Accelerated Broadband Spectra Using Transition Dipole Decomposition and Padé Approximants

We present a method for accelerating the computation of UV–visible and X-ray absorption spectra in large molecular systems using real-time time-dependent density functional theory (TDDFT). This approach is based on deconvolution of the dipole into molecular orbital dipole pairs developed by Repisky,...

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Bibliographic Details
Published in:Journal of chemical theory and computation 2016-08, Vol.12 (8), p.3741-3750
Main Authors: Bruner, Adam, LaMaster, Daniel, Lopata, Kenneth
Format: Article
Language:English
Subjects:
Approximants
Broadband
Computation
Computer simulation
Dipoles
Molecular orbitals
Nickel
Real time
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Summary:We present a method for accelerating the computation of UV–visible and X-ray absorption spectra in large molecular systems using real-time time-dependent density functional theory (TDDFT). This approach is based on deconvolution of the dipole into molecular orbital dipole pairs developed by Repisky, et al. [Repisky et al., J. Chem. Theory Comput. 2015, 11, 980–911] followed by Padé approximants to their Fourier transforms. By combining these two techniques, the required simulation time is reduced by a factor of 5 or more, and moreover, the transition dipoles yield the molecular orbital contributions to each transition, akin to the coefficients in linear-response TDDFT. We validate this method on valence and core-level spectra of gas-phase water and nickel porphyrin, where the results are essentially equivalent to conventional linear response. This approach makes real-time TDDFT competitive against linear response for large molecular and material systems with a high density of states.
ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.6b00511