Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 155, Issue 18, Pages -Publisher
AIP Publishing
DOI: 10.1063/5.0069322
Keywords
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Funding
- U.S. Department of Energy, Basic Energy Science [DE-SC0018164]
- NSF [AST-1908576]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences through the Computational Chemical Sciences Program [DE-AC02-06CH11357]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences through the Gas-Phase Chemical Physics Program [DE-AC02-06CH11357]
- U.S. Department of Energy (DOE) [DE-SC0018164] Funding Source: U.S. Department of Energy (DOE)
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This study establishes empirical, highly accurate non-relativistic electronic total atomization energies and analyzes the performance of high-level ab initio quantum chemical calculations and the HEAT family of theoretical methods. The results show that the HEAT-345(Q) method benefits from fortuitous error cancellation and lays the foundation for extended HEAT variants with substantial improvements in accuracy.
Empirical, highly accurate non-relativistic electronic total atomization energies (eTAEs) are established by combining experimental or computationally converged treatments of the nuclear motion and relativistic contributions with the total atomization energies of HF, CO, N-2, and H2O obtained from the Active Thermochemical Tables. These eTAEs, which have estimated (2 sigma) uncertainties of less than 10 cm(-1) (0.12 kJ mol(-1)), form the basis for an analysis of high-level ab initio quantum chemical calculations that aim at reproducing these eTAEs for the title molecules. The results are then employed to analyze the performance of the high-accuracy extrapolated ab initio thermochemistry, or High-Accuracy Extrapolated Ab Initio Thermochemistry (HEAT), family of theoretical methods. The method known as HEAT-345(Q), in particular, is found to benefit from fortuitous error cancellation between its treatment of the zero-point energy, extrapolation errors in the Hartree-Fock and coupled cluster contributions, neglect of post-(T) core-correlation, and the basis-set error involved in higher-level correlation corrections. In addition to shedding light on a longstanding curiosity of the HEAT protocol-where the cheapest HEAT-345(Q) performs comparably to the theoretically more complete HEAT-456QP procedure-this study lays the foundation for extended HEAT variants that offer substantial improvements in accuracy relative to the established approaches.
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