An explicitly correlated local coupled cluster method for calculations of large molecules close to the basis set limit

摘要

A new explicitly correlated local coupled-cluster method with single and double excitations and a perturbative treatment of triple excitations [DF-LCCSD(T0)-F12x (x=a,b)] is presented. By means of truncating the virtual orbital space to pair-specific local domains (domain approximation) and a simplified treatment of close, weak and distant pairs using LMP2-F12 (pair approximation) the scaling of the computational cost with molecular size is strongly reduced. The basis set incompleteness errors as well as the errors due to the domain approximation are largely eliminated by the explicitly correlated terms. All integrals are computed using efficient density fitting (DF) approximations. The accuracy of the method is investigated for 52 reactions involving medium size molecules. A comparison of DF-LCCSD(T0)-F12x reaction energies with canonical CCSD(T)-F12x calculations shows that the errors introduced by the domain approximation are indeed very small. Care must be taken to keep the errors due to the additional pair approximation equally small, and appropriate distance criteria are recommended. Using these parameters, the root mean square (RMS) deviations of DF-LCCSD(T0)-F12a calculations with triple-ζ basis sets from estimated CCSD(T) complete basis set (CBS) limits and experimental data amount to only 1.5 kJmol~(-1) and 2.9 kJmol ~(-1), respectively. For comparison, the RMS deviation of the CCSD(T)/CBS values from the experimental values amounts to 3.0 kJmol ~(-1). The potential of the method is demonstrated for five reactions of biochemical or pharmacological interest which include molecules with up to 61 atoms. These calculations show that molecules of this size can now be treated routinely and yield results that are close to the CCSD(T) complete basis set limits.