How to compute isomerization energies of organic molecules with quantum chemical methods
ABSTRACT The reaction energies for 34 typical organic isomerizations including oxygen and nitrogen heteroatoms are investigated with modern quantum chemical methods that have the perspective of also being applicable to large systems. The experimental reaction enthalpies are corrected for vibrational and thermal effects, and the thus derived "experimental" reaction energies are compared to corresponding theoretical data. A series of standard AO basis sets in combination with second-order perturbation theory (MP2, SCS-MP2), conventional density functionals (e.g., PBE, TPSS, B3-LYP, MPW1K, BMK), and new perturbative functionals (B2-PLYP, mPW2-PLYP) are tested. In three cases, obvious errors of the experimental values could be detected, and accurate coupled-cluster [CCSD(T)] reference values have been used instead. It is found that only triple-zeta quality AO basis sets provide results close enough to the basis set limit and that sets like the popular 6-31G(d) should be avoided in accurate work. Augmentation of small basis sets with diffuse functions has a notable effect in B3-LYP calculations that is attributed to intramolecular basis set superposition error and covers basic deficiencies of the functional. The new methods based on perturbation theory (SCS-MP2, X2-PLYP) are found to be clearly superior to many other approaches; that is, they provide mean absolute deviations of less than 1.2 kcal mol-1 and only a few (<10%) outliers. The best performance in the group of conventional functionals is found for the highly parametrized BMK hybrid meta-GGA. Contrary to accepted opinion, hybrid density functionals offer no real advantage over simple GGAs. For reasonably large AO basis sets, results of poor quality are obtained with the popular B3-LYP functional that cannot be recommended for thermochemical applications in organic chemistry. The results of this study are complementary to often used benchmarks based on atomization energies and should guide chemists in their search for accurate and efficient computational thermochemistry methods.
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ABSTRACT: Accurate barrier heights are obtained for the 26 pericyclic reactions in the BHPERI dataset by means of the high-level Wn-F12 thermochemical protocols. Very often, the complete basis set (CBS)-type composite methods are used in similar situations, but herein it is shown that they in fact result in surprisingly large errors with root mean square deviations (RMSDs) of about 2.5 kcal mol−1. In comparison, other composite methods, particularly G4-type and estimated coupled cluster with singles, doubles, and quasiperturbative triple excitations [CCSD(T)/CBS] approaches, show deviations well below the chemical-accuracy threshold of 1 kcal mol−1. With the exception of SCS-MP2 and the herein newly introduced MP3.5 approach, all other tested Møller-Plesset perturbative procedures give poor performance with RMSDs of up to 8.0 kcal mol−1. The finding that CBS-type methods fail for barrier heights of these reactions is unexpected and it is particularly troublesome given that they are often used to obtain reference values for benchmark studies. Significant differences are identified in the interpretation and final ranking of density functional theory (DFT) methods when using the original CBS-QB3 rather than the new Wn-F12 reference values for BHPERI. In particular, it is observed that the more accurate Wn-F12 benchmark results in lower statistical errors for those methods that are generally considered to be robust and accurate. Two examples are the PW6B95-D3(BJ) hybrid-meta-general-gradient approximation and the PWPB95-D3(BJ) double-hybrid functionals, which result in the lowest RMSDs of the entire DFT study (1.3 and 1.0 kcal mol−1, respectively). These results indicate that CBS-QB3 should be applied with caution in computational modeling and benchmark studies involving related systems.Journal of Computational Chemistry 02/2015; DOI:10.1002/jcc.23837
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ABSTRACT: The performances of two parametrized functionals (namely B3LYP and B2PYLP) have been compared with those of two non-parametrized functionals (PBE0 and PBE0-DH) on a relatively large benchmark set when three different types of dispersion corrections are applied [namely the D2, D3 and D3(BJ) models]. Globally, the MAD computed using non-parametrized functionals decreases when adding dispersion terms although the accuracy not necessarily increases with the complexity of the model of dispersion correction used. In particular, the D2 correction is found to improve the performances of both PBE0 and PBE0-DH, while no systematic improvement is observed going from D2 to D3 or D3(BJ) corrections. Indeed when including dispersion, the number of sets for which PBE0-DH is the best performing functional decreases at the benefit of B2PLYP. Overall, our results clearly show that inclusion of dispersion corrections is more beneficial to parametrized double-hybrid functionals than to non-parametrized ones. The same conclusions globally hold for the corresponding global hybrids, showing that the marriage between non-parametrized functionals and empirical corrections may be a difficult deal.Theoretical Chemistry Accounts 12/2014; 134(1). DOI:10.1007/s00214-014-1602-6
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ABSTRACT: We introduce a representative database of 60 accurate diene isomerization energies obtained by means of the high-level, ab initio Wn-F12 thermochemical protocols. The isomerization reactions involve a migration of one double bond that breaks the pi-conjugated system. The considered dienes involve a range of hydrocarbon functional groups, including linear, branched, and cyclic moieties. This set of benchmark isomerization energies allows an assessment of the performance of more approximate theoretical procedures for the calculation of pi-conjugation stabilization energies in dienes. We evaluate the performance of a large number of density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. We find that, with few exceptions (most notably BMK-D3 and M05-2X), conventional DFT procedures have difficulty describing reactions of the type: conjugated diene -> non-conjugated diene, with root mean square deviations (RMSDs) between 4.5 and 11.7 kJ mol (1). However, DHDFT procedures show excellent performance with RMSDs well below the 'chemical accuracy' threshold.Chemical Physics 09/2014; 441:166–177. DOI:10.1016/j.chemphys.2014.07.015