Scalable Electron Correlation Methods. 8. Explicitly Correlated Open-Shell Coupled-Cluster with Pair Natural Orbitals PNO-RCCSD(T)-F12 and PNO-UCCSD(T)-F12.

作者：Qianli Ma, H. Werner · 发表于：Journal of Chemical Theory and Computation · 年份：2021 · DOI：10.1021/acs.jctc.0c01129 · 被引用次数：39 · 研究领域：Medicine

We present explicitly correlated open-shell pair natural orbital local coupled-cluster methods, PNO-RCCSD(T)-F12 and PNO-UCCSD(T)-F12. The methods are extensions of our previously reported PNO-R/UCCSD methods (J. Chem. Theory Comput., 2020, 16, 3135-3151, https://pubs.acs.org/doi/10.1021/acs.jctc.0c00192) with additions of explicit correlation and perturbative triples corrections. The explicit correlation treatment follows the spin-orbital CCSD-F12b theory using Ansatz 3*A, which is found to yield comparable or better basis set convergence than the more rigorous Ansatz 3C in computed ionization potentials and reaction energies using double- to quaduple-ζ basis sets. The perturbative triples correction is adapted from the spin-orbital (T) theory to use triples natural orbitals (TNOs). To address the coupling due to off-diagonal Fock matrix elements, the local triples amplitudes are iteratively solved using small domains of TNOs, and a semicanonical (T0) domain correction with larger domains is applied to reduce the domain errors. The performance of the methods is demonstrated through benchmark calculations on ionization potentials, radical stabilization energies, reaction energies of fragmentations and rearrangements in radical cations, and spin-state energy differences of iron complexes. For a few test sets where canonical calculations are feasible, PNO-RCCSD(T)-F12 results agree with the canonical ones to within 0.4 kcal mol-1, and this maximum error is reduced to below 0.2 ...