Formulation and implementation of a relativistic unrestricted coupled-cluster method including noniterative connected triples

Abstract

The formalism for a relativistic open‐shell CCSD(T) method is presented and implemented in a computer program, RELCCSD. The code can be used for calculations with 2‐ or 4‐component relativistic reference wave functions and allows a full inclusion of the spin–orbit coupling. The code is interfaced to the MOLFDIR program system. We illustrate its use with ab initio calculations of the fine structure splittings of Cl, FO, ClO, O+ 2, and O− 2. The triples correction is found to make a large contribution to the Cl atom splitting, which is within 23 cm−1, of the experimental value. The molecular results are within 4 cm−1 of the experimental values where these are available. The value for FO is predicted to be −195±4 cm−1, in good agreement with experiment.