Multipole Traceless Forms

Traceless forms of the higher multipole operators have been given by Buckingham.12 Much of the work reviewed will refer to the case of a spatially uniform applied field, when the perturbed hamiltonian reduces to... 

Laplace s equation, V V = 0, means that the number of unique elements needed to evaluate an interaction energy can be reduced. For the second moment this amounts to a transformation into a traceless tensor form, a form usually referred to as the quadrupole moment [5]. Transformations for higher moments can be accomplished with the conditions that develop from further differentiation of Laplace s equation. With modern computation machinery, such reduction tends to be of less benefit, and on vector machines, it may be less efficient in certain steps. We shall not make that transformation and instead will use traced Cartesian moments. It is still appropriate, however, to refer to quadrupoles or octupoles rather than to second or third moments since for interaction energies there is no difference. Logan has pointed out the convenience and utility of a Cartesian form of the multipole polarizabilities [6], and in most cases, that is how the properties are expressed here. 

Tables III-XVII give calculated permanent moments. Selected comparisons with experimental values or calculations of others are also listed. All values are in atomic units, and traceless rather than Cartesian forms are distinguished with Greek letters, 6 (quadrupole) and G (octupole). Coordinates for the atomic centers are listed. These specify the geometry used, which were equilibrium geometries, and implicitly the multipole expansion center (x = 0, y = 0, z = 0). The moments are given at both the SCF level and at the well-correlated level of coupled-cluster theory [95-102]. ACCD [103-106] was the particular coupled-cluster approach, and the moments were evaluated by expectation [102] with the cluster expansion truncated at single and double substitutions.

In the static case, electric multipoles are often redefined to give forms that are traceless on any two indices. In this manner, the above restrictions (154) can be incorporated [49]. The general form of such traceless multipole operators is... 

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