Correlation Consistent Basis Sets for Explicitly Correlated Theory: The Transition Metals

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Abstract
We present correlationconsistent basis sets for explicitly correlated(F12) calculations, denoted VnZ(-PP)-F12-wis (n = D,T), for the d-block elements. Thecc-pVDZ-F12-wis basis set is contracted to [8s7p5d2f] for the 3d-block, while its ECP counterpart for the 4d and 5d-blocks, cc-pVDZ-PP-F12-wis, is contractedto [6s6p5d2f]. The corresponding contracted sizes for cc-pVTZ(-PP)-F12-wisare [9s8p6d3f2g] for the 3d-blockelements and [7s7p6d3f2g] for the 4d and 5d-block elements. Our VnZ(-PP)-F12-wisbasis sets are evaluated on challenging test sets for metal-organicbarrier heights (MOBH35) and group-11 metal clusters (CUAGAU-2). InF12 calculations, they are found to be about as close to the completebasis set limit as the combination of standard cc-pVnZ-F12 on main-group elements with the standard aug-cc-pV(n+1)Z(-PP) basis sets on the transition metal(s). Whileour basis sets are somewhat more compact than aug-cc-pV(n+1)Z(-PP), the CPU time benefit is negligible for catalytic complexesthat contain only one or two transition metals among dozens of main-groupelements; however, it is somewhat more significant for metal clusters.
Funding Information
  • Israel Science Foundation (1969/20)
  • Minerva Foundation (2020/05)
  • Weizmann Institute of Science
  • Alexander S. Onassis Public Benefit Foundation (FZP 052-2/2021-2022)

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