Reduced-Cost Four-Component Relativistic Double Ionization Potential Equation-of-Motion Coupled-Cluster Approaches with 4-Hole–2-Particle Excitations and Three-Body Clusters

Mukhopadhyay, Tamoghna; Mukherjee, Madhubani; Gururangan, Karthik; Piecuch, Piotr; Dutta, Achintya Kumar

doi:10.1021/acs.jctc.5c01791

Title: Reduced-Cost Four-Component Relativistic Double Ionization Potential Equation-of-Motion Coupled-Cluster Approaches with 4-Hole–2-Particle Excitations and Three-Body Clusters

Journal Article · Fri Mar 27 00:00:00 UTC 2026 · Journal of Chemical Theory and Computation

DOI: https://doi.org/10.1021/acs.jctc.5c01791 · OSTI ID:3365383

^[1]; Mukherjee, Madhubani ^[1];

^[2];

^[3]

Indian Inst. of Technology (IIT), Mumbai (India)
Michigan State Univ., East Lansing, MI (United States)
Indian Inst. of Technology (IIT), Mumbai (India); Comenius Univ., Bratislava (Slovakia)

The double ionization potential (DIP) equation-ofmotion (EOM) coupled-cluster (CC) method with 4-hole−2- particle (4h-2p) excitations on top of the CC with singles, doubles, and triples calculation, abbreviated as DIP-EOMCCSDT(4h-2p), along with its perturbative DIP-EOMCCSD(T)(a)(4h-2p) approximation, are extended to a relativistic four-component (4c) framework. In addition, we introduce and test a new computationally practical DIP-EOMCC approach, which we call DIPEOMCCSD( T)(ã)(4h-2p), that approximates the treatment of 4h- 2p correlations within the DIP-EOMCCSD(T)(a)(4h-2p) method and reduces the $$\mathcal{N}$$⁸ scaling characterizing DIP-EOMCCSDT(4h- 2p) and DIP-EOMCCSD(T)(a)(4h-2p) to $$\mathcal{N}$$⁷ with the system size $$\mathcal{N}$$. Further improvements in computational efficiency are obtained using the frozen natural spinor (FNS) approximation to reduce the numbers of unoccupied spinors entering the correlated steps of the DIP-EOMCC calculations according to a well-defined occupation-number-based threshold. The resulting 4c-FNS-DIPEOMCC approaches are used to compute DIPs for the series of inert gas atoms from argon to radon as well as the vertical DIPs in Cl₂, Br₂, HBr, and HI, which have been experimentally examined in the past. We demonstrate that, when using complete basis set extrapolations and FNS truncation threshold of 10^−4.5, the 4c-FNS-DIP-EOMCCSD(T)(ã)(4h-2p) calculations are capable of predicting DIPs in agreement with experimental data, improving upon their nonrelativistic and spin-free scalar-relativistic counterparts, particularly when examining DIPs characterized by stronger spin−orbit coupling effects.

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Research Organization:: Michigan State Univ., East Lansing, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-01ER15228

OSTI ID:: 3365383

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 7 Vol. 22; ISSN 1549-9626; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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