A set of standard enthalpies of formation for benchmarking, calibration, and parametrization of electronic structure methods

A comprehensive set of 600 experimental standard enthalpies of formation (D eltaH(f)(0)) is presented. With its diverse species, many possessing less u sual geometries and bonding situations, this compilation is capable of unco vering deficiencies in approaches of quantum chemistry that are not detecta ble with smaller sets of DeltaH(f)(0) values. Its usefulness in benchmarkin g, calibration, and parametrization of new electronic structure methods is illustrated with the development of the B3LYP/6-311++G** bond density funct ional scheme. This scheme, which is sufficiently inexpensive in terms of co mputer time and memory to allow predictions even for molecules as large as the C-60 fullerene, requires only single point calculations at optimized ge ometries. It yields values of DeltaH(f)(0) with the average absolute error of 3.3 kcal/mol, rivaling more expensive methods in accuracy (especially fo r larger systems). A list of species that are poorly handled by a typical h ybrid density functional used in conjunction with a moderate-size basis set is given. This list is intended for rigorous testing of new density functi onals. (C) 2000 American Institute of Physics. [S0021-9606(00)30345-2].