title: Linear-scaling implementation of molecular response theory in self-consistent field electronic-structure theory.
abstract: A linear-scaling implementation of Hartree-Fock and Kohn-Sham self-consistent field theories for the calculation of frequency-dependent molecular response properties and excitation energies is presented, based on a nonredundant exponential parametrization of the one-electron density matrix in the atomic-orbital basis, avoiding the use of canonical orbitals. The response equations are solved iteratively, by an atomic-orbital subspace method equivalent to that of molecular-orbital theory. Important features of the subspace method are the use of paired trial vectors (to preserve the algebraic structure of the response equations), a nondiagonal preconditioner (for rapid convergence), and the generation of good initial guesses (for robust solution). As a result, the performance of the iterative method is the same as in canonical molecular-orbital theory, with five to ten iterations needed for convergence. As in traditional direct Hartree-Fock and Kohn-Sham theories, the calculations are dominated by the construction of the effective Fock/Kohn-Sham matrix, once in each iteration. Linear complexity is achieved by using sparse-matrix algebra, as illustrated in calculations of excitation energies and frequency-dependent polarizabilities of polyalanine peptides containing up to 1400 atoms.
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Trieste, Via Licio Giorgieri 1, I-34127 Trieste, Italy.
authors.forename: Sonia
authors.initials: S
authors.lastname: Coriani
authors.forename: Stinne
authors.initials: S
authors.lastname: Høst
authors.forename: Branislav
authors.initials: B
authors.lastname: Jansík
authors.forename: Lea
authors.initials: L
authors.lastname: Thøgersen
authors.forename: Jeppe
authors.initials: J
authors.lastname: Olsen
authors.forename: Poul
authors.initials: P
authors.lastname: Jørgensen
authors.forename: Simen
authors.initials: S
authors.lastname: Reine
authors.forename: Filip
authors.initials: F
authors.lastname: Pawłowski
authors.forename: Trygve
authors.initials: T
authors.lastname: Helgaker
authors.forename: Paweł
authors.initials: P
authors.lastname: Sałek