Assessment of density matrix methods for linear scaling electronic structure calculations

Purification and minimization methods for linear scaling computation of the one-particle density matrix for a fixed Hamiltonian matrix are compared. This is done by considering the work needed by each method to achieve a given accuracy in terms of the difference from the exact solution. Numerical tests employing orthogonal as well as non-orthogonal versions of the methods are performed using both element magnitude and cutoff radius based truncation approaches. It is investigated how the convergence speed for the different methods depends on the eigenvalue distribution in the Hamiltonian matrix. An expression for the number of iterations required for the minimization methods studied is derived, taking into account the dependence on both the band gap and the chemical potential. This expression is confirmed by numerical tests. The minimization methods are found to perform at their best when the chemical potential is located near the center of the eigenspectrum. The results indicate that purification is considerably more efficient than the minimization methods studied even when a good starting guess for the minimization is available. In test calculations without a starting guess, purification is more than an order of magnitude more efficient than minimization.

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