Benchmarking TD-DFT and Wave Function Methods for Oscillator Strengths and Excited-State Dipole Moments

Abstract

Using a set of oscillator strengths and excited-state dipole moments of near full configuration interaction (FCI) quality determined for small compounds, we benchmark the performances of several single-reference wave function methods (CC2, CCSD, CC3, CCSDT, ADC(2), and ADC(3/2)) and time-dependent density-functional theory (TD-DFT) with various functionals (B3LYP, PBE0, M06-2X, CAM-B3LYP, and $\omega$B97X-D). We consider the impact of various gauges (length, velocity, and mixed) and formalisms: equation of motion (EOM) \emph{vs} linear response (LR), relaxed \emph{vs} unrelaxed orbitals, etc. Beyond the expected accuracy improvements and a neat decrease of formalism sensitivy when using higher-order wave function methods, the present contribution shows that, for both ADC(2) and CC2, the choice of gauge impacts more significantly the magnitude of the oscillator strengths than the choice of formalism, and that CCSD yields a notable improvement on this transition property as compared to CC2. For the excited-state dipole moments, switching on orbital relaxation appreciably improves the accuracy of both ADC(2) and CC2, but has a rather small effect at the CCSD level. Going from ground to excited states, the typical errors on dipole moments for a given method tend to roughly triple. Interestingly, the ADC(3/2) oscillator strengths and dipoles are significantly more accurate than their ADC(2) counterparts, whereas the two models do deliver rather similar absolute errors for transition energies. Concerning TD-DFT, one finds: i) a rather negligible impact of the gauge on oscillator strengths for all tested functionals (except for M06-2X); ii) deviations of ca.~0.10 D on ground-state dipoles for all functionals; iii) the better overall performance of CAM-B3LYP for the two considered excited-state properties.

arXiv comment18 pages, 7 figures

References in corpus (17)

• A Mountaineering Strategy to Excited States: Highly-Accurate Reference Energies and Benchmarks
• How accurate is density functional theory at predicting dipole moments? An assessment using a new database of 200 benchmark values
• A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Medium Size Molecules
• The Bethe-Salpeter Equation Formalism: From Physics to Chemistry
• Reference Energies for Double Excitations
• The Quest For Highly Accurate Excitation Energies: A Computational Perspective
• Absorption and Fluorescence Properties of Oligothiophene Biomarkers from Long-Range-Corrected Time-Dependent Density Functional Theory
• eT 1.0: an open source electronic structure program with emphasis on coupled cluster and multilevel methods
• A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Exotic Molecules and Radicals
• A Mountaineering Strategy to Excited States: Highly-Accurate Oscillator Strengths and Dipole Moments of Small Molecules
• Evaluating 0-0 Energies with Theoretical Tools: a Short Review
• Chemically Accurate 0-0 Energies with not-so-Accurate Excited State Geometries
• A Density-Based Basis-Set Correction For Wave Function Theory
• Review of biorthogonal coupled cluster representations for electronic excitation
• Is ADC(3) as Accurate as CC3 for Valence and Rydberg Transition Energies?
• Chemically Accurate Excitation Energies With Small Basis Sets
• Too big, too small or just right? A benchmark assessment of density functional theory for predicting the spatial extent of the electron density of small chemical systems

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