The MRCC program system: Accurate quantum chemistry from water to proteins.

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.

Novel strategy to implement active-space coupled-cluster methods.

A new approach is presented for the efficient implementation of coupled-cluster (CC) methods including higher excitations based on a molecular orbital space partitioned into active and inactive orbitals. In the new framework, the string representation of amplitudes and intermediates is used as long as it is beneficial, but the contractions are evaluated as matrix products. Using a new diagrammatic technique, the CC equations are represented in a compact form due to the string notations we introduced.

A quasiparticle-based multi-reference coupled-cluster method.

The purpose of this paper is to introduce a quasiparticle-based multi-reference coupled-cluster (MRCC) approach. The quasiparticles are introduced via a unitary transformation which allows us to represent a complete active space reference function and other elements of an orthonormal multi-reference (MR) basis in a determinant-like form. The quasiparticle creation and annihilation operators satisfy the fermion anti-commutation relations.

An efficient linear-scaling CCSD(T) method based on local natural orbitals.

An improved version of our general-order local coupled-cluster (CC) approach [Z. Rolik and M. Kállay, J.

A general-order local coupled-cluster method based on the cluster-in-molecule approach.

A general-order local coupled-cluster (CC) method is presented which has the potential to provide accurate correlation energies for extended systems. Our method combines the cluster-in-molecule approach of Li and co-workers [J. Chem.

High-accuracy theoretical thermochemistry of atmospherically important sulfur-containing molecules.

In this study, several sulfur-containing molecules with atmospherical importance were investigated by means of high-accuracy quantum chemical calculations including: HSO, HOS, HOSO2, HSNO, SH, CH2SO, CH2SH, S2COH, and SCSOH. After identifying the stable conformers of the molecules, a coupled-cluster-based composite model chemistry, which includes contributions up to quadruple excitations as well as corrections beyond the nonrelativistic and Born–Oppenheimer approximations, was applied to calculate the corresponding heat of formation (Δ(f)H(0)° and Δ(f)H(298)°) and entropy (S(298)°) values. In most of the cases, this study delivers more reliable estimates for the investigated thermodynamic properties than those reported in previous investigations.

Cost reduction of high-order coupled-cluster methods via active-space and orbital transformation techniques.

We discuss several techniques which have the potential to decrease the computational expenses of high-order coupled-cluster (CC) methods with a reasonable loss in accuracy. In particular, the CC singles, doubles, and triples (CCSDT) as well as the CC singles, doubles, triples, and perturbative quadruples [CCSDT(Q)] methods are considered, which are frequently used in high-precision model chemistries for the calculation of iterative triples and quadruples corrections. First, we study the possibilities for using active spaces to decrease the computational costs.

High-accuracy thermochemistry of atmospherically important fluorinated and chlorinated methane derivatives.

High-precision quantum chemical calculations have been performed for atmospherically important halomethane derivatives including CF, CF(3), CHF(2), CH(2)F, CF(2), CF(4), CHF, CHF(3), CH(3)F, CH(2)F(2), CCl, CCl(3), CHCl(2), CH(2)Cl, CCl(2), CCl(4), CHCl, CHCl(3), CH(3)Cl, CH(2)Cl(2), CHFCl, CF(2)Cl, CFCl(2), CFCl, CFCl(3), CF(2)Cl(2), CF(3)Cl, CHFCl(2), CHF(2)Cl, and CH(2)FCl. Theoretical estimates for the standard enthalpy of formation at 0 and 298.15 K as well as for the entropy at 298.

Comparative study of multireference perturbative theories for ground and excited states.

Three recently developed multireference perturbation theories (PTs)-generalized Van Vleck PT (GVVPT), state-specific multireference PT (SS-MRPT), and multiconfiguration PT (MCPT)-are briefly reviewed and compared numerically on representative examples, at the second order of approximations. We compute the dissociation potential curve of the LiH molecule and the BeH(2) system at various geometries, both in the ground and in the first excited singlet state. Furthermore, the ethylene twisting process is studied.

A sparse matrix based full-configuration interaction algorithm.

We present an algorithm related to the full-configuration interaction (FCI) method that makes complete use of the sparse nature of the coefficient vector representing the many-electron wave function in a determinantal basis. Main achievements of the presented sparse FCI (SFCI) algorithm are (i) development of an iteration procedure that avoids the storage of FCI size vectors; (ii) development of an efficient algorithm to evaluate the effect of the Hamiltonian when both the initial and the product vectors are sparse. As a result of point (i) large disk operations can be skipped which otherwise may be a bottleneck of the procedure.

Comparison of low-order multireference many-body perturbation theories.

Tests have been made to benchmark and assess the relative accuracies of low-order multireference perturbation theories as compared to coupled cluster (CC) and full configuration interaction (FCI) methods. Test calculations include the ground and some excited states of the Be, H(2), BeH(2), CH(2), and SiH(2) systems. Comparisons with FCI and CC calculations show that in most cases the effective valence shell Hamiltonian (H(v)) method is more accurate than other low-order multireference perturbation theories, although none of the perturbative methods is as accurate as the CC approximations.

Multiconfiguration perturbation theory: size consistency at second order.

A modified version of a previously elaborated multiconfiguration perturbation theory (MCPT) [Rolik et al. J. Chem.