Journal of Physical Chemistry A, Vol.114, No.6, 2344-2349, 2010
Relationships between Cumulant and Spin-Density Matrices: Application to the Decomposition of Spin
This paper reports the derivation of a relationship between some elements of the cumulant matrix of the second-order reduced density matrix and the elements of the spin-density matrix. This relationship turns out to be very useful to determine local spins through the partitioning of the spin expectation value < S-boolean AND 2 > of an N-electron system. The procedure enables expression of both one- and two-center contributions only in terms of one-electron matrix elements, the elements of the spin-density matrix. We report numerical determinations of local spins in the Hilbert space of atomic orbitals in selected molecules and radicals in triplet and doublet states.