Coupled-cluster with active space selected higher amplitudes: Performance of seminatural orbitals for ground and excited state calculations

Andreas Köhn, Jeppe Olsen
2006 Journal of Chemical Physics  
The active space approach for coupled-cluster models is generalized using the general active space concept and implemented in a string-based general coupled-cluster code. Particular attention is devoted to the choice of orbitals on which the subspace division is based. Seminatural orbitals are proposed for that purpose. These orbitals are obtained by diagonalizing only the hole-hole and particle-particle block of the one-electron density of a lower-order method. The seminatural orbitals are
more » ... al orbitals are shown to be a good replacement for complete active space self-consistent field orbitals and avoid the ambiguities with respect to the reference determinant introduced by the latter orbitals. The seminatural orbitals also perform well in excited state calculations, including excited states with strong double excitation contributions, which usually are difficult to describe with standard coupled-cluster methods. A set of vertical excitation energies is obtained and benchmarked against full configuration interaction calculations, and alternative hierarchies of active space coupled-cluster models are proposed. As a simple application the spectroscopic constants of the C 2 B 1 ⌬ g and BЈ 1 ⌺ g + states are calculated using active space coupled-cluster methods and basis sets up to quadruple-zeta quality in connection with extrapolation and additivity schemes.
doi:10.1063/1.2364491 pmid:17100432 fatcat:4j4yy6grpvcxra2lcadbalj5ta