GRADIENT THEORY APPLIED TO THE BRUECKNER DOUBLES METHOD

The Brueckner doubles variant of coupled cluster theory has recently been reintroduced by the authors. The use of Brueckner orbitals means that the governing equations for T2 take a particularly simple form. Here we give the details for the evaluation of the gradient of the Brueckner doubles energy for (a) the unrestricted spin-orbital formalism and (b) the closed-shell restricted formalism. Applications are presented for H2O, NH3, CH4, H2CO, C2H2, HCN, and CO2 and comparisons are made with the Hartree-Fock, second order Moller-Plesset and quadratic configuration interaction models and with experiment.