Ta. Keith et al., STRUCTURAL HOMEOMORPHISM BETWEEN THE ELECTRON-DENSITY AND THE VIRIAL FIELD, International journal of quantum chemistry, 57(2), 1996, pp. 183-198
The virial field V(r) is defined by the local statement of the quantum
mechanical virial theorem, as the trace of the Schrodinger stress ten
ser. This field defines the electronic potential energy density of an
electron at r and integrates to minus twice the electronic kinetic ene
rgy. It is the most short-ranged description possible of the local ele
ctronic potential energy and it exhibits the same transferable behavio
r over bounded regions of real space (corresponding to the functional
groups of chemistry) as does rho(r). This article establishes a struct
ural homeomorphism between - V(r) and rho(r), showing that the two fie
lds are homeomorphic over all of the nuclear configuration space. The
stable or unstable structure defined by the gradient vector field del
rho(r; chi) for any configuration chi of the nuclei can be placed in a
one-to-one correspondence with a structure defined by the field - del
V(r; chi'). In particular, a molecular graph for rho(r) defining a mo
lecular structure is mirrored by a corresponding virial graph for V(r)
and the lines of maximum density linking bonded nuclei in the former
field are matched by a set of lines of maximally negative potential en
ergy density in the latter. The homeomorphism is also geometrically fa
ithful, an equilibrium geometry in general, exhibiting equivalent stru
ctures in the two fields. The demonstration that the virial field, who
se integrated value equals twice the total energy, is essentially just
a locally scaled version of the electron density is suggestive of pos
sible new approaches in density functional theory. (C) 1996 John Wiley
& Sons, Inc.