For academic purposes, the package is available free of charge.

A general-order stochastic perturbation algorithm is obtained from the order-by-order expansion of the imaginary-time evolution of a configuration interaction wave function. A truncation of configuration space that is required for the practical treatment of the perturbative corrections, however, does not preserve size-consistency as is the case for a truncated configuration interaction. To circumvent this problem, we formulate a linked variant of stochastic perturbation theory based on the coupled-cluster ansatz. The implementation based on the linearized coupled-cluster is compared with several full configuration interaction results. We also compare the results with those obtained from deterministic coupled-cluster and many-body perturbation theories.

An improved version of our general-order local coupled-cluster (CC) approach [Z. Rolik and M. Kállay, J. Chem. Phys. 135, 104111 (2011)] and its efficient implementation at the CC singles and doubles with perturbative triples [CCSD(T)] level is presented. The method combines the cluster-in-molecule approach of Li and co-workers [J. Chem. Phys. 131, 114109 (2009)] with frozen natural orbital (NO) techniques. To break down the unfavorable fifth-power scaling of our original approach a two-level domain construction algorithm has been developed. First, an extended domain of localized molecular orbitals (LMOs) is assembled based on the spatial distance of the orbitals. The necessary integrals are evaluated and transformed in these domains invoking the density fitting approximation. In the second step, for each occupied LMO of the extended domain a local subspace of occupied and virtual orbitals is constructed including approximate second-order Mo̸ller-Plesset NOs. The CC equations are solved and the perturbative corrections are calculated in the local subspace for each occupied LMO using a highly-efficient CCSD(T) code, which was optimized for the typical sizes of the local subspaces. The total correlation energy is evaluated as the sum of the individual contributions. The computation time of our approach scales linearly with the system size, while its memory and disk space requirements are independent thereof. Test calculations demonstrate that currently our method is one of the most efficient local CCSD(T) approaches and can be routinely applied to molecules of up to 100 atoms with reasonable basis sets.