Kinetics and Thermodynamics of Reactions Involving Criegee Intermediates: An Assessment of Density Functional Theory and Ab Initio Methods Through Comparison with CCSDT(Q)/CBS Data

• Published in: Journal of computational chemistry Vol. 41; no. 4; pp. 328 - 339
• Main Authors: Smith, Cameron D., Karton, Amir
• Format: Journal Article
• Language: English
• Published: Hoboken, USA John Wiley & Sons, Inc 05.02.2020; Wiley Subscription Services, Inc
• Subjects: ab initio methods; Accuracy; Acetaldehyde; Atmospheric models; CCSDT(Q); Criegee intermediate; Density functional theory; G4(MP2) theory; Kinetics; Organic chemistry; Performance evaluation; Reaction kinetics; Thermodynamics; CCSDT(Q); Criegee intermediate; ab initio methods; density functional theory; G4(MP2) theory
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.26106

Reactions involving Criegee intermediates (CIs, R1R2COO) are important in atmospheric ozonolysis models. In recent years, density functional theory (DFT) and CCSD(T)‐based ab initio methods are increasingly being used for modeling reaction profiles involving CIs. We obtain highly accurate CCSDT(Q)/CBS reaction energies and barrier heights for ring‐closing reactions involving atmospherically important CIs (R1/R2 = H, Me, OH, OMe, F, CN, cyclopropene, ethylene, acetaldehyde, and acrolein). We use this benchmark data to evaluate the performance of DFT, double‐hybrid DFT (DHDFT), and ab initio methods for the kinetics and thermodynamics of these reactions. We find that reaction energies are more challenging for approximate theoretical procedures than barrier heights. Overall, taking both reaction energies and barrier heights into account, only one of the 58 considered DFT methods (the meta‐GGA MN12‐L) attains near chemical accuracy, with root‐mean‐square deviations (RMSDs) of 3.5 (barrier heights) and 4.7 (reaction energies) kJ mol−1. Therefore, MN12‐L is recommended for investigations where CCSD(T)‐based methods are not computationally feasible. For reaction barrier heights performance does not strictly follow Jacob's Ladder, for example, DHDFT methods do not perform better than conventional DFT methods. Of the ab initio methods, the cost‐effective CCSD(T)/CBS(MP2) approach gives the best performance for both reaction energies and barrier heights, with RMSDs of 1.7 and 1.4 kJ mol−1, respectively. All the considered Gaussian‐n methods show good performance with RMSDs below the threshold of chemical accuracy for both reaction energies and barrier heights, where G4(MP2) shows the best overall performance with RMSDs of 2.9 and 1.5 kJ mol−1, respectively. © 2019 Wiley Periodicals, Inc. This work shows that reaction profiles involving Criegee intermediates represent a challenging test for contemporary DFT and DHDFT methods with only one functional (MN12‐L) attaining near “chemical accuracy” relative to CCSDT(Q)/CBS reaction energies and barrier heights.