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Published October 15, 2020 | Supplemental Material + Accepted Version
Journal Article Open

Ground State Electronic Energy of Benzene


We report on the findings of a blind challenge devoted to determining the frozen-core, full configuration interaction (FCI) ground-state energy of the benzene molecule in a standard correlation-consistent basis set of double-ζ quality. As a broad international endeavor, our suite of wave function-based correlation methods collectively represents a diverse view of the high-accuracy repertoire offered by modern electronic structure theory. In our assessment, the evaluated high-level methods are all found to qualitatively agree on a final correlation energy, with most methods yielding an estimate of the FCI value around −863 mE_H. However, we find the root-mean-square deviation of the energies from the studied methods to be considerable (1.3 mE_H), which in light of the acclaimed performance of each of the methods for smaller molecular systems clearly displays the challenges faced in extending reliable, near-exact correlation methods to larger systems. While the discrepancies exposed by our study thus emphasize the fact that the current state-of-the-art approaches leave room for improvement, we still expect the present assessment to provide a valuable community resource for benchmark and calibration purposes going forward.

Additional Information

© 2020 American Chemical Society. Received: August 27, 2020; Accepted: September 25, 2020; Published: October 6, 2020. The authors thank Dr. Devin A. Matthews of the Southern Methodist University for help with obtaining the CCSDTQ result first reported in ref (92). J.J.E. is grateful to the Alexander von Humboldt Foundation and the Independent Research Fund Denmark for financial support. J.J.E. and J.G. gratefully acknowledge access awarded to the Galileo supercomputer at CINECA (Italy) through the 18th PRACE Project Access Call and the Johannes Gutenberg-Universität Mainz for computing time granted on the Mogon II supercomputer. D.H. and M.H.-G. were supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. P.P. and members of his group, J.E.D., I.M., and J.S., acknowledge support by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U.S. Department of Energy (Grant No. DE-FG02-01ER15228 to P.P.). N.Z. and W.L. acknowledge support from the National Natural Science Foundation of China (Grant Nos. 21033001 and 21973054). S.L. and G.K.-L.C. were supported by the U.S. National Science Foundation, via Grant No. 1665333. E.X. and S.L.T. acknowledge the financial support from the Japan Society for the Promotion of Science, Grant-in-Aids for Scientific Research (A) (Grant No. JP18H03900). M.R.H. acknowledges the North Dakota University System. S.S. was supported by the U.S. National Science Foundation Grant CHE-1800584 and by the Sloan research fellowship. T.A.A. and C.J.U. were supported in part by the U.S. Air Force Office of Scientific Research under Grant FA9550-18-1-0095. J.E.D. and Y.Y. acknowledge support from the Molecular Sciences Software Institute, funded by U.S. National Science Foundation Grant ACI-1547580. Some of the SHCI computations were performed at the Bridges cluster at the Pittsburgh Supercomputing Center supported by U.S. National Science Foundation Grant ACI-1445606. A.A. and K.G. thank the NECI developer team and the Max Planck Computing and Data Facility for their continuing work on the NECI code. The authors declare no competing financial interest.

Attached Files

Accepted Version - 2008.02678.pdf

Supplemental Material - jz0c02621_si_001.pdf


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