Augmented Lagrangian Method for Order-N Electronic Structure
Science Direct Working Paper No S1574-0331(04)70428-2
4 Pages Posted: 31 May 2017 Last revised: 16 Dec 2017
Date Written: February 2001
Molecular electronic ground state theories, whether ab initio, or semi-empirical are most often formulated as a variational principle, where the electronic ground state energy, considered a linear or non-linear functional of a reduced density matrix, obtains a constrained minimum. In this letter, 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.
Keywords: Physical Chemistry > Computational Chemistry, physchem/0102005 Chemistry > Environmental Chemistry
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