Addition/Correction pubs.acs.org/JPCA
Cite This: J. Phys. Chem. A 2018, 122, 9585−9586
Correction to “Testing Semiempirical QM Methods on a Data Set of Interaction Energies Mapping Repulsive Contacts in Organic Molecules” V. M. Miriyala and J. Ř ezác*̌ J. Phys. Chem. A 2018, 122 (10), 2801−2808. DOI: 10.1021/acs.jpca.8b00260
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S Supporting Information *
Table 1. RMSE, MSE, and MUE in kcal/mol for Various SQM Methods Tested on the R160 × 6 Benchmark Dataset and RMSE in kcal/mol for the S66 × 8 Benchmark Dataset
We have discovered an error in the processing of the benchmark CCSD(T) calculations reported in the paper. It affected all the points in the data set, with the average difference between the published and correct values being 0.47 kcal/mol. We sincerely apologize to the readers and to the users of our benchmark data. Here, we provide the corrected benchmark values and recalculated results based on them. Because the error in the benchmark results was smaller than errors of the semiempirical QM methods tested in the paper (which are typically in the range 1.5− 2.0 kcal/mol), the conclusions of the paper do not change at all. Overall, the new benchmark interaction energies are slightly more repulsive, so that the underestimation of the repulsion in the semiempirical methods discussed in the paper is only somewhat more pronounced. PM6-D3H4′ remains the best-performing dispersioncorrected SQM method among the methods tested. Even with the updated benchmark, it is still not possible to parametrize a simple repulsive correction that would be transferable to geometries closer to the equilibrium. Therefore, to minimize the extent of the errata, the results reported here were obtained using the original parametrization. Below, we provide the corrected benchmark values (which were verified to be corresponding to the originally published geometries), and all the tables and plots from the paper updated with the recalculated values. A corrected Table S4 is provided as Supporting Information.
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method
RMSE
MSE
MUE
RMSE (S66 × 8)
BLYP-D3 PBE-D3 MNDO AM1 RM1 PM6 PM6-D3H4 PM6-D3H4′ PM7 OM2 OM2-D3 OM3 OM3-D3 OM3-D3H4 DFTB DFTB-D DFTB3 DFTB3-D3H4 GFN-xTB PM6-D3H4R DFTB3-D3H4R
0.36 0.61 4.83 1.44 1.62 1.82 2.04 1.56 1.85 1.81 2.28 1.52 2.14 1.91 1.74 1.99 1.32 1.88 1.91 1.36 1.24
−0.02 −0.43 3.42 −0.09 −0.37 −0.75 −1.20 −0.68 −1.07 −0.93 −1.57 −0.63 −1.46 −1.26 −1.14 −1.50 −0.61 −1.36 −1.32 −0.24 −0.42
0.26 0.45 3.45 1.02 1.17 1.24 1.38 1.10 1.31 1.32 1.68 1.10 1.57 1.38 1.36 1.60 1.01 1.46 1.43 0.96 0.92
0.22 0.47 13.08 5.27 4.38 2.50 0.66 0.66 0.95 2.32 1.19 2.70 2.48 0.60 2.68 1.78 2.93 0.93 1.06 1.63 3.04
CORRECTIONS TO THE DISCUSSION OF THE RESULTS
(1) Additionally, we provide notes on the few statements in the text of the original paper that change with the new data:Page 2804, third paragraph of section “Performance of SQM Methods”: We’ve discussed the errors of DFT-D3, pointing out a surprising positive systematic error of the B-LYP-D3(BJ) setup. This systematic error (MSE) is now practically zero (−0.02 kcal/mol), and RMSE dropped from 0.94 to 0.36 kcal/mol. For PBE-D3, the systematic error increased from −0.11 to −0.43 kcal/mol, which is in agreement with previous evidence showing that this functional underestimates the repulsion. (2) Page 2805, fourth paragraph: Now, AM1 (instead of RM1) is the SQM method exhibiting the smallest systematic error in the data set. © 2018 American Chemical Society
Published: December 3, 2018 9585
DOI: 10.1021/acs.jpca.8b11266 J. Phys. Chem. A 2018, 122, 9585−9586
The Journal of Physical Chemistry A
Addition/Correction
Table 2. Heat Map of MSE in kcal/mol for Different SQM Methods Tested over the R160 × 6 Benchmark Dataseta
a
The color scheme is blue for minimum value, white for zero, and red for maximum value.
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CORRECTED TABLES AND FIGURES
ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpca.8b11266. Corrected benchmark interaction energies (Table S4) (PDF)
Figure 2. Plot of RMSE error (kcal/mol) for various SQM methods tested on the R160 × 6 benchmark data set.
Figure 3. Plot of RMSE error (kcal/mol) of different element pairs for SQM variants of PM6 tested on the R160 × 6 benchmark data set.
9586
DOI: 10.1021/acs.jpca.8b11266 J. Phys. Chem. A 2018, 122, 9585−9586
