On Achieving High Accuracy in Quantum Chemical Calculations of 3 d Transition Metal-Containing Systems: A Comparison of Auxiliary-Field Quantum Monte Carlo with Coupled Cluster, Density Functional Theory, and Experiment for Diatomic Molecules
[1];
[1];
- Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, United States
- Schrodinger Inc., 120 West 45th Street, New York, New York 10036, United States
- Center for Computational Quantum Physics, Flatiron Institute, 162 5th Avenue, New York, New York 10010, United States; Department of Physics, College of William and Mary, Williamsburg, Virginia 23187, United States
According to the article, the bond dissociation energies of a set of 44 3d transition metal-containing diatomics are computed with phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) utilizing a correlated sampling technique. We investigate molecules with H, N, O, F, Cl, and S ligands, including those in the 3dMLBE20 database first compiled by Truhlar and co-workers with calculated and experimental values that have since been revised by various groups. In order to make a direct comparison of the accuracy of our ph-AFQMC calculations with previously published results from 10 DFT functionals, CCSD(T), and icMR-CCSD(T), we establish an objective selection protocol which utilizes the most recent experimental results except for a few cases with well-specified discrepancies. With the remaining set of 41 molecules, we find that ph-AFQMC gives robust agreement with experiment superior to that of all other methods, with a mean absolute error (MAE) of 1.4(4) kcal/mol and maximum error of 3(3) kcal/mol (parentheses account for reported experimental uncertainties and the statistical errors of our ph-AFQMC calculations). In comparison, CCSD(T) and B97, the best performing DFT functional considered here, have MAEs of 2.8 and 3.7 kcal/mol, respectively, and maximum errors in excess of 17 kcal/mol (for the CoS diatomic). While a larger and more diverse data set would be required to demonstrate that ph-AFQMC is truly a benchmark method for transition metal systems, our results indicate that the method has tremendous potential, exhibiting unprecedented consistency and accuracy compared to other approximate quantum chemical approaches.
- Research Organization:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC/ORNL, Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); College of William and Mary, Williamsburg, VA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC)
- DOE Contract Number:
- AC05-00OR22725; SC0012704; SC0001303
- OSTI ID:
- 1565744
- Journal Information:
- Journal of Chemical Theory and Computation, Vol. 15, Issue 4; ISSN 1549-9618
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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