title: Multiresolution quantum chemistry in multiwavelet bases: excited states from time-dependent Hartree-Fock and density functional theory via linear response.
abstract: A fully numerical method for the time-dependent Hartree-Fock and density functional theory (TD-HF/DFT) with the Tamm-Dancoff (TD) approximation is presented in a multiresolution analysis (MRA) approach. From a reformulation with effective use of the density matrix operator, we obtain a general form of the HF/DFT linear response equation in the first quantization formalism. It can be readily rewritten as an integral equation with the bound-state Helmholtz (BSH) kernel for the Green's function. The MRA implementation of the resultant equation permits excited state calculations without virtual orbitals. The integral equation is efficiently and adaptively solved using a numerical multiresolution solver with multiwavelet bases. Our implementation of the TD-HF/DFT methods is applied for calculating the excitation energies of H2, Be, N2, H2O, and C2H4 molecules. The numerical errors of the calculated excitation energies converge in proportion to the residuals of the equation in the molecular orbitals and response functions. The energies of the excited states at a variety of length scales ranging from short-range valence excitations to long-range Rydberg-type ones are consistently accurate. It is shown that the multiresolution calculations yield the correct exponential asymptotic tails for the response functions, whereas those computed with Gaussian basis functions are too diffuse or decay too rapidly. We introduce a simple asymptotic correction to the local spin-density approximation (LSDA) so that in the TDDFT calculations, the excited states are correctly bound.
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki, Aichi 444-8585, Japan. yanait@ims.ac.jp.
authors.forename: Takeshi
authors.initials: T
authors.lastname: Yanai
authors.affiliation: Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
authors.forename: George I
authors.initials: GI
authors.lastname: Fann
authors.affiliation: Department of Applied Mathematics, University of Colorado at Boulder, 526 UCB, Boulder, CO 80309-0526, USA.
authors.forename: Gregory
authors.initials: G
authors.lastname: Beylkin
authors.affiliation: Institute for Advanced Computational Science, Stony Brook University, Stony Brook, New York 11794, USA. Robert.Harrison@stonybrook.edu and Computational Science Center, Brookhaven National Laboratory, Upton, New York 11973, USA.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Harrison