Chan, Bun

Karton, Amir

2022-08-05

<p>In the present study, we have investigated the performance of RIJCOSX DLPNOCCSD(T)-F12 methods for a wide range of systems. Calculations with a high-accuracy option ["DefGrid3 RIJCOSX DLPNO-CCSD(T₁)-F12"] extrapolated to the complete-basis-set limit using the maug-cc-pV[D+d,T+d]Z basis sets provides fairly good agreements with the canonical CCSD(T)/CBS reference for a diverse set of thermochemical and kinetic properties [with mean absolute deviations (MADs) of ~1– 2 kJ mol^-1 except for atomization energies]. On the other hand, the low-cost "RIJCOSX DLPNO-CCSD(T)-F12D" option leads to substantial deviations for certain properties, notably atomization energies (MADs of up to tens of kJ mol^-1). With the high-accuracy CBS approach, we have formulated the L-W1X method, which further includes a low-cost core–valence plus scalar-relativistic term. It shows generally good accuracy. For improved accuracies in specific cases, we advise replacing maug-cc-pV (<i>n</i>+d)Z with jun-cc-pV(<i>n</i>+d)Z for the calculation of electron affinities, and using well-constructed isodesmic-type reactions to obtain atomization energies. For medium-sized systems, DefGrid3 RIJCOSX DLPNO-CCSD(T₁)-F12 calculations are several times faster than the corresponding canonical computation" the use of the local approximations (RIJCOSX and DLPNO) leads to a better scaling than that for the canonical calculation (from ~6–7 down to ~2–4 for our test systems). Thus, the DefGrid3 RIJCOSX DLPNO-CCSD(T₁)-F12 method, and the L-W1X protocol that based on it, represent a useful means for obtaining accurate thermochemical quantities for larger systems.</p>

Journal of Computational Chemistry, 43(21), p. 1394-1402

1096-987X

0192-8651

35709311

https://hdl.handle.net/1959.11/56211

en

John Wiley & Sons, Inc

Assessment of DLPNO-CCSD(T)-F12 and its use for the formulation of the low-cost and reliable L-W1X composite method

Journal Article

Publication