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Title: Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

We present two iterative algorithms for approximating the absorption spectrum of molecules within linear response of time-dependent density functional theory (TDDFT) framework. These methods do not attempt to compute eigenvalues or eigenvectors of the linear response matrix. They are designed to approximate the absorption spectrum as a function directly. They take advantage of the special structure of the linear response matrix. Neither method requires the linear response matrix to be constructed explicitly. They only require a procedure that performs the multiplication of the linear response matrix with a vector. These methods can also be easily modified to efficiently estimate the density of states (DOS) of the linear response matrix without computing the eigenvalues of this matrix. We show by computational experiments that the methods proposed in this paper can be much more efficient than methods that are based on the exact diagonalization of the linear response matrix. We show that they can also be more efficient than real-time TDDFT simulations. We compare the pros and cons of these methods in terms of their accuracy as well as their computational and storage cost.
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Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1549-9618; 48614; KC0301020
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Theory and Computation; Journal Volume: 11; Journal Issue: 11
American Chemical Society
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
Absorption; spectrum; linear response; time-dependent density functional theory; Environmental Molecular Sciences Laboratory