Multiconfigurational second‐order perturbation theory: A test of geometries and binding energies

Abstract Multiconfigurational second‐order perturbation theory is tested for the calculation of molecular structure and binding energies. The scheme is based on the Complete Active Space ( CAS ) SCF method, which gives a proper description of the major features in the electronic structure, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic electron correlation effects are in a subsequent step added using second‐order perturbation theory with the CASSCF wave function as the reference state ( CASPT 2). The approach is applied to the calculation of equilibrium geometry and atomization energies for 27 benchmark molecules containing first‐row atoms (the “G1” test). Large atomic natural orbital ( ANO )‐type basis sets are applied (5 s 4 p 3 d 2 f for LiF and 3 s 2 p 1 d for H). It is shown that the CASSCF / CASPT 2 approach is able to predict the equilibrium geometry with an accuracy better than 0.01 Å for bond distances and 0°–2° for bond angles. Calculated atomization energies are underestimated with between 3 and 6 kcal/mol times the number of extra electron pairs formed. The error in the heat of reaction for a number of isogyric reaction (no difference in number of pairs) varies between −2.5 and +1.0 kcal/mol. The same type of accuracy is obtained in calculations for excited states. The molecules B 2 , C 2 , FO, FOO, and FOOF have also been studied. Results for the first three molecules are in accordance with those of the benchmark molecules. The FO bond distance in FOO is predicted to be 0.02 Å longer than experiment. The heat of formation for FOO is computed to be 2.9 kcal/mol with an uncertainty of ±3 kcal/mol. Preliminary results for FOOF (obtained with a smaller basis set) indicate that the approach yields a somewhat too long FO bond distance (1.64 Å compared to 1.58 Å experimentally). © 1993 John Wiley & Sons, Inc.