Block Effective Hamiltonian Theory and Its Application.

Abstract

Block effective Hamiltonian theory (BEHT) is presented in this work. Configuration interaction functions are divided into P, Q, and R spaces. Effective Hamiltonian is constructed with the partitioning technique within the P space. The eigenvalue problem of the effective Hamiltonian is then solved iteratively. It is demonstrated that the ground-state energies of N2, HF, and F2 calculated with BEHT converge to the multireference configuration interaction energies from below and the iteration number becomes smaller as BEHT energy becomes closer to the exact energy. The accuracy of BEHT is better than that of the second-order multireference perturbation theory, although the matrix elements in both methods are the same. The ionization potentials of the singlet state of HF, the doublet state of F, and the triplet state of NH and the potential energy curves of CH4, C2, and N2 are calculated with BEHT and compared with experiments and results of CASSCF, CCSD, and CCSD(T) and the results of the full configuration interaction if available. The iteration numbers are all less than 10 in this study. These calculations show the good performances of BEHT in comparison with other theoretical approximation methods.