Scalable Electron Correlation Methods. 7. Local Open-Shell Coupled-Cluster Methods Using Pair Natural Orbitals: PNO-RCCSD and PNO-UCCSD

• Published in: Journal of chemical theory and computation 2020-05, Vol.16 (5), p.3135-3151
• Main Authors: Ma, Qianli, Werner, Hans-Joachim
• Format: Article
• Language: English
• Subjects: Approximation; Clusters; Convergence; Coupling (molecular); Domains; Excitation; Mathematical analysis; Orbitals; Parallel processing
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00192

We present well-parallelized local implementations of high-spin open-shell coupled cluster methods with single and double excitations (CCSD) using pair natural orbitals (PNOs). The methods are based on the spin-orbital coupled cluster theory using restricted open-shell Hartree–Fock (ROHF) reference functions. Two variants, namely, PNO-UCCSD and PNO-RCCSD are implemented and compared. In PNO-UCCSD, the coupled cluster amplitudes are spin-unrestricted, while in PNO-RCCSD the linear terms are spin-adapted by a spin-projection approach as described in J. Chem. Phys. 1993, 99, 5219 −5227 . Near linear scaling of the computational cost with the number of correlated electrons is achieved by applying domain and pair approximations. The PNOs are spin-independent and obtained using a semicanonical spin-restricted MP2 approximation with large domains of projected atomic orbitals (PAOs). The pair approximations of our previously described closed-shell PNO-LCCSD method are carefully revised so that they are compatible to the UCCSD theory, and PNO-UCCSD or PNO-RCCSD calculations for closed-shell molecules yield exactly the same results as corresponding spin-free closed-shell PNO-LCCSD calculations. The convergence of the results with respect to the thresholds and options that control the domain and pair approximations is demonstrated. It is found that large domains are required for the single excitations in open-shell calculations in order to obtain converged results. In general, the errors of relative energies caused by the local approximations can be reduced to below 1 kcal mol–1, even for difficult cases. Presently, PNO-RCCSD and PNO-UCCSD calculations for molecules with 100–200 atoms and augmented triple-ζ basis sets can be carried out in a few hours of elapsed time using ∼100 CPU cores. In addition, the program is also capable of performing distinguishable cluster (PNO-RDCSD and PNO-UDCSC) calculations. The present work is a critical step in developing fully local open-shell PNO-RCCSD­(T)-F12 methods.