The recently developed high-accuracy extrapolated ab initio thermochemistry method for theoretical thermochemistry, which is intimately related to other high-precision protocols such as the Weizmann-3 and focal-point approaches, is revisited. Some minor improvements in theoretical rigor are introduced which do not lead to any significant additional computational overhead, but are shown to have a negligible overall effect on the accuracy. In addition, the method is extended to completely treat electron correlation effects up to pentuple excitations. The use of an approximate treatment of quadruple and pentuple excitations is suggested; the former as a pragmatic approximation for standard cases and the latter when extremely high accuracy is required. For a test suite of molecules that have rather precisely known enthalpies of formation {as taken from the active thermochemical tables of Ruscic and co-workers [Lecture Notes in Computer Science, edited by M. Parashar (Springer, Berlin, 2002), Vol. 2536, pp. 25–38; J. Phys. Chem. A 108, 9979 (2004)]}, the largest deviations between theory and experiment are 0.52, −0.70, and 0.51kJmol−1 for the latter three methods, respectively. Some perspective is provided on this level of accuracy, and sources of remaining systematic deficiencies in the approaches are discussed.

High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification