ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The shape wave u(r) is defined in such a way that the square of its absolute value gives the shape of the electron charge density for a nonrelativistic many-electron system: |u(r)|2 = ρ(r)/∫ρ(r) dr, where ρ(r) is the total electron charge density. The u(r) is treated as the probability amplitude for the shape of the electron charge density in the real three-dimensional space. The secular equation of the u(r) is given as L(r)u(r) = λu(r), where L(r) and λ are a real Hermitean operator and the eigenvalue, respectively. This equation has the form of the spinless one-particle Schrödinger equation. The potential is local and is a functional of ρ(r), and so we need a self-consistent field procedure to solve it. For equilibrium state shape wave u = ueq, which is temperature-dependent, and for stationary state shape wave u = u0, respectively, Leq(r)ueq(r) = λequeq(r) and L0(r)u0(r) = λ0u0(r). For one-electron systems, the latter equation reduces to the Schrödinger equation for a stationary state, with the usual eigenvalue λ0 = E0. In general, λ is identified with the Gibbs chemical potential μG. Boundary conditions such as the cusp condition at a nucleus and exponential decay at an infinitely large distance from the nucleus are easily implemented. In case L(r) allows complex eigenfunctions, u(r) = A(r)eiS(r), the hydrodynamical potential appears in the secular equation for the real amplitude A(r). The real phase S(r) satisfies the equation of continuity. By introducing «apparatus» operators [16], the excited state shape wave is also obtained. Comparisons are made with a recent discussion of Levy, Perdew, and Sahni [3].
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560340402
