Combined Density Functional and Algebraic-Diagrammatic Construction Approach for Accurate Excitation Energies and Transition Moments

Dávid Mester, M. Kállay

Research output: Contribution to journalArticle

Abstract

A composite of time-dependent density functional theory (TDDFT) and the second-order algebraic-diagrammatic construction [ADC(2)] approach is presented for efficient calculation of spectral properties of molecules. Our method can be regarded as a new excited-state double-hybrid (DH) approach or a dressed TDDFT scheme, but it can also be interpreted as an empirically tuned ADC(2) model. Several combinations of exchange-correlation functionals and spin-scaling schemes are explored. Our best-performing method includes the Perdew, Burke, and Ernzerhof exchange and Perdew's 1986 correlation functional and employs the scaled-opposite-spin approximation for the higher-order terms. The computation time of the new method scales as the fourth power of the system size, and an efficient cost-reduction approach is also presented, which further speeds up the calculations. Our benchmark calculations show that the proposed model outperforms not only the existing DH approaches and ADC(2) variants but also the considerably more expensive coupled-cluster methods.

Original languageEnglish
Pages (from-to)4440-4453
Number of pages14
JournalJournal of chemical theory and computation
Volume15
Issue number8
DOIs
Publication statusPublished - Aug 13 2019

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Excitation energy
Electron transitions
moments
excitation
Density functional theory
density functional theory
cost reduction
energy
Cost reduction
Excited states
functionals
scaling
Molecules
composite materials
Composite materials
approximation
molecules

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

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