화학공학소재연구정보센터
Chemical Physics Letters, Vol.338, No.4-6, 375-384, 2001
Size-consistent wave functions for bond-breaking: the equation-of-motion spin-flip model
A new approach to the bond-breaking problem is proposed. Both closed and open shell singlet states are described within a single reference formalism as spin-flipping, e.g., alpha --> beta, excitations from a triplet (M-s = 1) reference state for which both dynamical and non-dynamical correlation effects are much smaller than for the corresponding singlet state. Formally, the new theory can be viewed as an equation-of-motion (EOM) model where excited states are sought in the basis of determinants conserving the total number of electrons but changing the number of alpha and beta electrons. The results for two simplest members of the proposed hierarchy of approximations are presented.