State-Of-The-Art Computations of Vertical Electron Affinities with the Extended Koopmans' Theorem Integrated with the CCSD(T) Method.

Abstract

Accurate computation of electron affinities (EAs), within 0.10 eV, is one of the most challenging problems in modern computational quantum chemistry. The extended Koopmans' theorem (EKT) enables direct computations of electron affinities (EAs) from any level of the theory. In this research, the EKT approach based on the coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method is applied to computations of EAs for the first time. For efficiency, the density-fitting (DF) technique is used for two-electron integrals. Further, the EKT-CCSD(T) method is applied to three test sets of atoms and closed- and open-shell molecules, denoted A16, C10, and O33, respectively, for comparison with the experimental electron affinities. For the A16, C10, and O33 sets, the EKT-CCSD(T) approach, along with the aug-cc-pV5Z basis set, provide mean absolute errors (MAEs) of 0.05, 0.08, and 0.09 eV, respectively. Hence, our results demonstrate that high-accuracy computations of EAs can be achieved with the EKT-CCSD(T) approach. Further, when the EKT-CCSD(T) approach is not computationally affordable, the EKT-MP2.5, EKT-LCCD, and EKT-CCSD methods can be considered, and their results are also reasonably accurate. The huge advantage of the EKT method for the computation of IPs is that it comes for free in an analytic gradient computation. Hence, one needs neither separate computations for neutral and ionic species, as in the case of common approaches, nor additional efforts to obtain IPs, as in the case of equation-of-motion approaches. Overall, we believe that the present research may open new avenues in EA computations.