ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Molecular electronic ground-state theories, whether ab initio, or semiempirical are most often formulated as a variational principle, where the electronic ground-state energy, considered a linear or nonlinear functional of a reduced density matrix, obtains a constrained minimum. In this communication, we present a Lagrangian analysis of the self-consistent-field electronic structure problem, which does not resort to the concept of orthogonal molecular orbitals. We also develop a method of constrained minimization efficiently applicable to nonlinear energy functional minimization, as well as to linear models such as tight-binding. The method is able to treat large molecules with an effort that scales linearly with the system size. It has built-in robustness and leads directly to the desired minimal solution. Performance is demonstrated on linear alkane and polyene chains. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1383590
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