Multireference perturbation theory with optimized partitioning. II. Applications to molecular systems

The second‐order multireference perturbation theory using an optimized partitioning, denoted as MROPT(2), is applied to calculations of various molecular properties—excitation energies, spectroscopic parameters, and potential energy curves—for five molecules: ethylene, butadiene, benzene, N₂, and O₂. The calculated results are compared with those obtained with second‐ and third‐order multireference perturbation theory using the traditional partitioning techniques. We also give results from computations using the multireference configuration interaction (MRCI) method. The presented results show very close resemblance between the new method and MRCI with renormalized Davidson correction. The accuracy of the new method is good and is comparable to that of second‐order multireference perturbation theory using Møller‐Plesset partitioning. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1390–1400, 2003