Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

doi:10.1021/acs.jctc.5b00887

Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

2015-10-22

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DOI：10.1021/acs.jctc.5b00887

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We present a special symmetric Lanczos algorithm and a kernel polynomial method (KPM) for approximating the absorption spectrum of molecules within the linear response time-dependent density functional theory (TDDFT) framework in the product form. In contrast to existing algorithms, the new algorithms are based on reformulating the original non-Hermitian eigenvalue problem as a product eigenvalue problem and the observation that the product eigenvalue problem is self-adjoint with respect to an appropriately chosen inner product. This allows a simple symmetric Lanczos algorithm to be used to compute the desired absorption spectrum. The use of a symmetric Lanczos algorithm only requires half of the memory compared with the nonsymmetric variant of the Lanczos algorithm. The symmetric Lanczos algorithm is also numerically more stable than the nonsymmetric version. The KPM algorithm is also presented as a low-memory alternative to the Lanczos approach, but the algorithm may require more matrix-vector multiplications in practice. We discuss the pros and cons of these methods in terms of their accuracy as well as their computational and storage cost. Applications to a set of small and medium-sized molecules are also presented.

Keywords:

DENSITY-FUNCTIONAL THEORY

HARTREE-FOCK

MINIMIZATION PRINCIPLES

LARGE MOLECULES

BASIS-SETS

EQUATIONS

KERNEL

ENERGIES

EXCHANGE

STATES

Efficient Algorithms for Estimating the Absorption Spectrum within Linear Response TDDFT

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