Reduced-cost second-order algebraic-diagrammatic construction method for excitation energies and transition moments

Dávid Mester, Péter R. Nagy, M. Kállay

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

A reduced-cost implementation of the second-order algebraic-diagrammatic construction [ADC(2)] method is presented. We introduce approximations by restricting virtual natural orbitals and natural auxiliary functions, which results, on average, in more than an order of magnitude speedup compared to conventional, density-fitting ADC(2) algorithms. The present scheme is the successor of our previous approach [D. Mester, P. R. Nagy, and M. Kállay, J. Chem. Phys. 146, 194102 (2017)], which has been successfully applied to obtain singlet excitation energies with the linear-response second-order coupled-cluster singles and doubles model. Here we report further methodological improvements and the extension of the method to compute singlet and triplet ADC(2) excitation energies and transition moments. The various approximations are carefully benchmarked, and conservative truncation thresholds are selected which guarantee errors much smaller than the intrinsic error of the ADC(2) method. Using the canonical values as reference, we find that the mean absolute error for both singlet and triplet ADC(2) excitation energies is 0.02 eV, while that for oscillator strengths is 0.001 a.u. The rigorous cutoff parameters together with the significantly reduced operation count and storage requirements allow us to obtain accurate ADC(2) excitation energies and transition properties using triple-ζ basis sets for systems of up to one hundred atoms.

Original languageEnglish
Article number094111
JournalJournal of Chemical Physics
Volume148
Issue number9
DOIs
Publication statusPublished - Mar 7 2018

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Excitation energy
Electron transitions
costs
moments
excitation
Costs
approximation
energy
oscillator strengths
cut-off
orbitals
Atoms
requirements
thresholds
atoms

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Reduced-cost second-order algebraic-diagrammatic construction method for excitation energies and transition moments. / Mester, Dávid; Nagy, Péter R.; Kállay, M.

In: Journal of Chemical Physics, Vol. 148, No. 9, 094111, 07.03.2018.

Research output: Contribution to journalArticle

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