Three-Body Excitations in Fock-Space Coupled-Cluster: Fourth Order Perturbation Correction to Electron Affinity and Its Relation to Bondonic Formalism

• Published in: International journal of molecular sciences 2021-08, Vol.22 (16), p.8953
• Main Authors: Basumallick, Suhita, Putz, Mihai V., Pal, Sourav
• Format: Article
• Language: English
• Subjects: Adiabatic; Affinity; Anions; Approximation; bondonic formalism; Chemical bonds; Electron affinity; electronic affinity; Electrons; Energy; Fock-space coupled-cluster theory; Ionization; Ionization potentials; Methods; multi-reference coupled-cluster; perturbative triples
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms22168953

In this paper, we present a formulation of highly correlated Fock-space multi-reference coupled-cluster (FSMRCC) methods, including approximate triples on top of the FSMRCC with singles and doubles, which correct the electron affinities by at least at third and up to the fourth order in perturbation. We discuss various partial fourth-order schemes, which are reliable and yet computationally more efficient than the full fourth-order triples scheme. The third-order scheme is called MRCCSD+T*(3). We present two approximate fourth-order schemes, MRCCSD+T*−a(4) and MRCCSD+T*(4). The results that are presented allow one to choose an appropriate fourth-order scheme, which is less expensive and right for the problem. All these schemes are based on the effective Hamiltonian scheme, and provide a direct calculation of the vertical electron affinities. We apply these schemes to a prototype Li2 molecule, using four different basis sets, as well as BeO and CH+. We have calculated the vertical electron affinities of Li2 at the geometry of the neutral Li2 molecule. We also present the vertical ionization potentials of the Li2 anion at the geometry of the anion ground state. We have also shown how to calculate adiabatic electron affinity, though in that case we lose the advantages of direct calculation. BeO has been examined in two basis sets. For CH+, four different basis sets have been used. We have presented the partial fourth-order schemes to the EA in all the basis sets. The results are analyzed to illustrate the importance of triples, as well as highlight computationally efficient partial fourth-order schemes. The choice of the basis set on the electron affinity calculation is also emphasized. Comparisons with available experimental and theoretical results are presented. The general fourth-order schemes, which are conceptually equivalent with the Fock-space multi-reference coupled-cluster singles, doubles, and triplets (MRCCSD+T) methods, based on bondonic formalism, are also presented here in a composed way, for quantum electronic affinity.