It is discussed that the Lowdin atomic populations (atomic populations computed in a Lowdin-orthogonalized basis) are invariant only under unitary transformations of the basis orbitals centered on the same atom, but not under the general rotationalhybridizational transformations as are the Mulliken populations. As a consequence, if basis sets containing 6 d-orbitals (or 10 f-orbitals, etc.) are used, then the Lowdin populations do not possess correct rotational invariance and equivalent atoms may be assigned different populations. Therefore, usual Lowdin populations are not appropriate tools of analysis if such basis sets are used. No such difficulty arises in the version proposed by Davidson, in which the basis orbitals belonging to the individual atoms are pre-orthogonalized; it, however, gives quite different results than the conventional scheme. (C) 2004 Elsevier B.V. All rights reserved.