Unitary group approach to spin‐adapted open‐shell coupled cluster theory

Abstract

AbstractWe show that the irreducible tensor operators of the unitary group provide a natural operator basis for the exponential Ansatz which preserves the spin symmetry of the reference state, requires a minimal number of independent cluster amplitudes for each substitution order, and guarantees the invariance of the correlation energy under unitary transformations of core, open‐shell, and virtual orbitals. When acting on the closed‐shell reference state with nc doubly occupied and nv unoccupied (virtual) orbitals, the irreducible tensor operators of the group U(nc) ⊗ U(nV) generate all Gelfand‐Tsetlin (GT) states corresponding to appropriate irreducible representation of U(nc + nv). The tensor operators generating the M‐tuply excited states are easily constructed by symmetrizing products of M unitary group generators with the Wigner operators of the symmetric group SM. This provides an alternative to the Nagel‐Moshinsky construction of the GT basis. Since the corresponding cluster amplitudes, which are also U(nc) ⊗ U(ns) tensors, can be shown to be connected, the irreducible tensor operators of U(nc) ⊗ U(nv) represent a convenient basis for a spin‐adapted full coupled cluster calculation for closed‐shell systems. For a high‐spin reference determinant with n, singly occupied open‐shell orbitals, the corresponding representation of U(n), n=nc + nv + ns is not simply reducible under the group U(nc) ⊗ U(ns) ⊗ U(nv). The multiplicity problem is resolved using the group chain U(n) ⊃ U(nc + nv) ⊗ U(ns) ⊃ U(nc) ⊗U(ns)⊗ U(nv) ⊗ U(nv). The labeling of the resulting configuration‐state functions (which, in general, are not GT states when nc > 1) by the irreducible representations of the intermediate group U(nc + nv) ⊗U(ns) turns out to be equivalent to the classification based on the order of interaction with the reference state. The irreducible tensor operators defined by the above chain and corresponding to single, double, and triple substitutions from the first‐, second‐, and third‐order interacting spaces are explicitly constructed from the U(n) generators. The connectedness of the corresponding cluster amplitudes and, consequently, the size extensivity of the resulting spin‐adapted open‐shell coupled cluster theory are proved using group theoretical arguments. The perturbation expansion of the resulting coupled cluster equations leads to an explicitly connected form of the spin‐restricted open‐shell many‐body perturbation theory. Approximation schemes leading to manageable computational procedures are proposed and their relation to perturbation theory is discussed. © 1995 John Wiley & Sons, Inc.