Assessment of the DLPNO Binding Energies of Strongly Noncovalent Bonded Atmospheric Molecular Clusters

Gunnar Schmitz, Jonas Elm*

*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

49 Citations (Scopus)

Abstract

This work assesses the performance of DLPNO-CCSD(T 0), DLPNO-MP2, and density functional theory methods in calculating the binding energies of a representative test set of 45 atmospheric acid-acid, acid-base, and acid-water dimer clusters. The performance of the approximate methods is compared to high level explicitly correlated CCSD(F12*)(T)/complete basis set (CBS) reference calculations. Out of the tested density functionals, ωB97X-D3(BJ) shows the best performance with a mean deviation of 0.09 kcal/mol and a maximum deviation of 0.83 kcal/mol. The RI-CC2/aug-cc-pV(T+d)Z level of theory severely overpredicts the cluster binding energies with a mean deviation of-1.31 kcal/mol and a maximum deviation up to-3.00 kcal/mol. Hence, RI-CC2/aug-cc-pV(T+d)Z should not be utilized for studying atmospheric molecular clusters. The DLPNO variants are tested both with and without the inclusion of explicit correlation (F12) in the wavefunction, with different pair natural orbital (PNO) settings (loosePNO, normalPNO, and tightPNO) and using both double and triple zeta basis sets. The performance of the DLPNO-MP2 methods is found to be independent of PNO settings and yield low mean deviations of-0.84 kcal/mol or below. However, DLPNO-MP2 requires explicitly correlated wavefunctions to yield maximum deviations below 1.40 kcal/mol. For obtaining high accuracy, with maximum deviation below âˆ1.0 kcal/mol, either DLPNO-CCSD(T 0)/aug-cc-pVTZ (normalPNO) calculations or DLPNO-CCSD(T 0)-F12/cc-pVTZ-F12 (normalPNO) calculations are required. The most accurate level of theory is found to be DLPNO-CCSD(T 0)-F12/cc-pVTZ-F12 using a tightPNO criterion which yields a mean deviation of 0.10 kcal/mol, with a maximum deviation of 0.20 kcal/mol, compared to the CCSD(F12*)(T)/CBS reference.

Original languageEnglish
JournalACS Omega
Volume5
Issue13
Pages (from-to)7601-7612
Number of pages12
ISSN2470-1343
DOIs
Publication statusPublished - Apr 2020

Keywords

  • AUTOXIDATION PRODUCT C6H8O7
  • BASIS-SETS
  • COUPLED-CLUSTER
  • DENSITY-FUNCTIONAL THERMOCHEMISTRY
  • ELECTRON CORRELATION METHODS
  • GENERALIZED GRADIENT APPROXIMATION
  • ORBITAL CONFIGURATION-INTERACTION
  • PAIR APPROXIMATION
  • PARTICLE FORMATION
  • SULFURIC-ACID

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